Name: 5392-40-5|3,7-Dimethylocta-2,6-dienal|98%
Brand: Ambeed
SKU: A477712
Price: 12.0 USD
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2
[ 6666-75-7 ]
[ 5392-40-5 ]
2-cyano-3,7,11-trimethyl-dodeca-2,4,6,10-tetraenoic acid methyl ester [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1945,vol. 67,p. 716,717

3
[ 5392-40-5 ]
[ 59204-02-3 ]

Yield	Reaction Conditions	Operation in experiment
99%	With hydrogen In ethyl acetate at 80℃; Inert atmosphere; Sealed tube; Autoclave;	1a All of the hydrogenations have been carried out according as described below. The temperature, pressure, solvent and catalyst are listed in the table: The nickel catalyst (300 mg) was added to a 100 ml reactor fitted with a gas entrainment stirrer. The catalyst was washed with 3x anhydrous ethanol and 2x the reaction solvent. Citral (3 g) and the solvent (30 g) were added and the autoclave was sealed. The reactor was purged 5 times with nitrogen and 5 times with hydrogen. The reactor was heated to the desired temperature and then pressurized to the desired pressure. The reaction mixture was stirred for 20 hours or until no further hydrogen uptake was observed. At the end of the reaction the reactor was cooled to room temperature, the pressure released and purged once with nitrogen. The reaction mixture was filtered and analysed by GC for conversion and selectivity. In Table 1, three different commercially available nickel catalysts have been tested. All of them do show the same excellent results in regard to conversion (conv.) and yield of THGOL.
95%	With hydrogen In methanol at 120℃; for 8h;
95%	With sodium tetrahydroborate; palladium diacetate In methanol at 20℃; for 4h;

95%	With hydrogen In tetrahydrofuran at 150℃; for 3h; Autoclave; chemoselective reaction;
	With hydrogen; palladium at 110℃;
	With ethanol; hydrogen; platinum
	With nickel at 150℃; Hydrogenation_.unter Druck;
	With ethanol; iron(II) sulfate; platinum Hydrogenation;
	With platinum(IV) oxide; ethanol; iron(II) sulfate Hydrogenation;
	Multi-step reaction with 2 steps 1: alcohol; platinum black; zinc acetate; hydrogen 2: platinum black; alcohol / Hydrogenation
	With Pt(5wt%)Sn(1wt%)/MgAl2O4; hydrogen In isopropyl alcohol at 70℃; for 2h;

Reference： [1]Current Patent Assignee: KONINKLIJKE DSM N.V. - EP2765126, 2014, A1 Location in patent: Paragraph 0022; 0023; 0024; 0025
[2]Savoia, Diego; Tagliavini, Emilio; Trombini, Claudio; Umani-Ronchi, Achille [Journal of Organic Chemistry, 1981, vol. 46, p. 5344 - 5348]
[3]Location in patent: experimental part De Castro, Kathlia A.; Oh, Seungchan; Yun, Jongchan; Lim, Jin Kyu; An, Gwangil; Kim, Dong Kook; Rhee, Hakjune [Synthetic Communications, 2009, vol. 39, # 19, p. 3509 - 3520]
[4]Mitsudome, Takato; Matoba, Motoshi; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi [Chemistry - A European Journal, 2013, vol. 19, # 17, p. 5255 - 5258]
[5]Ipatjew [Chemische Berichte, 1912, vol. 45, p. 3216][Chemische Berichte, 1910, vol. 43, p. 3385]
[6]Vavon [Annales de Chimie (Cachan, France), 1914, vol. <9> 1, p. 173][Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1912, vol. 155, p. 286]
[7]v.Braun; Kaiser [Chemische Berichte, 1923, vol. 56, p. 2270]
[8]Adams; Garvey [Journal of the American Chemical Society, 1926, vol. 48, p. 478]
[9]Adams; Garvey [Journal of the American Chemical Society, 1926, vol. 48, p. 478]
[10]Adams; Garvey [Journal of the American Chemical Society, 1926, vol. 48, p. 478]
[11]Location in patent: experimental part Zgolicz, Patricia D.; Rodríguez, Virginia I.; Vilella, Irene M.J.; De Miguel, Sergio R.; Scelza, Osvaldo A. [Applied Catalysis A: General, 2011, vol. 392, # 1-2, p. 208 - 217]

4
[ 5392-40-5 ]
[ 26489-02-1 ]

Yield	Reaction Conditions	Operation in experiment
98%	With tri-n-butyl-tin hydride In tetrahydrofuran Ambient temperature;
96%	With diphenylsilane; zinc(II) chloride In chloroform for 1.5h; Ambient temperature;
93%	With dibenzylammonium trifluoroacetate salt In dichloromethane at 20℃; for 20h;

92%	With hydrogen In cyclohexane at 79.9℃;
92%	With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; dibenzylammonium trifluoroacetate salt In tetrahydrofuran at 20℃; for 5h;
92%	With triethylsilane; palladium dichloride; tricyclohexylphosphine In tetrahydrofuran; water at 20℃; for 1h;
91%	With sodium tetrahydroborate; nickel dichloride In methanol; water at 20℃; for 1.5h;
89%	With LaNi₅ hydride In tetrahydrofuran; methanol at 0℃; for 3h;
83%	With tri-n-butyl-tin hydride; acetic acid In benzene Ambient temperature;
81%	With bis-triphenylphosphine-palladium(II) chloride; potassium fluoride; polymethylhydrosiloxane; tributyltin chloride In tetrahydrofuran for 18h; Heating;
81%	With 1,3-di-tert-butyl-2-(neopentyloxy)-2,3-dihydro-1H-1,3,2-diazaphosphole; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In acetonitrile at 40℃; for 12h; Glovebox; Inert atmosphere;
80.7%	With (acetylacetonato)dicarbonylrhodium (l); (R,R)-chiraphos; hydrogen In toluene at 25 - 60℃; for 15h; Autoclave;	2 comparative example 1 Under argon atmosphere, dissolve 25.8mg Rh(CO)2acac and 42.6mg(2R,3R)-bis(diphenylphosphino)butane ligand in 30g toluene. Completely stir for 3h at 25C. Transfer mixture to 200mL autoclave and add 15.22g neral (ratio of neral/genarial cis-trans isomer =50.1:49.9; substrate / transition metal catalyst ratio = 1000) to the autoclave. Inject with H2 containing 1000ppm(v/v)CO. Adjust reaction pressure to 6.0 MPa by continuously injecting H2 containing 1000 ppm (v / v) of CO. Increase temperature of autoclave to 60C. After 12 h, the conversion rate was 81.3% using gas chromatography, the product was racemic citronellal, and the yield was 80.7%.
70.2%	With Gluconobacter oxydans old yellow enzyme family protein Gox0502 (a.a 1–315), recombinant, W100F mutant; NADPH In aq. phosphate buffer; ethanol at 30℃; for 1h; Enzymatic reaction;	Biocatalysis assay and data analysis. General procedure: Biotransformationswere typically performed in a standard reactionsystem containing 30 μg/mL enzyme, 2 mM substrate,2.1 mM NADPH, 100 mM PBS buffer pH 7.0, and10% (v/v) ethanol to a final volume of 0.5 mL. Themixtures were incubated in an orbital shaker at150 rpm at 30 °C for 1 h. Reactions were terminatedby extraction through chloroform (0.5 mL) containing0.15% (v/v) 2-octanone (as internal standard). Aftercentrifugation, the lower organic phase samples weretaken for GC (Gas chromatography) analysis.Concentrations and diastereomeric excesses (de) weredetermined by a GC-6890 N equipped with a30 m × 0.25 mm DB-5 column (Agilent Technologies).The injection volume was 1 μL with a split ratio of 10: 1.The following program was applied for GC analysis:40 °C for 3 min; 10 °C/min increase to 220 °C and maintainedat 220 °C for 3 min. For (S)-carvone’s catalysisexperiment, the corresponding retention times were asfollows: (S)-carvone 14.28 min, (1R, 4S)-dihydrocarvone13.60 min, and (1S, 4S)-dihydrocarvone 13.72 min. For(R)-carvone’s catalysis experiment, the correspondingretention times were as follows: (R)-carvone 14.28 min,(1R, 4R)-dihydrocarvone 13.72 min, and (1S, 4R)-dihydrocarvone13.60 min. The concentrations of the reactionproducts were calculated based on absorption. 2-Octanonewas used as an internal standard, which had beensubjected to chloroform during the extraction step.
69%	With sodium dithionite; sodium hydrogencarbonate In water; benzene at 80℃; for 1.5h;
67%	With silica gel In benzene for 20h; Heating; dark;
65%	With hydrogen In ethanol at 25℃; for 12h; regioselective reaction;
60%	With hydrogen In hexane at 23℃; for 1h;	12 Comparison experiments (hydrogenation of citral) using a non-acid catalytic system (with basic carrier and no modifier). The catalytic system has been added in amount of 8.6 wt-%, based on the total amount of citral, the reaction temperature was 23 °C and the pressure was 10 bar, the reaction time was 60 minutes.
57%	With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate In benzene at 80℃; for 17h;
26.1%	With recombinant old yellow enzyme from Bacillus subtilis; water; chromium; Flavin mononucleotide In aq. buffer at 21℃; for 4h; Glovebox; Darkness; Inert atmosphere; Enzymatic reaction; chemoselective reaction;
96 % Chromat.	With diphenylsilane In chloroform for 1.5h; Ambient temperature;
	With hydrogen In methanol; water for 1.5h; Ambient temperature; Yield given;
	With dimethylmonochlorosilane In acetone Heating;
	With sodium hydrogen telluride In ethanol Ambient temperature; Yield given;
95 % Chromat.	With hydrogen In methanol for 4h; Ambient temperature;
	With hydrogen In methanol; water for 1.5h; Ambient temperature; further catalyst, other time, other methanol/water ratio;
	With aluminum nickel Hydrogenation;
	With nickel at 180℃; Hydrogenation_.unter gewoehnlichem Druck;
	With nickel at 190℃; Hydrogenation_.unter vermindertem Druck;
	With palladium on activated charcoal; ethanol Hydrogenation;
	Multi-step reaction with 2 steps 1: 87 percent / tris(triphenylphosphine)rhodium chloride / 3 h / 50 °C 2: 3 percent aqueous sodium carbonate / acetone; methanol / 2.5 h / Ambient temperature
	Multi-step reaction with 2 steps 1: Wilkinson's catalyst
	With Pd/SiO₂; hydrogen; 1-buthyl-3-methylimidazolium dicyanamide In hexane at 49.84℃; for 6h; regioselective reaction;
	With palladium on silica gel; hydrogen In hexane at 49.84℃; for 6h; Autoclave; Ionic liquid; regioselective reaction;
	With carbon dioxide; hydrogen at 80℃; for 4h;
	With 1%Pd/TiO2; 1 wt% Au/TiO₂; hydrogen In carbon dioxide at 80℃; for 1h; Supercritical conditions; chemoselective reaction;
52 %Chromat.	With 1%Pd/SiO₂; hydrogen; 1-buthyl-3-methylimidazolium dicyanamide In hexane at 70℃; trickle-bed reactor; chemoselective reaction;
	With hydrogen; 1-ethyl-3-methylimidazolium acetate In n-heptane at 70℃; for 0.5h; Microwave irradiation;
	With dichloro(benzene)ruthenium(II) dimer; sodium formate In water at 80℃; for 0.5h; Microwave irradiation; Sealed tube;	General procedures for the reduction of citral with microwave irradiation General procedure: The reduction of citral was carried out in a quartz tube (10 mL) under microwave irradiation. The order of addition of the reagents plays an important role in the reactions [27]. We selected the following standard protocol. Hydrogen donor was first dissolved in a solvent in the reactor, catalyst was then added, and finally the substrate was added. Then, the reaction vessel was sealed and the reaction was carried out under microwave irradiation at 300 W with a stirring speed of 900 r/min. The reaction time was started to count when the reaction mixture reached the desired temperature. After the reaction, the mixture was extracted with n-hexane and the resulting solution was analyzed with gas chromatography (GC-Shimadzu-14C, FID, Capillary column Rtx-Wax 30 m-0.53 mm- 0.25 mm) and gas chromatography/mass spectrometry (GC/MS, Agilent 5890). The gas phases were analyzed by Shimadzu GC-14C with TCD and a TDX-01 packed column. The reactions in the autoclave (50 mL) were also carried out in a water-bath with the same procedures.
95 %Chromat.	With hydrogen In ethyl acetate at 45℃; for 12h; Inert atmosphere; Schlenk technique;
	With hydrogen at 99.84℃; Inert atmosphere;
	With hydrogen In ethanol at 50℃; for 0.0666667h;
	With ene-reductase from Deinococcus radiodurans; NADH; sodium chloride In aq. buffer at 30℃; for 5h; Enzymatic reaction;	2.4. Enzyme assays General procedure: Biotransformation for substrate scope and selectivity analysis were performed in 1 mL reaction volumes consisting of 2 mM NADH and 1 mM substrate, purified enzyme (20 μg) in 20 mM MOPS-NaOH (pH 7.4) with 0.1 M NaCl buffer at 30 °C. Conversions were determined after 5 h of incubation. For GC-MS analysis, reaction mixtures were extracted using an equal volume of ethyl acetate and samples separated on a FactorFour VF-5 ms column (30 m×0.25 mm×0.25 μm, Varian). Chiral separation of the reduction products of R- and S-carvone, 2-methylcyclopentenone and ketoisophorone were performed on a Astec Chiraldex G-TA column (30 m×0.25 mm×0.25 μm, Sigma-Aldrich) and compared to reference activities [37] or the MS fragmentation of diastereomers [38]. For HPLC analysis, reactions were stopped by the addition of 10 μL of concentrated HCl and samples separated on a Jupiter 5 μm C18 300 column (250 mm×4.6 mm, Phenomenex).
	With hydrogen In decane; cyclohexane at 90℃; for 4h; Autoclave;	2.3. Hydrogenation of citral The hydrogenation of citral was performed in a Parr stainless steelautoclave with a volume of 100 cm3 fitted with a teflon cup, operated in batch mode and stirred at 1200 rpm. Depending on the reaction,the reaction conditions were set at 90 °C, 110 °C and 130 °C and a H2 pressure of 10 bar and 30 bar. The catalyst (0.08-0.1 wt.% Ru, 0.2-0.3 g, 1.84μmol Ru) was transferred to the autoclave. The autoclave was charged with cyclohexane (30 cm3) and citral (0.156 cm3,0.1393 g, 921.6μmol) with n-decane as the internal standard(0.156 cm3). The reactor was purged thrice at ambient temperature with H2gas, depressurised and heated to 90 °C and allowed to stir at this temperature for 1 h to allow for catalyst activation. The desired temperature, either 90, 110 or 130 °C, was set and the reactor was pressurised to a H2 pressure of 10 bar or 30 bar to commence reaction.Samples of the reaction mixture were taken every 30 min over a 240 min period and analysed by gas chromatography on a Shimadzu GC-2010 Plus equipped with a 30 m Restek Rtx-5 capillary column.
	With Pd_0.4Ag_0.6 nanocrystals supported on SnO₂/C In isopropyl alcohol at 25℃; for 12h;
	With hydrogen In isopropyl alcohol at 100℃; for 0.75h; Autoclave;
	With hydrogen In acetonitrile at 50℃; for 24h; chemoselective reaction;
	With Chr-OYE₁ (old yellow enzyme from chryseobacterium sp. CA₄₉); β-nicotinamide adenine dinucleotide reduced In aq. phosphate buffer at 30℃; for 0.0333333h; Enzymatic reaction;	2.5 Bioreduction of activated alkenes and product analysis General procedure: The bioreduction of various substrates was performed in 1-ml reaction system containing 100mM potassium phosphate buffer (pH 7.0), 10mM NADH, 5mM substrate, and 50μg purified Chr-OYE1 or 500μg purified Chr-OYE2. After 2-min or 16-h incubation at 30°C for Chr-OYE1 and Chr-OYE2, respectively, the reactions were terminated by extraction with ethyl acetate. The organic phase was analyzed using GC or HPLC. (0013) Preparative-scale biotransformation was performed in 30-ml reaction system for substrates 4a, 6a, and 12a-17a catalyzed with Chr-OYE1. The incubation was continued for 12h. The extracted organic phase was combined and concentrated under reduced pressure. The final product was purified with column chromatography and subjected to GC or HPLC analysis, as well as NMR analysis to confirm the structure and purity.
	With hydrogen; potassium carbonate In water at 25℃; for 1.25h; chemoselective reaction;
	With water; hydrogen In ethanol at 65℃; Flow reactor; chemoselective reaction;
	With ethanol; palladium Hydrogenation; dihydrocitral;
	With ethanol; platinum Hydrogenation; dihydrocitral;
	With formaldehyd; sodium hydroxide at 65 - 75℃; for 3h; Milling;	1 Example 1 General procedure: 3L of 5cm diameter steel ball was added to the 10L vertical ball mill reactor, and 1.33kg of sodium hydroxide, 1.00kg of paraformaldehyde, and 2.5g of tetrabutylphosphonium bromide were added thereto. Start the ball mill and heated to 70 ° C to preheat the material, and after 10 minutes of grinding, the jacketed hot water was removed. 5.07 kg of citral was added to the ball mill reactor in 3 batches through the feed port (charging aperture). At this time, the reaction was exothermic, and the temperature was lowered by cooling water to maintain the reaction at 65 to 75 °C. After the addition of citral, the grinding reaction was continued for 3 hours to ensure the conversion of citral was completed. Tracking method: A small amount of the reaction material was taken out, dissolved in water, then extracted once with ethyl acetate, and the upper layer was subjected to gas chromatography analysis. The grinding was stopped, the material was transferred to a vibrating screen to separate the slurry and the steel ball, and the steel ball was rinsed with 15 kg of anhydrous ethanol during the screening. The slurry was transferred to a centrifuge, centrifuged to adjust the rotation speed to 5000 rpm for centrifugation, and the filter cake was rinsed with 15 kg of absolute ethanol to finally collect the filtrate and the filter cake by-product sodium formate. The filtrate was subjected to rotary evaporation at 50 ° C to remove the solvent, and then distilled under reduced pressure at 40 Pa to collect a fraction of 120 to 140 ° C to obtain 4.93 kg of geraniol 60 product. The nerol content was 31%, the geraniol content was 66%, the total content was 97%, and the yield was 96%.The product has a single impurity content of
	With nicotinamide adenine dinucleotide phosphate; Paenibacillus polymyxa enzyme Ppo-ER₃ In aq. phosphate buffer; N,N-dimethyl-formamide at 30℃; for 1h; Enzymatic reaction;
	With 1,3-diisopropylimidazolium tetrafluoroborate; hydrogen; potassium carbonate; cobalt acetylacetonate; aluminium In ethanol at 50℃; for 5h; Sealed tube; Autoclave; stereoselective reaction;	12 Example 12Selective hydrogenation of citral to synthesize citronellal In the glove box, cobalt (II) acetylacetonate (39.0mg),1,3-diisopropylimidazole tetrafluoroborate (47.3mg),Potassium carbonate (35.4mg) and ethanol (10.0g) were added to a single-mouth bottle with a magnetic stir bar,Turn on stirring, dissolve the metal precursor and ligand, and coordinate for 20 minutes to obtain a catalyst solution. Seal the single-necked bottle, remove it from the glove box, and protect it with nitrogen balloon. Seal the autoclave,There was no problem with pressure-holding and leak detection. The reactor was replaced 3 times with nitrogen. Feed,First, add a solution of activator aluminum powder (5.5mg) in ethanol (10.0g) to the reaction kettle with a flat-flow pump, then add the catalyst solution prepared previously, and finally add the solvent ethanol (45.0g)Substrate citral (15.377 g). After all the materials have been added, replace the nitrogen with hydrogen three times.2.0MPa each time, and finally filled with 3.0MPa (gauge pressure) hydrogen,Turn on the autoclave for stirring and heat tracing. When the internal temperature of the reactor reaches 50 ° C, start timing.Incubation reaction for 5 hours, sampling analysis, GC detection,The conversion of citral was 99.3%, and the selectivity of racemic citronellal was 96.5%.

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[47]Pei, Xiao-Qiong; Xu, Meng-Yu; Wu, Zhong-Liu [Journal of Molecular Catalysis B: Enzymatic, 2016, vol. 123, p. 91 - 99]
[48]Doherty; Knight; Backhouse; Abood; Alshaikh; Fairlamb; Bourne; Chamberlain; Stones [Green Chemistry, 2017, vol. 19, # 7, p. 1635 - 1641]
[49]Giziński, Damian; Błachucki, Wojciech; Śrębowata, Anna; Zienkiewicz-Machnik, Małgorzata; Goszewska, Ilona; Matus, Krzysztof; Lisovytskiy, Dmytro; Pisarek, Marcin; Szlachetko, Jakub; Sá, Jacinto [ChemCatChem, 2018, vol. 10, # 17, p. 3641 - 3646]
[50]Current Patent Assignee: Paal - DE298193, 1800, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 13, p. 630][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 13, p. 630]
[51]Current Patent Assignee: Paal - DE298193, 1800, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 13, p. 630][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 13, p. 630]
[52]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN108947768, 2018, A Location in patent: Paragraph 0032-0052
[53]Peters, Christin; Frasson, David; Sievers, Martin; Buller, Rebecca [ChemBioChem, 2019, vol. 20, # 12, p. 1569 - 1577]
[54]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN110437054, 2019, A Location in patent: Paragraph 0070-0072

5
[ 5392-40-5 ]
[ 2385-77-5 ]

Yield	Reaction Conditions	Operation in experiment
99.8%	With dodecacarbonyltetrarhodium⁽⁰⁾; (S)-bis(4-(tert-butyl)phenyl)methyl-3-(1-acetyl-1H-indol-3-yl)-2-aminopropanoate; hydrogen; triphenylphosphine In toluene at 90℃; for 10h; Autoclave;	2 Example 2 Under argon atmosphere52.7 mg of (S) -bis (4- (tert-butyl) phenyl) methyl 3- (1-acetyl-1H-indol-3-yl) -2-aminopropanoate, 18.7 mg Rh4 (CO) 12,26.2 mg of triphenylphosphine was dissolved in 40 mL of toluene,And transferred to a 100 mL autoclave,Will be 15.22gOrange aldehyde(Orange aldehyde / geraniol aldehyde = 99.1: 0.9 (mol)Substrate / transition metal catalyst = 1000 (mol)) into the autoclave,Pass the hydrogen to replace the gas inside the tank three times to adjust the pressure to 80 bar. After the reaction was carried out at 90 ° C for 10 h, the conversion was 99.9% by gas chromatography, the product was R-citronellal, the yield99.8%, optical purity of 99ee%.
99%	With (acetylacetonato)dicarbonylrhodium (l); carbon monoxide; (R,R)-chiraphos; hydrogen at 60 - 80℃; for 8h; Autoclave; stereoselective reaction;	6-13 Example 6 (Preparation of R-citronellal) Under a nitrogen gas atmosphere, 7.5 mg of Rh(CO)2acac, 18.6 mg of (R,R)-chiraphos (compound of formula (V)) (molar ratio of both 0.66:1) and 0.045 g of 10-20 from Example 1 Activated carbon with 10% loading of mesh TiO2 is added to 450g of nerol (molar ratio of neryl aldehyde/geranial double bond isomer = 99:1; mole of substrate/catalyst (calculated as transition metal in the catalyst) Ratio = 101842), and transferred it to a 1000 mL autoclave that has been previously purged 3 times with a mixture of carbon monoxide and hydrogen (1:1 volume/volume). The mixture was stirred at 1:1 (volume/volume) CO/H 2 pressure of 0.8 MPa and 60° C. for 3 h, and then it was cooled to room temperature. The reaction pressure was adjusted to 8 MPa by injecting hydrogen containing 1000 ppm carbon monoxide. To reduce the CO partial pressure, the pressure was reduced to 0.8 MPa three times and restored to 8 MPa three times by injecting hydrogen gas containing 1000 ppm of carbon monoxide. After heating to 80 for 5h, the conversion rate measured by gas chromatography was 99.9%.The yield of R-citronellal with an optical purity of 99ee% was 99%.The turnover of the whole reaction based on R-citronellal and Rh(CO)2acac is 100823.
78.6%	With 5% palladium on barium sulphate; (2R,4R)-2-(bis-(4'-t-butylphenyl)methyl)-4-(ethylcarbamoyloxy)pyrrolidine; trifluoroacetic acid In <i>tert</i>-butyl alcohol at 60℃; for 21h; Inert atmosphere;	41 Example 41 Asymmetric Hydrogenation of Citral Example 41 Asymmetric Hydrogenation of Citral In a 3-L reaction flask were added 500.0 g (3.28 mol) of citral, 2.50 g (0.5 wt % based on the citral) of 5 wt. % Pd/barium sulfate, 10.0 g (22.9 mmol, 2.0 wt % based on the citral) of (2R,4R)-2-(bis-(4'-t-butylphenyl)methyl)-4-(ethylcarbamoyloxy)pyrrolidine, 2.6 g (22.9 mmol) of trifluoroacetic acid, and 500 mL of 10 wt % hydrous t-butanol in a nitrogen atmosphere. The resulting mixture was stirred and the atmosphere was exchanged with a hydrogen atmosphere (0.1 MPa (atmospheric pressure)). After stirring at 60° C. for 21 hours, the catalyst was filtered off and the residue was analyzed using gas chromatography. As a result, it was found that a conversion ratio from citral to citronellal was 99.4% and an optical purity was 90.9% e.e. The crude-citronellal thus obtained was distilled to obtain 398 g (2.58 mol, yield: 78.6%) of d-citronellal having a purity of 98%.

71%	Stage #1: (E/Z)-3,7-dimethyl-2,6-octadienal In tetrahydrofuran at 20℃; for 0.0333333 - 0.0833333h; Stage #2: With dimethyl 2-isopropyl-6-methyl-1,4-dihydropyridine-3,5-dicarboxylate In tetrahydrofuran at 20℃; for 24h;	This reaction can be extended to the industrially important substance citral, which is reduced highly enantioselectively to the perfume ingredient citronellal (Scheme 10).
	With nickel Hydrogenation;
84 % ee	With di-tert-butyl 1,4-dihydro-2,6-dimethyl-3,5-pyridine-dicarboxylate at -70℃; for 11h;
	With β-D-glucose; glucose dehydrogenase 102; Pseudomonas stipitis OYE 2.6-GST fusion protein, OYE: old yellow enzyme, GST: glutathione S-transferase; NADPH Enzymatic reaction; optical yield given as %ee;
38 %Chromat.	Stage #1: (E/Z)-3,7-dimethyl-2,6-octadienal With 5% Pd-BaSO4; <i>L</i>-proline In water; <i>tert</i>-butyl alcohol at 50℃; Inert atmosphere; Stage #2: With hydrogen In water; <i>tert</i>-butyl alcohol at 50℃; for 21h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;
	Multi-step reaction with 3 steps 1.1: phosphoric acid / ethyl acetate / 2.5 h / 65 °C / Inert atmosphere 2.1: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 2,3-bis[(S)-(1,1-dimethylethyl)methylphosphino]quinoxaline / 0.25 h / 20 °C / Inert atmosphere 2.2: 6 h / 80 °C / 22502.3 Torr 3.1: hydrogenchloride; water / ethanol / 1.5 h / 70 °C / Inert atmosphere
	Multi-step reaction with 3 steps 1.1: phosphoric acid / ethyl acetate / 2.5 h / 70 °C / Inert atmosphere 2.1: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 2,3-bis[(S)-(1,1-dimethylethyl)methylphosphino]quinoxaline / 0.25 h / 20 °C / Inert atmosphere 2.2: 9 h / 70 °C / 52505.3 Torr 3.1: hydrogenchloride; water / ethanol / 2 h / 80 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN106905124, 2017, A Location in patent: Paragraph 0081; 0082; 0083; 0084; 0085; 0086-0099; 0102-0103
[2]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN111056933, 2020, A Location in patent: Paragraph 0071-0085
[3]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - US2013/253228, 2013, A1 Location in patent: Paragraph 0558
[4]Current Patent Assignee: EVONIK INDUSTRIES AG - US2009/30216, 2009, A1 Location in patent: Page/Page column 6
[5]Armstrong; Hilditch [Proceedings of the Royal Society of London, Series A: Mathematical, Physical and Engineering Sciences, 1925, vol. 108, p. 128][Chemisches Zentralblatt, 1925, vol. 96, # II, p. 1505]
[6]Current Patent Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY - US2006/161024, 2006, A1 Location in patent: Page/Page column 21
[7]Location in patent: body text Bougioukou, Despina J.; Walton, Adam Z.; Stewart, Jon D. [Chemical Communications, 2010, vol. 46, # 45, p. 8558 - 8560]
[8]Maeda, Hironori; Yamada, Shinya; Itoh, Hisanori; Hori, Yoji [Chemical Communications, 2012, vol. 48, # 12, p. 1772 - 1774]
[9]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN111718250, 2020, A
[10]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN111718250, 2020, A

6
[ 5392-40-5 ]
[ 106-25-2 ]
[ 106-24-1 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium amalgam; ethanol
	With aluminum isopropoxide; isopropyl alcohol
	With hydrotalcite; isopropyl alcohol at 82℃; for 5h; Title compound not separated from byproducts;

	With magnesium ethylate; isopropyl alcohol
	With Ru/β-Ga2O3; hydrogen at 119.84℃; for 6h; Autoclave; Neat (no solvent);
	With platinum doped titanium oxide; hydrogen In n-heptane at 89.84℃; for 1h; Autoclave; Inert atmosphere;
	With hydrogen at 99.84℃; for 8h; Inert atmosphere; Overall yield = 80 %;
42.222 % de	With hydrogen In water at 29.84℃; for 6h; Autoclave; Sealed tube; Overall yield = 88 %Spectr.; chemoselective reaction;
	With 3,7-dimethyl-oct-6-enal; 5 % platinum on carbon; hydrogen In water; isopropyl alcohol at 100℃; Autoclave;
33.333 % de	With [{RuCl₂(sodium 3-diphenylphosphinobenzenesulfonate)₂}₂]; water; sodium formate; sodium 3-(diphenylphosphanyl)benzenesulfonate In propan-1-ol at 30℃; for 1h; Inert atmosphere;	2.1. Catalytichydrogenationofcinnamaldehyde General procedure: In a typical reaction, 408mg (6mmol) sodiumformate and 126 L (1mmol) cinnamaldehyde were added to a mixture of 4.0mL water and 3.5m L2-propanolat T=30C. 5mg (0.005mmol) [{RuCl2(mtppms)2}2] and 16mg(0.04mmol) mtppms weredis-solved in the deoxygenated solution and the mixture was stirred vigorously. Samples(0.2mL) were withdrawn periodically and diluted with 1mL of water before extraction by chlorobenzene.The organic layers were filtered through short silica plugs and analyzed by gas chromatography.
4 % de	With formic acid; 4-methoxy-N-(1-(naphthalen-2-yl)ethylidene)aniline; sodium formate In water at 80℃; for 6h; Inert atmosphere; Overall yield = 90 %; chemoselective reaction;
	With hydrogen In hexane at 60℃; for 18h; Autoclave; chemoselective reaction;
	With potassium formate In water; N,N-dimethyl-formamide at 100℃; for 24h; Inert atmosphere; chemoselective reaction;
	With hydrogen In ethanol; water at 100℃; for 3h; Autoclave; chemoselective reaction;	2.1.3 2.3. Catalytic performance measurement General procedure: CAL hydrogenation was carried out in a 100 mL stainless steel autoclave (Parr 4848 reactor controller), in which 25 mg of catalyst, 2 mmol of CAL, 20 mL of EtOH and 30 mL of H2O were loaded. The reactor was sealed and purged with H2 to remove the air for 3 times, and then the reactor was heated to the desired temperature. Hydrogen (2 MPa) was purged into the reactor after desired temperature was reached and the stirrer was started. The products were analyzed by Shizumadu GC-2014C with a FID detector.
	With hydrogen In water at 29.84℃; for 8h; Autoclave;	18 As the reactor, an autoclave made of SUS 316 (content volume: 190 ml) and the autoclaveAnd a glass inner container inside the Reube were used.First, as shown in Table 3, 0.050 g of the Ir - Re catalyst [Ir - ReOX / SiO 2 - 1] obtained in Production Example 1 and 3.0 g of water were placed in a glass inner container,The reactor was sealed,After replacing the inside of the reactor with hydrogen, the temperature was raised to 200 ° C.,The Ir - Re catalyst was reduced by heating at 8 MPa for 1 hour.After completion of the reduction,Cooling and opening the autoclave,0.21 g of crotonaldehyde was added,The reactor was sealed again and replaced with hydrogen.Subsequently, the temperature of the reactor was controlled to 30 ° C.,Hydrogen was added so that the pressure became 0.8 MPa,The reaction was carried out at a stirring rotation number of 500 rpm for 8 hours.Incidentally,After completion of the reaction, gas chromatography (GC) or NMR measurement was carried out on the obtained reaction liquid, and quantitative analysis was carried out.The reaction results are shown in Table 3. Reduction reaction of each substrate (unsaturated carbonyl compound) with hydrogen was carried out in the same manner as in Example 12 except that the substrate and the reaction time were changed as shown in Table 3. The reaction results are shown in Table 3.
	With hydrogen In isopropyl alcohol at 70℃; for 2h; Autoclave; chemoselective reaction;
	With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H₂O); isopropyl alcohol at 82℃; for 6h; Inert atmosphere; Schlenk technique; Overall yield = 94 %; Overall yield = 145 mg; chemoselective reaction;
	With hydrogen In methanol; water at 30℃; for 3h;
	With magnesium ethylate; isopropyl alcohol
	With formaldehyd; tetrabutyl phosphonium bromide; sodium hydroxide at 65 - 75℃; for 3h; Milling; Large scale;	1-5 Example 1 3L of 5cm diameter steel ball was added to the 10L vertical ball mill reactor, and 1.33kg of sodium hydroxide, 1.00kg of paraformaldehyde, and 2.5g of tetrabutylphosphonium bromide were added thereto. Start the ball mill and heated to 70 ° C to preheat the material, and after 10 minutes of grinding, the jacketed hot water was removed. 5.07 kg of citral was added to the ball mill reactor in 3 batches through the feed port (charging aperture). At this time, the reaction was exothermic, and the temperature was lowered by cooling water to maintain the reaction at 65 to 75 °C. After the addition of citral, the grinding reaction was continued for 3 hours to ensure the conversion of citral was completed. Tracking method: A small amount of the reaction material was taken out, dissolved in water, then extracted once with ethyl acetate, and the upper layer was subjected to gas chromatography analysis. The grinding was stopped, the material was transferred to a vibrating screen to separate the slurry and the steel ball, and the steel ball was rinsed with 15 kg of anhydrous ethanol during the screening. The slurry was transferred to a centrifuge, centrifuged to adjust the rotation speed to 5000 rpm for centrifugation, and the filter cake was rinsed with 15 kg of absolute ethanol to finally collect the filtrate and the filter cake by-product sodium formate. The filtrate was subjected to rotary evaporation at 50 ° C to remove the solvent, and then distilled under reduced pressure at 40 Pa to collect a fraction of 120 to 140 ° C to obtain 4.93 kg of geraniol 60 product. The nerol content was 31%, the geraniol content was 66%, the total content was 97%, and the yield was 96%.The product has a single impurity content of
	With C₃₆H₃₅N₂O₅PRu; sodium isopropylate; potassium carbonate In isopropyl alcohol at 82℃; for 0.166667h; Inert atmosphere; Schlenk technique;
	With methyl 4-phenyl-2-oxo-3-butenoate; (acetylacetonato)dicarbonyliridium(I); hydrogen; zinc(II) acetylacetonate at 70℃; for 9h; Autoclave;	1-5: 1; 3 Example 4 In an oxygen-free and anhydrous atmosphere, 0.070 g of acetylacetone dicarbonyliridium, 0.044 g of zinc acetylacetonate, 5.562 mg of 2-oxo-4-phenylbut-3-enoic acid methyl ester and 500 Gram citral. Seal the autoclave, replace with nitrogen and hydrogen three times each, start heating and stirring, and charge hydrogen to 4 MPa when the temperature rises to 70°C, and maintain it for 9 hours until the end of the reaction. The results of the reaction were analyzed by GC and the results are shown in Table 1.
	With isopropyl alcohol at 80℃; for 10h; chemoselective reaction;

Reference： [1]Zeitschel [Chemische Berichte, 1906, vol. 39, p. 1782,1784]
[2]Ponndorf [Angewandte Chemie, 1926, vol. 39, p. 140]
[3]Kumbhar, Pramod S. [Chemical Communications, 1998, # 5, p. 535 - 536]
[4]Ponndorf [Angewandte Chemie, 1926, vol. 39, p. 140]
[5]Location in patent: body text Nishiyama, Hiroshi; Takeuchi, Junichi; Hayase, Hiroshi; Saito, Nobuo; Inoue, Yasunobu [Chemistry Letters, 2008, vol. 37, # 12, p. 1256 - 1257]
[6]Location in patent: experimental part Ananthan; Narayanan [Asian Journal of Chemistry, 2011, vol. 23, # 1, p. 183 - 188]
[7]Santiago-Pedro, Smid; Tamayo-Galván, Victoria; Viveros-García, Tomas [Catalysis Today, 2013, vol. 213, p. 101 - 108]
[8]Tamura, Masazumi; Tokonami, Kensuke; Nakagawa, Yoshinao; Tomishige, Keiichi [Chemical Communications, 2013, vol. 49, # 63, p. 7034 - 7036]
[9]Daly; Manyar; Morgan; Thompson; Delgado; Burch; Hardacre [ACS Catalysis, 2014, vol. 4, # 8, p. 2470 - 2478]
[10]Szatmári, Imre; Papp, Gábor; Joó, Ferenc; Kathó, Ágnes [Catalysis Today, 2015, vol. 247, p. 14 - 19]
[11]Talwar, Dinesh; Wu, Xiaofeng; Saidi, Ourida; Salguero, Noemí Poyatos; Xiao, Jianliang [Chemistry - A European Journal, 2014, vol. 20, # 40, p. 12835 - 12842]
[12]Cano, Israel; Huertos, Miguel A.; Chapman, Andrew M.; Buntkowsky, Gerd; Gutmann, Torsten; Groszewicz, Pedro B.; Van Leeuwen, Piet W. N. M. [Journal of the American Chemical Society, 2015, vol. 137, # 24, p. 7718 - 7727]
[13]Gao, Yanxiu; Wang, Jie; Han, Aijuan; Jaenicke, Stephan; Chuah, Gaik Khuan [Catalysis science and technology, 2016, vol. 6, # 11, p. 3806 - 3813]
[14]He, Sina; Xie, Lifang; Che, Minwei; Chan, Hang Cheong; Yang, Lichun; Shi, Zhangping; Tang, Yi; Gao, Qingsheng [Journal of Molecular Catalysis A: Chemical, 2016, vol. 425, p. 248 - 254]
[15]Current Patent Assignee: DAICEL CORPORATION; TOHOKU UNIVERSITY - JP2015/48349, 2015, A Location in patent: Paragraph 0074-0076
[16]Hu, Duo; Fan, Wenqian; Liu, Zhi; Li, Ling [ChemCatChem, 2018, vol. 10, # 4, p. 779 - 788]
[17]Wang, Rongzhou; Tang, Yawen; Xu, Meng; Meng, Chong; Li, Feng [Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 2274 - 2281]
[18]Liu, Hangyu; Mei, Qingqing; Li, Shaopeng; Yang, Youdi; Wang, Yanyan; Liu, Huizhen; Zheng, Lirong; An, Pengfei; Zhang, Jing; Han, Buxing [Chemical Communications, 2018, vol. 54, # 8, p. 908 - 911]
[19]Current Patent Assignee: WOLFGANG PONNDORF DR; SCHIMMEL AKT GES - DE535954, 1924, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 17, p. 581][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 17, p. 581]
[20]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN108947768, 2018, A Location in patent: Paragraph 0032-0046
[21]Giboulot, Steven; Baldino, Salvatore; Ballico, Maurizio; Figliolia, Rosario; Pöthig, Alexander; Zhang, Shuanming; Zuccaccia, Daniele; Baratta, Walter [Organometallics, 2019, vol. 38, # 5, p. 1127 - 1142]
[22]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN111018666, 2020, A Location in patent: Paragraph 0042-0053; 0056-0059
[23]Akinnawo, Christianah Aarinola; Bingwa, Ndzondelelo; Meijboom, Reinout [New Journal of Chemistry, 2021, vol. 45, # 17, p. 7878 - 7892]

7
[ 5392-40-5 ]
[ 110-93-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With pyrrolidine; water In acetonitrile at 20℃; for 12h;
	With water; potassium carbonate man destilliert mit Wasserdampf und fraktioniert im Vakuum;
	With potassium carbonate

	With potassium carbonate
	With sodium hydroxide In water	O.III OPERATING EXAMPLE III OPERATING EXAMPLE III Approximately 500 ml water, 5 g (90% active) sodium hydroxide, and 88 g terpeneless lemon grass oil containing approximately 95% citral were charged into a one-liter round bottom flask. The round bottom flask was equipped additionally with a trap having means of permitting removal of the lower density liquid while recirculating the higher density liquid, a fractionating column, and a means for stirring. The stirred contents of the flask were heated to reflux by means of a heating mantle. The pH of the contents was set at 12 and maintained at that level during the remainder of the run by addition of sodium hydroxide when necessary. The contents were refluxed for one hour, after which time the steam distillate was slowly collected. The distillate take-off was regulated so that little or no citral distilled over. The distillation was continued until no additional oil was collected. The oil phase distillate was separated from the steam condensate. The separated oil was then short-path vacuum distilled. The main cut yielded 72 g of the citral hydrolysis product, 6-methyl-5-hepten-2-one. The other reaction product, acetaldehyde, was vented from the flask through the fractionating column during the reaction. The yield of 6-methyl-5-hepten-2-one was approximately 90% under the above conditions.
	With palladium 10% on activated carbon; sodium formate In water at 180℃; for 0.333333h; Microwave irradiation; Sealed tube;	General procedures for the reduction of citral with microwave irradiation General procedure: The reduction of citral was carried out in a quartz tube (10 mL) under microwave irradiation. The order of addition of the reagents plays an important role in the reactions [27]. We selected the following standard protocol. Hydrogen donor was first dissolved in a solvent in the reactor, catalyst was then added, and finally the substrate was added. Then, the reaction vessel was sealed and the reaction was carried out under microwave irradiation at 300 W with a stirring speed of 900 r/min. The reaction time was started to count when the reaction mixture reached the desired temperature. After the reaction, the mixture was extracted with n-hexane and the resulting solution was analyzed with gas chromatography (GC-Shimadzu-14C, FID, Capillary column Rtx-Wax 30 m-0.53 mm- 0.25 mm) and gas chromatography/mass spectrometry (GC/MS, Agilent 5890). The gas phases were analyzed by Shimadzu GC-14C with TCD and a TDX-01 packed column. The reactions in the autoclave (50 mL) were also carried out in a water-bath with the same procedures.
	With β-lactoglobulin from milk In aq. phosphate buffer; ethanol at 37℃; for 96h; Darkness; Enzymatic reaction;

Reference： [1]Location in patent: scheme or table Enders, Dieter; Nguyen, Thanh V. [Tetrahedron Letters, 2012, vol. 53, # 16, p. 2091 - 2095]
[2]Verley [Bulletin de la Societe Chimique de France, 1897, vol. <3>17, p. 175][Chemische Berichte, 1899, vol. 32, p. 107]
[3]Verley [Bulletin de la Societe Chimique de France, 1897, vol. <3>17, p. 175][Chemische Berichte, 1899, vol. 32, p. 107] Barbe [Bulletin de l'Institut du pin, 1929, p. 246]
[4]Prileshajew [Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1911, vol. 43, p. 617][Chemisches Zentralblatt, 1911, vol. 82, # II, p. 268]
[5]Current Patent Assignee: GIVAUDAN SA - US4766249, 1988, A
[6]Liu, Ruixia; Wang, Yu; Cheng, Haiyang; Yu, Yancun; Zhao, Fengyu; Arai, Masahiko [Journal of Molecular Catalysis A: Chemical, 2013, vol. 366, p. 315 - 320]
[7]Gowda, Vishruth; Foley, Brendan; Du, Jasmine; Esteb, Megan; Watanabe, Coran M. H. [Organic and Biomolecular Chemistry, 2018, vol. 16, # 13, p. 2210 - 2213]

8
[ 5392-40-5 ]
[ 459-80-3 ]

Yield	Reaction Conditions	Operation in experiment
92%	With sodium chlorite; sodium dihydrogenphosphate In water; <i>tert</i>-butyl alcohol Ambient temperature;
46%	With sodium chlorite; sodium dihydrogenphosphate; dimethyl sulfoxide In water Ambient temperature;
17.4%	With oxygen In dichloromethane at 60℃; for 4h; autoclave;	In a 35-ml steel autoclave was added 3.21 g (20 mmol) Citral (1), 394 mg (0.02mmol Au) catalyst (3) followed by 15 ml Dichloromethane. The suspension was stirred at 250 RPM and heated to 60°C (internal temperature) under oxygen gas (10 bar) for 4 hours. After cooling (2O0C), the catalyst was separated by filtration and the cake rinsed with Dichlromethane. The mother liquor was evaporated under reduced pressure (30 mbar, 4O0C) and the resulting oil analyzed by GC-MS. ResultsWeight: 3.07 gCitral [BIZ) (1): 52.7 % Geranic acid (2): 19.4 %Conversion of 1; 46.9 %Yield of 2: 17.4 %Selectivity: 37.1 %

	With silver(l) oxide
	With silver(l) oxide
	With manganese(IV) oxide In hexane at 0℃; for 0.5h;
	With aldehyde dehydrogenase from pseudomonas putida KT₂₄₄₀; water; nicotinamide adenine dinucleotide phosphate
	With sodium chlorite; sodium dihydrogenphosphate; limonene. In water; <i>tert</i>-butyl alcohol at 15 - 35℃; for 16h;	1.1 Step 1: Using citral as raw material,The modified Pinnick oxidation reaction gives a geranic acid intermediate. specifically:Add citral (100g) and dipentene (446g) to a 5L three-necked flask.Tert-butanol (486 g), 902 g of a 16.8% aqueous solution of sodium dihydrogen phosphate was added.Slowly add 379.6 g of a 20% sodium chlorite solution at 15 ° C.The temperature is not higher than 35 ° C; after the completion of the dropwise addition, the reaction is stirred at room temperature for 16 h;After the raw material is completely reacted, the liquid is separated, and the upper organic phase is separated.The lower aqueous phase was extracted with toluene (2 x 100 mL) and the organic phases were combined.Rotating to remove t-butanol and toluene therein;Then 10% sodium hydroxide solution 400g, stirred for 0.5h,The liquid phase was separated, and the aqueous phase was extracted with toluene (2×100 mL), and the organic phase was discarded.The extracted aqueous phase was adjusted to pH 2.0 with 31% sulfuric acid to separate the organic phase.The aqueous phase was extracted with toluene (2×50 mL), and the organic phases were combined and evaporated.The crude product was 117.8 g, which was geranic acid, and the content was 77.4% (the sum of the two isomers).Directly invest in the next step;

Reference： [1]Bal, Balkrishna S.; Childers, Wayne E.; Pinnick, Harold W. [Tetrahedron, 1981, vol. 37, p. 2091 - 2096]
[2]Dalcanale, Enrico; Montanari, Fernando [Journal of Organic Chemistry, 1986, vol. 51, # 4, p. 567 - 569]
[3]Current Patent Assignee: KONINKLIJKE DSM N.V. - WO2008/148549, 2008, A2 Location in patent: Page/Page column 27-28
[4]Bernhauer; Forster [Journal fur praktische Chemie (Leipzig 1954), 1936, vol. <2> 147, p. 199,201]
[5]Semmler [Chemische Berichte, 1890, vol. 23, p. 3556]
[6]Duettmann,H.; Weyerstahl,P. [Justus Liebigs Annalen der Chemie, 1976, p. 1753 - 1756]
[7]Andersen, John F.; Walding, Jennifer K.; Evans, Philip H.; Bowers, William S.; Feyereisen, Rene [Chemical Research in Toxicology, 1997, vol. 10, # 2, p. 156 - 164]
[8]Winkler, Till; Groeger, Harald; Hummel, Werner [ChemCatChem, 2014, vol. 6, # 4, p. 961 - 964]
[9]Current Patent Assignee: XIAMEN OAMIC BIOTECH CO LTD - CN109053407, 2018, A Location in patent: Paragraph 0048; 0049; 0050

9
[ 5392-40-5 ]
[ 99-87-6 ]

Yield	Reaction Conditions	Operation in experiment
61%	With oxygen; acetic anhydride In 1,2-dichloro-ethane at 25℃;
61%	With oxygen; acetic anhydride In 1,2-dichloro-ethane at 25℃; for 20h;
25%	With dioxane*SO₃ In dichloromethane at 0℃; for 1h;

	With iodine Destillation;
	With pyrographite at 135℃;
	With sulfuric acid at 25℃;
	With sulfuric acid
	With potassium pyrosulfate
	With acetic acid at 150℃;
	With acid

Reference： [1]Bhatia, Beena; Iqbal, Javed [Tetrahedron Letters, 1992, vol. 33, # 51, p. 7961 - 7964]
[2]Bhatia, Beena; Punniyamurthy, T.; Iqbal, Javed [Journal of Organic Chemistry, 1993, vol. 58, # 20, p. 5518 - 5523]
[3]Zaks, I. M.; Moiseenkov, A. M. [Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, 1982, vol. 31, # 11, p. 2308 - 2309][Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1982, # 11, p. 2614 - 2615]
[4]Bogert; Fourman [American perfumer, 1933, vol. 28, p. 345]
[5]Kimura [Bulletin of the Chemical Society of Japan, 1935, vol. 10, p. 330,333]
[6]Okuda [Nippon Kagaku Kaishi/Journal of the Chemical Society of Japan, 1940, vol. 61, p. 161][Chem.Abstr., 1942, p. 3166] Horiuchi; Otsuki; Okuda [Bulletin of the Chemical Society of Japan, 1939, vol. 14, p. 501,505]
[7]Horiuchi [Memoirs of the College of Science, Kyoto Imperial University, vol. <A> 11, p. 190][Chemisches Zentralblatt, 1928, vol. 99, # II, p. 1326]
[8]Horiuchi [Memoirs of the College of Science, Kyoto Imperial University, vol. <A> 11, p. 190][Chemisches Zentralblatt, 1928, vol. 99, # II, p. 1326]
[9]Horiuchi [Memoirs of the College of Science, Kyoto Imperial University, vol. <A> 11, p. 190][Chemisches Zentralblatt, 1928, vol. 99, # II, p. 1326]
[10]Semmler [Chemische Berichte, 1891, vol. 24, p. 208] Barbier; Bouveault [Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1894, vol. 118, p. 1051] Dodge [American Chemical Journal, 1890, vol. 12, p. 561] Tiemann [Chemische Berichte, 1899, vol. 32, p. 117]

10
[ 106-24-1 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With 4-(acetylamino)-2,2,6,6-tetramethylpiperidinyl-1-oxo-piperidinium p-toluenesulfonate In dichloromethane for 1.5h; Ambient temperature;
93%	With 4 A molecular sieve; tetrabutylammonium periodite In dichloromethane at 20℃; for 24h;
93%	With 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxoammonium nitrate; silica gel In dichloromethane at 20℃; for 12h;	GENERAL PROCEDURE FOR ALCOHOL OXIDATION General procedure: Alcohol (7, 2 mmol, 1 eq.), silica gel (1 wt. equiv. to 7), and CH2Cl2 (50 mL, 0.04 M in 7) were added to a round-bottom flask equipped with a magnetic stir bar and the mixture stirred at r.t. for 5 min before adding 5 (0.275 g, 1 mmol, 0.5 eq.). The reaction mixture was stirred at r.t. until the oxidation was deemed complete by 1H-NMR spectroscopy monitoring. Upon completion, the product mixture was filtered through a pad of silica, the silica washed with dichloromethane to elute any remaining product. The solvent was then removed from the filtrate under vacuum, affording the pure product.

86%	With dipyridinium dichromate In N,N-dimethyl-formamide at -10℃;
86%	With Oxone; sodium ortho-iodobenzenesulfonate; sodium sulfate In nitromethane at 70℃; for 2h; Inert atmosphere;
85%	Stage #1: Geraniol With (-N(SO₂C₈F₁₇)-(biphenyl-2,2'-diyl)-O-)AlCH₃ In toluene at 21℃; for 0.5h; Stage #2: With pivalaldehyde In toluene at 21℃; for 0.5h; Further stages.;
78%	In benzene for 15h; Heating;
73%	With K-birnessite MnO₂ In dichloromethane at 20℃;
72%	With potassium chlorochromate on alumina In dichloromethane for 24h; Ambient temperature;
72%	With (1,3-diarylimidazol-2-ylidene)-based Pd; oxygen; tetrabutylammonium acetate In toluene at 60℃; for 18h;
25%	With oxygen; triethylamine In tetrahydrofuran; toluene at 45℃; for 20h;
22%	With tert.-butylhydroperoxide In dichloromethane for 1h; Ambient temperature;
	With aluminium(III) phenoxide; benzene Oxydation des erhaltenen Aluminiumverbindungen mit Benzochinon;
	With aluminum isopropoxide at 75 - 120℃; im Vakuum, und Oxydation des erhaltenen Aluminiumverbindungen mit Piperonal;
	With pyridine; p-toluenesulfonyl chloride Versetzen des entstandenen Geranyl-pyridinium-toluolsulfonats in Aethanol mit 4-Nitroso-dimethylanilin in verd. NaOH und Zersetzung des so erhaltenen Nitrons mit 2 n-HCl;
	in Ficus retusa Linn_.;
	With chromic acid
	With copper at 200℃; unter vermindertem Druck;
	With quinoline; meta-dinitrobenzene; copper(II) oxide at 160 - 170℃;
	With silver-asbestos; oxygen at 300 - 310℃;
84 % Turnov.	With dipyridinium dichromate; dihydrogen peroxide; sodium carbonate In 1,2-dichloro-ethane at 80℃; for 24h;
30 % Chromat.	With molecular sieve; tetrabutylammonium periodite In dichloromethane for 3h; Ambient temperature;
58 % Chromat.	With acetyl nitrate on montmorillonite K₁₀ for 2h; Ambient temperature;
		3 EXAMPLE 3 Following the procedure of Example 2 but using geraniol in place of p-chlorobenzyl alcohol and 5 mol % of copper (I) chloride and 1,10-phenanthroline gave the title compound in 80% conversion (by 1 H NMR analysis) after 6 hours.
	With aluminum isopropoxide In cyclohexanone	9 EXAMPLE 9 A flask was charged with 3.1 grams of geraniol, 0.25 grams of aluminum isopropoxide, and 1.9 grams (1 equivalent) of cyclohexanone and stirred for 16 hours at ambient temperature. Analysis by glpc showed only a 15% conversion to citral.
68 %Chromat.	With 6-(N-phenylbenzimidazoyl)-2-pyridinecarboxylic acid; dihydrogen peroxide; sodium carbonate; iron(II) chloride In dichloromethane at 20℃; for 0.5h; chemoselective reaction;
99 %Spectr.	With oxygen In water at 30℃; for 20h;
	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene In tetrahydrofuran at 60℃; for 0.075h;

Reference： [1]Ma, Zhenkun; Bobbitt, James M. [Journal of Organic Chemistry, 1991, vol. 56, # 21, p. 6110 - 6114]
[2]Friedrich, Holger B.; Singh, Nirad [Tetrahedron Letters, 2000, vol. 41, # 20, p. 3971 - 3974]
[3]Miller, Shelli A.; Sandoval, Arturo León; Leadbeater, Nicholas E. [Tetrahedron Letters, 2020, vol. 61, # 6]
[4]Ognyanov, Vassil I.; Datcheva, Violeta K.; Kyler, Keith S. [Journal of the American Chemical Society, 1991, vol. 113, # 18, p. 6992 - 6996]
[5]Uyanik, Muhammet; Akakura, Matsujiro; Ishihara, Kazuaki [Journal of the American Chemical Society, 2009, vol. 131, p. 251 - 262]
[6]Ooi, Takashi; Otsuka, Hidehito; Miura, Tomoya; Ichikawa, Hayato; Maruoka, Keiji [Organic Letters, 2002, vol. 4, # 16, p. 2669 - 2672]
[7]Masuyama, Yoshiro; Tsuhako, Akira; Kurusu, Yasuhiko [Tetrahedron Letters, 1981, vol. 22, # 40, p. 3973 - 3976]
[8]Location in patent: scheme or table Kamimura, Akio; Nozaki, Yuichiro; Ishikawa, Shingo; Inoue, Ryota; Nakayama, Masaharu [Tetrahedron Letters, 2011, vol. 52, # 4, p. 538 - 540]
[9]Carlsen, Per H. J.; Husbyn, Mette; Braenden, Jon E,; Eliason, Robert [Acta Chemica Scandinavica, 1989, vol. 43, # 5, p. 485 - 488]
[10]Schultz, Mitchell J.; Hamilton, Steven S.; Jensen, David R.; Sigman, Matthew S. [Journal of Organic Chemistry, 2005, vol. 70, # 9, p. 3343 - 3352]
[11]Batt, Frédéric; Bourcet, Emmanuel; Kassab, Youssef; Fache, Fabienne [Synlett, 2007, # 12, p. 1869 - 1872]
[12]Muzart, Jacques [Tetrahedron Letters, 1987, vol. 28, # 19, p. 2133 - 2134]
[13]Yamashita; Matsumura [Nippon Kagaku Kaishi/Journal of the Chemical Society of Japan, 1943, vol. 64, p. 506][Chem.Abstr., 1947, p. 3753]
[14]Lauchenauer; Schinz [Helvetica Chimica Acta, 1949, vol. 32, p. 1273]
[15]Karrer; Epprecht [Helvetica Chimica Acta, 1941, vol. 24, p. 1043]
[16]Fujita [Nippon Kagaku Kaishi/Journal of the Chemical Society of Japan, 1944, vol. 65, p. 91][Chem.Abstr., 1947, p. 3511]
[17]Semmler [Chemische Berichte, 1890, vol. 23, p. 2966][Chemische Berichte, 1891, vol. 24, p. 201]
[18]Bouveault [Bulletin de la Societe Chimique de France, 1908, vol. <4> 3, p. 123]
[19]Zetzsche; Zala [Helvetica Chimica Acta, 1926, vol. 9, p. 289]
[20]Moureu; Mignonac [Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1920, vol. 171, p. 652][Bulletin de la Societe Chimique de France, 1921, vol. <4>29, p. 100]
[21]Muzart, Jacques; Ajjou, Abdelaziz N'Ait; Ait-Mohand, Samia [Tetrahedron Letters, 1994, vol. 35, # 13, p. 1989 - 1990]
[22]Bailey, Alan J.; Griffith, William P.; Savage, Paul D. [Journal of the Chemical Society, Dalton Transactions, 1995, # 21, p. 3537 - 3542]
[23]De Oliveira Filho; Moreira; Moran, Paulo J. S.; Rodrigues, J. Augusto R. [Tetrahedron Letters, 1996, vol. 37, # 29, p. 5029 - 5032]
[24]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD; Syngenta (in: Sinochem Holdings) - US5912388, 1999, A
[25]Current Patent Assignee: SCM GLIDCO ORGANICS - US4055601, 1977, A
[26]Join, Benoit; Moeller, Konstanze; Ziebart, Carolin; Schroeder, Kristin; Goerdes, Dirk; Thurow, Kerstin; Spannenberg, Anke; Junge, Kathrin; Beller, Matthias [Advanced Synthesis and Catalysis, 2011, vol. 353, # 16, p. 3023 - 3030]
[27]Location in patent: experimental part Ohtaka, Atsushi; Kono, Yuki; Inui, Shigeki; Yamamoto, Syusei; Ushiyama, Tomoki; Shimomura, Osamu; Nomura, Ryôki [Journal of Molecular Catalysis A: Chemical, 2012, vol. 360, p. 48 - 53]
[28]Ambreen, Nida; Wirth, Thomas [European Journal of Organic Chemistry, 2014, vol. 2014, # 34, p. 7590 - 7593]

11
[ 105-56-6 ]
[ 5392-40-5 ]
[ 69891-96-9 ]

Yield	Reaction Conditions	Operation in experiment
74%	With water In 1,4-dioxane at 100℃; for 12h; Sealed tube;	2.1.2. General experimental procedure for the synthesis of PS General procedure: In a 50 mL round bottom flask citral (0.152 g, 1 mmol) and acetone(0.116 g, 2 mmol) were taken along with specially dried 1,4-dioxane (5 mL) as a solventH2O (1 mL) was used as an additive,the catalyst amount was fixed at 0.100 g. The round bottom flaskwas connected to a water cooled Liebig condenser which wastightly sealed at the other end to prevent any evaporation. Thereaction mixture was heated up to 100 C (reflux) in an oil bath.The reaction was monitored by using thin layer chromatography.After the completion of the reaction, reaction mixture was filtered,water removed using anhydrous MgSO4 and the mixture was analyzedby Gas Chromatograph equipped with Mass Detector and/orisolated using column chromatography and confirmed by 1H NMR.
	With N-benzyl-N,N,N-triethylammonium chloride; sodium carbonate
	With tert-butylammonium hexafluorophosphate(V); potassium carbonate In toluene at 20℃; for 2h;

Reference： [1]Vernekar, Dnyanesh; Sakate, Sachin S.; Rode, Chandrashekhar V.; Jagadeesan, Dinesh [Journal of Catalysis, 2019, vol. 378, p. 80 - 89]
[2]Kryshtal,G.V. et al. [Synthesis, 1979, p. 107 - 109]
[3]Kryshtal, G. V.; Zhdankina, G. M.; Zlotin, S. G. [Russian Chemical Bulletin, 2011, vol. 60, # 11, p. 2286 - 2290,5][Izvestiya Akademi Nauk, Seriya Khimicheskaya, 2011, # 11, p. 2244 - 2247,4]

12
[ 24621-61-2 ]
[ 5392-40-5 ]
(+)-(2R,4S,Z)-2-2',6'-Dimethylhepta-1',5'-dienyl-4-methyl-1,3-dioxane [ No CAS ]
(+)-(2R,4S,E)-2-2',6'-Dimethylhepta-1',5'-dienyl-4-methyl-1,3-dioxane [ No CAS ]

Reference： [1]Helvetica Chimica Acta,1980,vol. 63,p. 1598 - 1603

13
[ 6290-03-5 ]
[ 5392-40-5 ]
(-)-(2S,4R,Z)-2-2',6'-dimethylhepta-1',5'-dienyl-1,3-dioxane [ No CAS ]
(-)-(2S,4R,E)-2-2',6'-Dimethylhepta-1',5'-dienyl-4-methyl-1,3-dioxane [ No CAS ]

Reference： [1]Helvetica Chimica Acta,1980,vol. 63,p. 1598 - 1603

14
[ 917-54-4 ]
[ 5392-40-5 ]
[ 17920-90-0 ]

Yield	Reaction Conditions	Operation in experiment
75%	With copper(l) iodide In diethyl ether; hexane 1.) -78 deg C, 20 min, 2.) -20 deg C, 4 h;
75%	Stage #1: methyllithium With copper(l) iodide In diethyl ether at 0 - 5℃; for 2h; Inert atmosphere; Stage #2: (E/Z)-3,7-dimethyl-2,6-octadienal In diethyl ether at -60 - 20℃; for 2h;	1 [Example 1] Synthesis of 3-methyl citronellal The reaction was performed under a nitrogen atmosphere. A 1 L four-neck flask equipped with a dropping funnel was prepared, and copper iodide (27.3 g, 1.05 eq) and diethyl ether (200 ml) were added to the flask. The temperature of the inside of the system was lowered to 0°C. to 5°C. while stirring the mixture. A methyl lithium/ether solution (1.13 mol/L, 260 ml, 2.05 eq. vs CuI) was added dropwise through the dropping funnel over one and a half hours. After the completion of the dropwise addition, stirring was performed for 30 minutes while maintaining the temperature, and the temperature of the inside of the system was lowered to -60°C. or lower. Citral (20.8 g, 137 mmol) and diethyl ether (100 ml) were slowly added dropwise through the dropping funnel over 1 hour. After the completion of the dropwise addition, stirring was performed for 1 hour while maintaining the temperature, and the temperature of the inside of the system was gradually raised to room temperature. As a post-treatment, the temperature of the inside of the system was lowered to 0°C. to 5°C., and a saturated aqueous ammonium chloride solution was slowly added dropwise. The oil layer was washed three times with the saturated aqueous ammonium chloride solution and was washed once with saturated saline solution, followed by drying with anhydrous magnesium sulfate and the concentration under reduced pressure was performed, and the resulting product was purified with column chromatography, thereby obtaining desired 3-methyl citronellal (17.2 g, 75% yield) 3-methyl citronellal [0112] 1H-NMR (500 MHz, CDCl3): δ 0.93 (s, 6H), 1.33-1.39 (m, 2H), 1.60 (s, 3H), 1.68 (3H, d, J=0.85 Hz), 1.94-2.01 (m, 2H), 2.27 (2H, d, J=3.2 Hz), 5.06-5.11 (1H, m), 9.85 (1H, t, J=3.1Hz). [0113] 13C-NMR (125 MHz, CDCl3): 17.6 (CH3), 22.7 (CH2), 25.7 (CH3), 27.4 (2C, CH3), 33.5 (C), 42.7 (CH2), 54.7 (CH2), 124.3 (CH), 131.6 (C), 203.6 (C).
	With copper(l) iodide; acetic acid; lithium chloride 1) ether, -75 deg C to 0 deg C, 2) ether, -75 deg C; Yield given. Multistep reaction;

Reference： [1]Sakane, Soichi; Maruoka, Keiji; Yamamoto, Hisashi [Tetrahedron, 1986, vol. 42, # 8, p. 2203 - 2210]
[2]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - US2021/47283, 2021, A1 Location in patent: Paragraph 0111-0113
[3]Clive, Derrick L. J.; Farina, Vittorio; Beaulieu, Pierre [Journal of the Chemical Society. Chemical communications, 1981, # 13, p. 643 - 644]

15
[ 5392-40-5 ]
[ 106-22-9 ]
[ 26489-02-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	With hydrogen In cyclohexane at 79.9℃; other catalysts, hydrogenation rates, selectivity of catalysts;
1: 26% 2: 68%	With hydrogen In methanol at 45℃; for 18h;
1: 0.6 % Chromat. 2: 97.5 % Chromat.	With hydrogen; sodium carbonate In water; isopropyl alcohol at 120℃; other temperature, other solvent, other pressure, other catalysts;

	With hydrogen; trimethylamine In methanol at 80℃;
1: 95.6 %Chromat. 2: 3.7 %Chromat.	With hydrogen In water at 60℃; for 4h; Autoclave; chemoselective reaction;
	With hydrogen In water at 70℃; for 3h;
	With Pt(5wt%)/MgAl2O4; hydrogen In isopropyl alcohol at 70℃; for 2h;
	With hydrogen In isopropyl alcohol at 100℃; for 2.5h; Autoclave;
	With hydrogen at 20℃; for 4h; Autoclave;
	With water; hydrogen In ethanol at 100℃; Flow reactor; chemoselective reaction;
	With hydrogen In toluene at 20℃;

Reference： [1]Court, J.; Janati-Idrissi, F.; Vidal, S.; Wierzchowsi, P. [Journal de Chimie Physique et de Physico-Chimie Biologique, 1990, vol. 87, p. 379 - 391]
[2]Savoia, Diego; Tagliavini, Emilio; Trombini, Claudio; Umani-Ronchi, Achille [Journal of Organic Chemistry, 1981, vol. 46, p. 5344 - 5348]
[3]Sokol'skii, D. V.; Pak, A. M.; Turganbaeva, S. M.; Konuspaev, S. R.; Ginzburg, M. A. [Journal of applied chemistry of the USSR, 1981, vol. 54, # 7, p. 1345 - 1347][Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation), 1981, vol. 54, # 7, p. 1574 - 1578]
[4]Current Patent Assignee: BASF SE - WO2004/7414, 2004, A1 Location in patent: Page/Page column 6-7
[5]Location in patent: experimental part Hu, Yu; Yu, Yinyin; Zhao, Xiuge; Yang, Hanming; Feng, Bo; Li, Huan; Qiao, Yunxiang; Hua, Li; Pan, Zhenyan; Hou, Zhenshan [Science China Chemistry, 2010, vol. 53, # 7, p. 1541 - 1548]
[6]Location in patent: experimental part Hu, Yu; Yu, Yinyin; Hou, Zhenshan; Yang, Hanming; Feng, Bo; Li, Huan; Qiao, Yunxiang; Wang, Xiangrui; Hua, Li; Pan, Zhenyan; Zhao, Xiuge [Chemistry - An Asian Journal, 2010, vol. 5, # 5, p. 1178 - 1184]
[7]Location in patent: experimental part Zgolicz, Patricia D.; Rodríguez, Virginia I.; Vilella, Irene M.J.; De Miguel, Sergio R.; Scelza, Osvaldo A. [Applied Catalysis A: General, 2011, vol. 392, # 1-2, p. 208 - 217]
[8]Han, Ruirui; Nan, Chunshi; Yang, Lan; Fan, Guoli; Li, Feng [RSC Advances, 2015, vol. 5, # 42, p. 33199 - 33207]
[9]Martínez-Prieto; Ferry; Rakers; Richter; Lecante; Philippot; Chaudret; Glorius [Chemical Communications, 2016, vol. 52, # 26, p. 4768 - 4771]
[10]Giziński, Damian; Błachucki, Wojciech; Śrębowata, Anna; Zienkiewicz-Machnik, Małgorzata; Goszewska, Ilona; Matus, Krzysztof; Lisovytskiy, Dmytro; Pisarek, Marcin; Szlachetko, Jakub; Sá, Jacinto [ChemCatChem, 2018, vol. 10, # 17, p. 3641 - 3646]
[11]López-Vinasco, Angela M.; Martínez-Prieto, Luis M.; Asensio, Juan M.; Lecante, Pierre; Chaudret, Bruno; Cámpora, Juan; Van Leeuwen, Piet W. N. M. [Catalysis science and technology, 2020, vol. 10, # 2, p. 342 - 350]

16
[ 5392-40-5 ]
[ 106-22-9 ]
[ 26489-02-1 ]
[ 106-25-2 ]
[ 106-24-1 ]

Yield	Reaction Conditions	Operation in experiment
1: 8 % Chromat. 2: 18 % Chromat.	With methanol; samarium diiodide In tetrahydrofuran for 24h; Ambient temperature; Yields of byproduct given. Title compound not separated from byproducts;
	With methanol; samarium diiodide In tetrahydrofuran for 24h; Ambient temperature; Yields of byproduct given. Title compound not separated from byproducts;
	With hydrogen In hexane at 174.84℃; for 2.5h;

	With hydrogen In carbon dioxide at 49.84℃; for 0.25 - 3h;
	With hydrogen In hexane
	With hydrogen
	With hydrogen In hexane
	With hydrogen In carbon dioxide at 35 - 70℃; for 0.25 - 6h;
	With hydrogen
	With hydrogen In toluene at 70℃; for 4h;
	With hydrogen In hexane at 70℃; for 4h;
	With hydrogen In benzene at 70℃; for 4h;
	With hydrogen In ethanol at 70℃; for 4h;
	With hydrogen In carbon dioxide at 35 - 80℃; for 0.25 - 6h;
	With hydrogen at 70℃; for 4h;
	With Pt/MCM-41; carbon dioxide; hydrogen at 70℃; for 4h; Supercritical conditions; Autoclave;
	With dichloro(benzene)ruthenium(II) dimer; sodium formate In water at 70℃; for 3h; Sealed glass reactor;
	With hydrogen In water at 80℃; Autoclave;
1: 43.5 %Chromat. 2: 19.4 %Chromat. 3: 16.2 %Chromat. 4: 15.1 %Chromat.	With C₅₄H₄₂ClO₉P₃RhS₃^(3-)*3Na⁽¹⁺⁾; sodium formate; sodium 3-(diphenylphosphanyl)benzenesulfonate In water; isopropyl alcohol at 70℃; for 1h; Inert atmosphere;
	With hydrogen In ethanol at 80℃; for 3.5h; Autoclave;
	With hydrogen In isopropyl alcohol at 160℃; Sealed tube;
	With hydrogen; sodium hydroxide In ethanol at 25℃; for 1h; chemoselective reaction;	Catalytic Testing The liquid-phase hydrogenation of citral was carriedout at P = 1 atm and T = 25°C. The catalyst (13 or 25 mg) was placed in a two-necked flask, and the systemwas purged with hydrogen for 30 min. A solutionof 0.3 mmol of citral in 1.5 mL of EtOH was then poured into the reactor using a feed valve. Depending on the content of platinum in the catalyst, the amount of Pt in the reaction mixture was 0.8-0.2 mol %. The reaction mixture was stirred with a magnetic stirrer at a speed of 1400 rpm. At the end of each experiment, the liquid phase was separated from the catalyst via centrifugation and the supernatant was sampled to analyze the reaction products.

Reference： [1]Girard, P.; Namy, J. L.; Kagan, H. B. [Journal of the American Chemical Society, 1980, vol. 102, # 8, p. 2693 - 2698]
[2]Girard, P.; Namy, J. L.; Kagan, H. B. [Journal of the American Chemical Society, 1980, vol. 102, # 8, p. 2693 - 2698]
[3]Gieck, Christine; Schreyer, Martin; Faessler, Thomas F.; Cavet, Sylwia; Claus, Peter [Chemistry - A European Journal, 2006, vol. 12, # 7, p. 1924 - 1930]
[4]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 15-17; 1/4-3/4
[5]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 17; 3/4
[6]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 15-17; 3/4
[7]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 17; 3/4
[8]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 14-17; 1/4-3/4
[9]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 17; 3/4
[10]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 19
[11]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 19
[12]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 19
[13]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 19
[14]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 17-21
[15]Current Patent Assignee: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - WO2007/13156, 2007, A1 Location in patent: Page/Page column 19
[16]Location in patent: experimental part Chatterjee; Ikushima; Yokoyama; Sato [Advanced Synthesis and Catalysis, 2008, vol. 350, # 4, p. 624 - 632]
[17]Location in patent: experimental part Cheng, Haiyang; Liu, Ruixia; Hao, Jianmin; Wang, Qiang; Yu, Yancun; Cai, Shuxia; Zhao, Fengyu [Applied Organometallic Chemistry, 2010, vol. 24, # 11, p. 763 - 766]
[18]Ming, Jun; Liu, Ruixia; Liang, Guanfeng; Cheng, Haiyang; Yu, Yancun; Zhao, Fengyu [Journal of Materials Chemistry, 2011, vol. 21, # 29, p. 10929 - 10934]
[19]Kathó, Ágnes; Szatmári, Imre; Papp, Gábor; Joó, Ferenc [Chimia, 2015, vol. 69, # 6, p. 339 - 344]
[20]Li, Wei; Fan, Guoli; Yang, Lan; Li, Feng [Catalysis science and technology, 2016, vol. 6, # 7, p. 2337 - 2348]
[21]Zhou, Junyao; Yang, Yusen; Li, Changming; Zhang, Shitong; Chen, Yudi; Shi, Shuxian; Wei, Min [Journal of Materials Chemistry A, 2016, vol. 4, # 33, p. 12825 - 12832]
[22]Vikanova; Redina [Russian Journal of Physical Chemistry, 2019, vol. 93, # 12, p. 2566 - 2569][Zh. Fiz. Khim., 2019, vol. 93, # 12, p. 1917 - 1920,4]

17
[ 5392-40-5 ]
[ 106-22-9 ]
[ 106-25-2 ]
[ 106-24-1 ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid In water; N,N-dimethyl-formamide electochemical reduction, various reaction conditions;
	With dichloro(benzene)ruthenium(II) dimer; sodium formate In water at 80℃; for 3h; Sealed glass reactor;
	With Pt(5wt%)Sn(3wt%)/Al2O3; hydrogen In isopropyl alcohol at 70℃; for 2h;

1: 39.8 %Chromat. 2: 8.9 %Chromat. 3: 7.2 %Chromat.	With C₅₄H₄₂ClO₉P₃RhS₃^(3-)*3Na⁽¹⁺⁾; sodium formate; sodium 3-(diphenylphosphanyl)benzenesulfonate In water; isopropyl alcohol at 40℃; for 1h; Inert atmosphere;
	With hydrogen In ethanol at 80℃; for 3.5h; Autoclave;
	With hydrogen In n-heptane at 90℃; chemoselective reaction;	2.4. Catalytic performance The citral hydrogenation was carried out in 100 ml heptanesolution at a constant hydrogen pressure of 8.3 bar and 90 °C usinga Parr reactor model 5500. The experimental conditions such ascitral concentration, catalyst weight and stirring speed, were previouslyoptimized in order to avoid mass transfer limitations (resultsnot showed) and fixed in 0.05 M, 500 mg and 1500 rpm, respectively.A small volume of the sample (1 mL) was periodically withdrawnand analysed by chromatography using a Bruker 430-GCequipped with a FID detector and a Varian GC Capillary ColumnCP7485 (25 m 0.32 mm 0.45 μm). Citral and all possible productswere previously calibrated.
	With hydrogen; zinc(II) acetylacetonate at 85℃; for 5h; Autoclave;	2 Comparative Example 2 Under the anaerobic and anhydrous atmosphere,Into a 1 L hydrogenation kettle, 0.009 g of zinc acetylacetonate and 500 g of citral were successively added.Seal the autoclave, replace with nitrogen and hydrogen three times, and start heating and stirring.When the temperature rose to 85 , hydrogen gas was charged to 2MPa, and maintained for 5h until the end of the reaction.The results of the reaction were analyzed by GC and the results are shown in Table 1.

Reference： [1]Saplay, K. M.; Damodaran, N. P.; Dev, Sukh [Tetrahedron, 1983, vol. 39, # 48, p. 2999 - 3004]
[2]Korotyaeva, L. M.; Rubinskaya, T. Ya.; Gultyai, V. P. [Russian Chemical Bulletin, 1993, vol. 42, # 11, p. 1830 - 1834][Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1993, # 11, p. 1915 - 1919] Rubinskaya, T. Ya.; Korotayeva, L. M.; Gul'tyai, V. P. [Russian Chemical Bulletin, 1993, vol. 42, # 11, p. 1835 - 1838][Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1993, # 11, p. 1919 - 1923]
[3]Location in patent: experimental part Cheng, Haiyang; Liu, Ruixia; Hao, Jianmin; Wang, Qiang; Yu, Yancun; Cai, Shuxia; Zhao, Fengyu [Applied Organometallic Chemistry, 2010, vol. 24, # 11, p. 763 - 766]
[4]Location in patent: experimental part Zgolicz, Patricia D.; Rodríguez, Virginia I.; Vilella, Irene M.J.; De Miguel, Sergio R.; Scelza, Osvaldo A. [Applied Catalysis A: General, 2011, vol. 392, # 1-2, p. 208 - 217]
[5]Kathó, Ágnes; Szatmári, Imre; Papp, Gábor; Joó, Ferenc [Chimia, 2015, vol. 69, # 6, p. 339 - 344]
[6]Li, Wei; Fan, Guoli; Yang, Lan; Li, Feng [Catalysis science and technology, 2016, vol. 6, # 7, p. 2337 - 2348]
[7]Bailón-García, Esther; Carrasco-Marín, Francisco; Pérez-Cadenas, Agustín F.; Maldonado-Hódar, Francisco J. [Journal of Catalysis, 2016, vol. 344, p. 701 - 711]
[8]Current Patent Assignee: WANHUA CHEMICAL GROUP CO LTD - CN111018666, 2020, A Location in patent: Paragraph 0054-0055; 0058-0059

18
[ 5392-40-5 ]
[ 106-25-2 ]

Yield	Reaction Conditions	Operation in experiment
97%	With isopropyl alcohol for 6h; Heating;
97%	With isopropyl alcohol for 6h; Heating;
95%	With sodium formate In water at 80℃; for 7h;

92%	With potassium hydroxide; tris(triphenylphosphine)ruthenium(II) chloride; hydrogen; ethylenediamine In isopropyl alcohol; toluene at 28℃; for 0.3h;
90%	With BER In methanol at 25℃; for 3h;
88%	With zinc(II) tetrahydroborate; silica gel In tetrahydrofuran at -10 - -5℃; for 7h;
86%	With sodium tetrahydroborate; acetic acid In tetrahydrofuran at 25℃; for 20h;
	With lithium aluminium tetrahydride for 0.166667h; Ambient temperature; Without catalyst;
	With sodium tetrahydroborate In methanol; dichloromethane at -78℃; Competition with ..(aldehyde 1a).. and ..(ketones 3a, 3d, 3e, 3b).. and ..(enones 4a, 4f).. Studies on the chemoselective reduction of various types of aldehydes and ketones with sodium borohydride.;
62 % Turnov.	With hydrogen In benzene at 50℃; for 2h; other catalysts;
	With Compound ⁽³⁾ In tetrahydrofuran; diethyl ether at 20℃; for 0.583333h; Yield given;
100 % Chromat.	With sodium tetrahydroborate; erbium(III) chloride In ethanol; water The reaction was carried out in the presence of citronellal. Condition used was described in ref. 3. (J_. Am_. Chem_. Soc_. ⁽¹⁹⁷⁹⁾, 44, 4187). Addition of other non-conjugated aldehydes was investigated as well.;
100 % Chromat.	With lithium aluminium tetrahydride In tetrahydrofuran for 0.166667h; Ambient temperature;
62 % Turnov.	With hydrogen In benzene at 50℃; for 2h;
	With Ru/GaOOH; hydrogen at 119.84℃; for 6h; Autoclave; Neat (no solvent);
88 %Chromat.	With methylamine-borane In water at 20℃; for 0.5h; Green chemistry; chemoselective reaction;	General Procedure for the Hydrogenation of Carbonyl Compounds to Alcohols General procedure: A mixture of carbonyl compound (1 mmol) and MeAB (1 mmol) in neat water (2 mL) was stirred at room temperature for an appropriate time. The reaction was monitored by TLC and gas chromatography (GC). After completion, the reaction mixture was extracted with ethyl acetate (310 mL). Then, the organic extracts were concentrated by rotary evaporation, and the residue was purified by silica-gelcolumn chromatography (elution by using petroleum ether=ethyl acetate 5:1) to obtain the alcohol product.

Reference： [1]Shibagaki, Makoto; Takahashi, Kyoko; Matasushita, Hajime [Bulletin of the Chemical Society of Japan, 1988, vol. 61, p. 3283 - 3288]
[2]Shibagaki, Makoto; Takahashi, Kyoko; Matasushita, Hajime [Bulletin of the Chemical Society of Japan, 1988, vol. 61, p. 3283 - 3288]
[3]Joo, Ferenc; Benyei, Attila [Journal of Organometallic Chemistry, 1989, vol. 363, p. C19 - C21]
[4]Ohkuma, Takeshi; Ooka, Hirohito; Ikariya, Takao; Noyori, Ryoji [Journal of the American Chemical Society, 1995, vol. 117, # 41, p. 10417 - 10418]
[5]Sande, A. R.; Jagadale, M. H.; Mane, R. B.; Salunkhe, M. M. [Tetrahedron Letters, 1984, vol. 25, # 32, p. 3501 - 3504]
[6]Ranu, Brindaban C.; Das, Asish R. [Journal of Organic Chemistry, 1991, vol. 56, # 15, p. 4796 - 4798]
[7]Nutaitis, Charles F.; Bernardo, Joseph E. [Journal of Organic Chemistry, 1989, vol. 54, # 23, p. 5629 - 5630]
[8]Fukuzawa, Shin-ichi; Fujinami, Tatsuo; Yamauchi, Shoji; Sakai, Shizuyoshi [Journal of the Chemical Society. Perkin transactions I, 1986, p. 1929 - 1932]
[9]Ward, Dale E.; Rhee, Chung K. [Canadian Journal of Chemistry, 1989, vol. 67, p. 1206 - 1211]
[10]Li, Rui-Xiang; Tin, Kam-Chung; Wong, Ning-Bew; Mak, Thomas C.W.; Zhang, Ze-Ying; Li, Xian-Jun [Journal of Organometallic Chemistry, 1998, vol. 557, # 2, p. 207 - 212]
[11]Babler, James H.; Invergo, Benedict J. [Tetrahedron Letters, 1981, vol. 22, p. 621 - 622]
[12]Gemal, A. L.; Luche, J. L. [Tetrahedron Letters, 1981, vol. 22, # 41, p. 4077 - 4080]
[13]Fukuzawa, Shin-ichi; Fujinami, Tatsuo; Yamauchi, Shoji; Sakai, Shizuyoshi [Journal of the Chemical Society. Perkin transactions I, 1986, p. 1929 - 1932]
[14]Li, Rui-Xiang; Tin, Kam-Chung; Wong, Ning-Bew; Mak, Thomas C.W.; Zhang, Ze-Ying; Li, Xian-Jun [Journal of Organometallic Chemistry, 1998, vol. 557, # 2, p. 207 - 212]
[15]Location in patent: body text Nishiyama, Hiroshi; Takeuchi, Junichi; Hayase, Hiroshi; Saito, Nobuo; Inoue, Yasunobu [Chemistry Letters, 2008, vol. 37, # 12, p. 1256 - 1257]
[16]Duan, Yifan; Bai, Ruijiao; Tian, Jun; Chen, Ligong; Yan, Xilong [Synthetic Communications, 2014, vol. 44, # 17, p. 2555 - 2564]

19
[ 106-25-2 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	With bis(pentafluorophenyl)borinic acid; magnesium sulfate; pivalaldehyde In toluene for 3h; Ambient temperature;
95%	With Ba<RuO3(OH)2> In dichloromethane for 48h;
91%	With 4-acetylamino-2,2,6,6-tetramethylpiperidine-N-oxyl; toluene-4-sulfonic acid In dichloromethane 1) 0 deg C, 1 h, 2) r.t., 2 h;

90%	With chromium (VI) oxide In chloroform for 3h; Heating;
84%	With tetrabutylammonium chlorochromate In chloroform for 52h; Ambient temperature;
82%	With imidazolium dichromate In N,N-dimethyl-formamide for 2h; Ambient temperature;
78%	With sodium bromate; NaHCO₃ buffer pH:10; sodium carbonate In water; 1,2-dichloro-ethane at 70℃; for 1.5h;
74%	With potassium chlorochromate In acetone for 2h;
63%	With bromine; oxygen In acetic acid at 40℃; for 24h;
62%	With furfural; t-BuOSmI₂ In tetrahydrofuran at 65℃; for 24h; other oxidant;
56%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; oxygen In toluene Heating;
51%	With potassium chlorochromate on SiO₂ In dichloromethane for 5h; Ambient temperature;
35%	With tert.-butylhydroperoxide In dichloromethane for 20h; Ambient temperature;
	With silver(I) nitrite In N,N-dimethyl-formamide
	With chromium (VI) oxide In chloroform for 4h; Heating; various oxidant, various yield of product;
95 % Turnov.	With dipyridinium dichromate; dihydrogen peroxide; sodium carbonate In 1,2-dichloro-ethane at 80℃; for 24h;
	With tert.-butylhydroperoxide; oxygen In decane; toluene at 80℃;
	With dmap; [2,2]bipyridinyl; copper(l) iodide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In acetonitrile at 20℃; for 2h;

Reference： [1]Ishihara, Kazuaki; Kurihara, Hideki; Yamamoto, Hisashi [Journal of Organic Chemistry, 1997, vol. 62, # 17, p. 5664 - 5665]
[2]Green, Graham; Griffith, William P.; Hollinshead, David M.; Ley, Steven V.; Schroeder, Martin [Journal of the Chemical Society. Perkin transactions I, 1984, # 4, p. 681 - 686]
[3]Ma, Zhenkun; Bobbitt, James M. [Journal of Organic Chemistry, 1991, vol. 56, # 21, p. 6110 - 6114]
[4]Lee, Ross A.; Donald, Dennis S. [Tetrahedron Letters, 1997, vol. 38, # 22, p. 3857 - 3860]
[5]Santaniello, Enzo; Milani, Fulvia; Casati, Rosangela [Synthesis, 1983, # 9, p. 749 - 751]
[6]Kim, Sunggak; Lhim, Dong Chul [Bulletin of the Chemical Society of Japan, 1986, vol. 59, p. 3297 - 3298]
[7]Kanemoto, Shigekazu; Tomioka, Hiroki; Oshima, Koichiro; Nozaki, Hitosi [Bulletin of the Chemical Society of Japan, 1986, vol. 59, p. 105 - 108]
[8]Carlsen, Per H.J.; Braenden, Jon Eric [Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1987, vol. 41, # 5, p. 313 - 317]
[9]Hirano, Masao; Morimoto, Takashi; Itoh, Keiko [Bulletin of the Chemical Society of Japan, 1988, vol. 61, # 10, p. 3749 - 3751]
[10]Namy, J. L.; Souppe, J.; Collin, J.; Kagan, H. B. [Journal of Organic Chemistry, 1984, vol. 49, # 11, p. 2045 - 2049]
[11]Gomez-Bengoa, Enrique; Noheda, Pedro; Echavarren, Antonio M. [Tetrahedron Letters, 1994, vol. 35, # 38, p. 7097 - 7098]
[12]Carlsen, Per H. J.; Husbyn, Mette; Braenden, Jon E,; Eliason, Robert [Acta Chemica Scandinavica, 1989, vol. 43, # 5, p. 485 - 488]
[13]Muzart, Jacques [Tetrahedron Letters, 1987, vol. 28, # 19, p. 2133 - 2134]
[14]Abidi, S. L. [Tetrahedron Letters, 1986, vol. 27, # 3, p. 267 - 270]
[15]Lee, Ross A.; Donald, Dennis S. [Tetrahedron Letters, 1997, vol. 38, # 22, p. 3857 - 3860]
[16]Muzart, Jacques; Ajjou, Abdelaziz N'Ait; Ait-Mohand, Samia [Tetrahedron Letters, 1994, vol. 35, # 13, p. 1989 - 1990]
[17]Giorgi, Pascal D.; Elizarov, Nelli; Antoniotti, Sylvain [ChemCatChem, 2017, vol. 9, # 10, p. 1830 - 1836]
[18]Bulska, Ewa; Enciso, Alan E.; Fantin, Marco; Grela, Karol; Lorandi, Francesca; Matyjaszewski, Krzysztof; Nogas, Wojciech; Piatkowski, Jakub; Ruszczynska, Anna; Szczepaniak, Grzegorz; Yerneni, Saigopalakrishna S. [Chemical Science, 2020, vol. 11, # 16, p. 4251 - 4262]

20
[ 480-39-7 ]
[ 5392-40-5 ]
rubranine [ No CAS ]

Reference： [1]Australian Journal of Chemistry,1984,vol. 37,p. 449 - 453

21
[ 201017-90-5 ]
[ 5392-40-5 ]
(E)-2,7-Dimethyl-1-(2-methylsulfanyl-oxazol-5-yl)-octa-2,6-dien-1-ol [ No CAS ]
(E)-2,7-Dimethyl-1-(2-methylsulfanyl-oxazol-5-yl)-octa-2,6-dien-1-ol [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1998,vol. 63,p. 551 - 555

22
[ 5392-40-5 ]
[ 624-15-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	With formic acid; C₁₉H₂₅ClF₃IrN₂O₂S; triethylamine In ethyl acetate at 23℃;	2 Example 2: Selective transfer hydrogenation of Citral To the solution (obtained according to Example 1 ) 6 mL solvent, 4 mmol (621 mg=700 μΙ_) citral and 20 mmol reducing agent were added and stirred at the desired temperature (for all the following hydrogenation room temperature = 23 °C was used).. The reaction mixture was concentrated at 100 mbar by 40 °C. The residue was filtered over 10 g Si02 and washed with 50 mL ethyl acetate. The solution was concentrated at 100 mbar, 40 °C and the residue analyzed by gas chromatography with internal standard. In the following table the results of the transfer hydrogenation with the catalysts of Example 1 are summarized.
99%	With formic acid; C₁₉H₂₅ClF₃IrN₂O₂S; triethylamine In ethyl acetate at 23℃;	2 Example 2: Selective transfer hydrogenation of Citral General procedure: To the solution (obtained according to Example 1 ) 6 mL solvent, 4 mmol (621 mg=700 μΙ_) citral and 20 mmol reducing agent were added and stirred at the desired temperature (for all the following hydrogenation room temperature = 23 °C was used).. The reaction mixture was concentrated at 100 mbar by 40 °C. The residue was filtered over 10 g Si02 and washed with 50 mL ethyl acetate. The solution was concentrated at 100 mbar, 40 °C and the residue analyzed by gas chromatography with internal standard. In the following table the results of the transfer hydrogenation with the catalysts of Example 1 are summarized.
98%	With triscarbonyl-(2,4-bis(trimethylsilyl)bicyclo[3.3.0]nona-1,4-dien-3-one)iron; hydrogen; potassium carbonate In water monomer; isopropanol at 100℃; for 17h; Inert atmosphere;

98%	With C₃₆H₁₀₃AlO₄Si₁₄; isopropanol In neat (no solvent) at 50℃; for 24h; Glovebox; Schlenk technique;
98%	With C₅₅H₄₄O₂P₄Ru; hydrogen In toluene at 80℃; for 18h; Glovebox; Autoclave;	4 Example 4 In an argon glove box,A 5 mL vial equipped with a magnetic stir bar was charged with the desired amount of catalyst 2 (0.005 mol%),Citral 3b (5 mmol) and toluene (1.5 mL) were added and the mixture was transferred to a non-polluting autoclave,Then use the H2 (10atm) pressure / exhaust three cycles for ventilation.It was then pressurized with H2 (50 atm) and disconnected from the H2 source, the autoclave was placed in an oil bath preheated to 80 ° C,After the reaction was stirred for 18h, the autoclave was cooled in an ice bath and the hydrogen was slowly released.The silica gel column gave product 4b in a yield of 98%The selectivity of the double bond without being reduced is 97%.
98%	With C₅₅H₄₄O₂P₄Ru; hydrogen In toluene at 80℃; for 18h; Inert atmosphere; Glovebox; Autoclave;
98.85%	With zirconium hydroxycarbonate In isopropanol at 80℃; for 15h; Autoclave; Sealed tube;
97%	With mesoporous silica; sodium cyanotrihydridoborate at 70 - 80℃; for 0.0138889h; Neat (no solvent); regioselective reaction;
97%	With sodium tetrahydridoborate; diammonium oxalate In acetonitrile at 20℃; for 0.333333h; regioselective reaction;
97%	With iron(II) fluoro{tris[2-(diphenylphosphino)phenyl]phospino}tetrafluoroborate; hydrogen; trifluoroacetic acid In isopropanol at 120℃; Inert atmosphere; Autoclave; chemoselective reaction;
97%	With C₂₉H₃₄BNOP₂Ru In ethanol; dichloromethane Schlenk technique; Inert atmosphere; Reflux;
97%	With C₄₆H₄₉CoN₃P₄⁽²⁺⁾*2BF₄^(1-); hydrogen; potassium hydroxide In ethanol; acetonitrile at 60℃; for 24h; Autoclave; Glovebox; chemoselective reaction;
96%	With iron(II) fluoride; water monomer; aluminium for 24h;
96%	With di-μ-chlorobis-[(η⁶-p-cymene)chlororuthenium(II)]; C₁₃H₁₉N₄O₂S⁽¹⁺⁾ClHCl^(1-); sodium formate dihydrate In water monomer at 80℃; for 3.5h; Inert atmosphere; chemoselective reaction;
96%	With hydrogen; silver⁽⁰⁾ In tetrahydrofuran at 150℃; for 72h;	11 Catalysts E to G for Examples obtained in Production Example 4 were each 0.008 mmol in terms of metal equivalent of silver, incidentally, as a substrate having a carbon-carbon double bond and an aldehyde group, 0.25 mmol of citral (a mixture of cis-trans isomers geranial and neral 2: 1) Solvent 5 ml of tetrahydrofuran (THF), hydrogen pressure 1.5 MPa, Hydrogenation reduction treatment was carried out at a reaction temperature of 150 ° C. reaction time is In each of Examples 11 to 13, it was 72 hours, by using gas chromatograph, yield, selectivity was measured. The results are shown in Table 5.
95%	With (Ppyz)Zr(BH₄)2Cl₂ In diethyl ether at 20℃; for 2h;
95%	Stage #1: (E/Z)-3,7-dimethyl-2,6-octadienal With [(N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine)Mn(CO)₂H] In 1,2-dimethoxyethane at 110℃; for 18h; Inert atmosphere; Sealed tube; Stage #2: With sodium hydroxide at 25℃; for 18h; Inert atmosphere; chemoselective reaction;	General procedure for hydrosilylation reactions General procedure: Inside an Ar-flushed glovebox, an 8 cm3 microwave vial was charged with complex (0.01-0.03 mol%), carbonyl substrate (0.35 mmol), 2 cm3 solvent, and silane (0.035-0.1 mmol) in this order. A stirring bar was added, and the vial was sealed. The closed vial was removed from the glovebox and stirred for 18 h at the indicated temperature in a heated aluminum block. The vial was allowed to reach room temperature and the reaction was quenched by exposure to air. In case of screening reactions, fluorobenzene (0.35 mmol) was added and the reaction mixture was analyzed by 19F{1H} NMR. Isolation of the product To the reaction mixture 2 cm3 of a 20 wt% NaOH-solution were added and the solution was stirred for 18 h at room temperature. The phases were separated, and the aqueous phase was three times extracted with 2 cm3 diethyl ether. The combined organic phases were filtrated over a pad of silica, dried over Na2SO4 and the solvent was removed. Spectroscopic data of all isolated products are in line with the literature [11, 42-49].
94%	With hydrogen In tetrahydrofuran at 150℃; for 12h; Autoclave; chemoselective reaction;
94%	With hydrogen; Cs₂CO₃ In tetrahydrofuran at 150℃; for 6h; Autoclave; chemoselective reaction;
94%	With sodium tetrahydridoborate In tetrahydrofuran at 20℃; for 0.333333h;
94%	With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H₂O); isopropanol at 82℃; for 6h; Inert atmosphere; Green chemistry;	15 3,7-dimethyl-2,6-octadienol Citral (152 mg, 1.0 mmol), cat. [Ir] (1.1 mg, 0.002 mmol, 0.2 mol%) and isopropanol (5 mL) were sequentially added to a 25 mL Kelvin tube, protected with N2 and reacted at 82 ° C for 6 h. Cool to room temperature and remove the solvent by rotary evaporation.The pure target compound was obtained by column chromatography (developing solvent: petroleum ether / ethyl acetate), yield: 94%
93%	With sodium tetrahydridoborate; poly[N-(2-aminoethyl)acrylamido]trimethyl ammonium chloride In tetrahydrofuran; water monomer at 20℃; for 0.416667h;
93%	With Zn⁽²⁺⁾2BH₄^(1-)C₆H₇NO In acetonitrile at 20℃; for 0.0166667h; chemoselective reaction;	Reduction of Benzaldehyde to Benzyl alcoholwith [Zn(BH4)2(2-MeOpy)] General procedure: A Typical ProcedureIn a round-bottomed flask (10 mL),equipped with a magnetic stirrer, a solution ofbanzaldehye (0.106 g, l mmol) in CH3CN (3 mL)was prepared. The complex reducing agent (0.1 g,0.5 mmol) was then added and the mixture wasstirred at room temperature. TLC monitored theprogress of the reaction (eluent; Hexane/EtOAc: 9/1). After completion of the reaction within 1 min, asolution of 5% HCl (5 mL) was added to the reactionmixture and stirred for 5 min. The mixture was extracted with CH2Cl2 (3 × 10 mL) and dried overthe anhydrous sodium sulfate. Evaporation of thesolvent and short column chromatography of theresulting crude material over silica gel (0.015-0.040mm) by eluent of (Hexane/EtOAc: 9/1) afforded thepure liquid benzyl alcohol (0.105 g, 98% yield)
93%	With NaNO₃; sodium tetrahydridoborate; acetophenone In water monomer at 20℃; for 1h; regioselective reaction;
92%	With sodium tris(acetoxy)borohydride In benzene for 3h; Heating;
92%	With aluminum(III) oxide; zinc(II) tetrahydroborate In tetrahydrofuran at 20℃; for 0.08h; regioselective reaction;	The typical procedure for the regioselective 1,2-reduction of conjugated carbonyl compoundswith the Zn(BH4)2/Al2O3 system in THF General procedure: In a round-bottomed flask (10 mL) equipped with a magnetic stirrer, a solution of benzylideneacetone(0.146 g, 1 mmol) in THF (3 mL) was prepared. To this solution, Zn(BH4)2(0.0.95 g, 1 mmol) and then neutral Al2O3 (0.101 g, 1 mmol) were added. The resulting mixturewas stirred at room temperature. The progress of the reaction was monitored by TLC(eluent, CCl4/Et2O: 5/2). After completion of the reaction within 60 min, distilled water (1mL) was added to the reaction mixture and this mixture was then stirred for an additional 5min. The mixture was extracted with CH2Cl2 (3×10 mL) and dried over anhydrous sodiumsulfate. Evaporation of the solvent and short column chromatography of the resulting crudematerial over silica gel (eluent, CCl4/Et2O: 5/2) afforded pure liquid 4-phenyl-3-buten-2-ol(0.140 g, 95 % yield, Table VIII, entry 3).
92%	With Co-doped ammonia borane In methanol at 20℃; for 0.0833333h; chemoselective reaction;
91%	With isopropanol at 120℃; for 4h;	2.4. Catalytic reaction General procedure: The MPV reaction of the biomass-derived compounds with 2-propanol was carried out in an oil-heated condition in a 15 ml Ace pressure tube (Synthware, Beijing). Typically, aldehydes (1.0 mmol), catalysts (0.1 g), and 2-propanol (10 mL) were added into the reactor, and then placed into the oil bath at stated temperature of 80-140 °C, followed bythe magnetic stirring for specific time at 600 rpm. After completion, the reaction tube was cooled to room temperature with cold water in a beaker. The reaction mixture was centrifuged and collected for analysis. Quantitative analysis of reactants and products on a standard sample using toluene as an internal standard on a GC (Shimadzu Nexis GC-2030) equipped with an HP-5 capillary column (30.0m×250mm×0.25 mm) and a flame ionization detector. Identification of products were observed using GC-MS (GCMS-QP2010 Ultra) equipped with HP-5MS capillary column (30.0m×250mm×0.25 mm).
90%	With benzoic acid sodium salt; sodium tetrahydridoborate; benzalacetophenone In water monomer at 20℃; for 0.5h; Sonication; Green chemistry; regioselective reaction;	A typical Procedure for Competitive Reduction of aldehydes and ketones with NaBH4/PhCO2Na/H2O/U.S. system General procedure: In a round-bottomed flask (10 ml) equipped with a magnetic stirrer, a solution of benzaldehyde (0.106 g, l mmol) and acetophenone (0.120 g, 1 mmol) in H2O (3 mL) was prepared. To this solution, NaBH4(0.047 g, 1.25 mmol) and PhCO2Na (0.138 g, 2 mmol) was added. The mixture was stirred and irradiated with ultrasound waves at room temperature for 60 minutes. TLC monitored the progress of reaction. After 60 min, the reaction mixture was quenched by addition of distilled water (5 ml) and this mixture was then stirred for an additional 1 min. The mixture was extracted with CH2Cl2(5×10 ml) and dried over anhydrous sodium sulfate.Evaporation of the solvent and short column chromatography of the resulting crude material over silicagel by eluent of Hexane/EtOAc: 9/1 affords the pure liquid benzyl alcohol (0.099 g, 92%) as a sole product of reduction and acetophenone as an intact material (table 2, entry 1)
85%	With iron(III) chloride; magnesium In water monomer; N,N-dimethyl-formamide at 20℃; for 2.5h;
85%	With (ethylenediamine)[1,2-bis(diphenylphosphino)ethane]ruthenium(II)(bisbenzoate); hydrogen In n-heptane at 80℃; Autoclave; Inert atmosphere;	6 3,7-dimethylocta-2,6-dien-1-ol synthesis 3,7-Trimethyl-octa-2,6-dienal (as a 40/60 Z/E isomers mixture) (152 g, 1 mol.), heptane (304 g, 200 wt. %, technical grade) and (ethylenediamine)[1,2-bis(diphenylphosphino)ethane]ruthenium(bisbenzoate) (80.1 mg, 0.1 mmol, 0.01 mol.%) were loaded altogether in a 11 autoclave equipped with a mechanical stirring device. Sealed autoclave was then purged under stirring with nitrogen (3 times 5 bars) and hydrogen (3 times 5 bars) before being pressurized to 30 bars hydrogen. It was then heated to 80° C. and hydrogen pressure was maintained to 30 bars during all the reaction to afford desired product with 90% selectivity. Upon reaction completion (checked by both hydrogen consumption and GC), autoclave was cooled down to 25° C. It was then depressurized and purged with nitrogen (3 times 5 bars) and reaction mixture was then transferred to a round-bottomed flask and solvent was removed under vacuum. After initial flash distillation followed by further fractional distillation, pure 3,7-dimethyloct-2,6-dien-1-ol was obtained in 85% yield.
80%	With Zrβ-NO₃-12.5 In isopropanol at 82℃; for 4h;
74%	With water monomer; 1,8-diazabicyclo[5.4.0]undec-7-ene; 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl-4',4',5',5'-tetramethyl-1,3,2-dioxaborolane at 20℃; for 10h; Sealed tube; chemoselective reaction;
	With sodium hydroxide; sodium tetrahydridoborate; zinc 2-ethylhexanoate 1.) THF, reflux, 2.) 40 deg, 1 h; Yield given; Multistep reaction;
	With anhydrous sodium formate; isopropanol at 83℃; for 1h;
	With hydrogen at 120℃; Inert atmosphere; Autoclave;	4 Example 4Selective Hydrogenation of Citral2 g of catalyst powder obtained in Example 1 was introduced into an autoclave of 200 ml in volume and then added with 130 ml of citral. After sealing the autoclave, nitrogen gas was repeatedly introduced into and discharged from the autoclave 3 times at a pressure of 1 MPa while stirring. Subsequently, the nitrogen gas was substituted with hydrogen gas at a pressure of 1.3 MPa and then heated up to 120° C. During the hydrogenation, samples were taken from a reaction vessel at regular intervals and analyzed by gas chromatography.The conversion rate of citral, the selectivity of nerol/geraniol generated on the basis of such a conversion rate, and the by-products are listed in Table 1. TABLE 1 Citral Selectivity of product (%) conversion Nerol/ Tetrahydro Unknown rate (%) geraniol Citronellal Citronellol geraniol substance 11.35 100.00 0.00 0.00 0.00 0.00 35.44 97.52 0.00 0.00 0.00 2.48 55.32 96.80 0.00 0.86 0.00 2.34 60.87 96.90 0.00 0.87 0.00 2.23 84.72 96.44 0.00 1.40 0.00 2.16
	With hydrogen at 200℃; for 1h; Gas phase; chemoselective reaction;
	With gold supported on mesoporous ceria; hydrogen In water monomer at 100℃; for 2.5h; chemoselective reaction;
52 %Chromat.	With hydrogen; potassium hydroxide In isopropanol at 23℃; for 18h; autoclave;	47 Examples 24-48; Catalytic hydrogenation of ketones or aldehydes using various invention's ruthenium complexes; The hydrogenation substrate (20 mmol), the base (as in Table 2), ο-propanol (10 ml), and the catalyst precursor RuCl2(L4) (0.01 mmol) were placed into a pressure reactor and stirred under ¾ (50 bar) at the given temperature for the given amount of time as indicated in Table 2.
99 %Chromat.	With formic acid; iron(II) tetrafluoroborate hexahydrate; tris(2-diphenylphosphinoethyl)phosphine In tetrahydrofuran at 60℃; for 2h; Schlenk technique; Inert atmosphere;	2. Experimental General procedure: Fe(BF4)2·6H2O (0.7 mg; 0.002 mmol) and tris[2-(diphenyl-phosphino)-ethyl]phosphine [P(CH2CH2PPh2)3; tetraphos] (1.4 mg; 0.002 mmol) are placed in a Schlenk-tube under argon atmosphere. 1 mL dry tetrahydrofurane is added and the purple solution is stirred for 2 min. Cinnamaldehyde (63 μL; 0.5 mmol) and 100 μL n-hexadecane as an internal GC-standard are injected and a sample is taken for GC-analysis. The solution is heated to 60 °C and the reaction starts by addition of 1.1 equiv formic acid (22 μL; 0.55 mmol). After 2 h, a second sample is taken for GC-analysis and conversion and yield are determined by comparison with authentic samples. For the isolation, the reaction is scaled up by a factor of 20. When the reaction is completed, the reaction solution is diluted with a mixture of n-hexane and ethyl acetate (3:1), filtered through a plug of silica and the solvent removed in vacuum.
52 %Chromat.	With (N,N'-bis(2-(tert-butylthio-kS)benzylidene)-1,2-ethanediamino-kN,kN')dichlororuthenium(II); hydrogen; potassium hydroxide In isopropanol at 23℃; for 18h; Inert atmosphere; Autoclave;	47 General procedure: The hydrogenation substrate (20 mmol), the base (as in Table 2), iso-propanol (10 ml), and the catalyst precursor RuCl2(L4) (0.01 mmol) were placed into a pressure reactor and stirred under H2 (50 bar) at the given temperature for the given amount of time as indicated in Table 2.
	With [(ethylenediamine)(9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene)Ru(OCOtBu)2]; hydrogen; benzoic acid at 100℃; for 5h; Autoclave;
	With hydrogen In hexane at 60℃; for 18h; Autoclave; chemoselective reaction;
	With hydrogen In isopropanol at 90℃;
	With hydrogen In ethanol; butan-1-ol at 80℃; for 1h; chemoselective reaction;
	With hydrogen In hexane at 60℃; for 18h; Autoclave; chemoselective reaction;
> 99 %Chromat.	With C₁₆H₃₃Cl₂CoN₅P₂; hydrogen; sodium tertiary butoxide In tert-Amyl alcohol at 20℃; for 24h; Autoclave;
87.6 %Chromat.	With porous zirconium-phytic acid hybrid In isopropanol at 100℃; for 6h;
	Multi-step reaction with 2 steps 1: [bis(2,6-diisopropylaniline)acenaphthene]Fe(η⁶-toluene) / neat (no solvent) / 70 °C / Glovebox; Schlenk technique 2: N,N,N-tributylbutan-1-aminium fluoride / tetrahydrofuran / 3 h / 0 - 20 °C
73 %Spectr.	With C₁₆H₂₆AlNO; isopropanol for 0.25h; Reflux; Inert atmosphere; Schlenk technique;	4.3 Typical procedure employed for MPV reactions General procedure: A 25mL Schlenk flask was charged with aluminum complex (0.2mmol) and the carbonyl compound (4.0mmol) was added, followed by the addition of 2-propanol (0.37mL, 4.8mmol). The reaction mixture was then refluxed for 15min, and the yield was determined by 1H NMR spectroscopic studies based on the integration in the methylene and the CHO region of the benzyl group.
	With hydrogen In ethanol; water monomer at 99.84℃; for 4h; Autoclave; Green chemistry; chemoselective reaction;
99 %Spectr.	With [Fe(PNP^Me-iPr)(CO)(H)(Br)]; hydrogen; 1,8-diazabicyclo[5.4.0]undec-7-ene In ethanol at 40℃; for 16h; chemoselective reaction;
	With isopropanol at 120℃; for 24h; chemoselective reaction;	2.3.2. MPV-reduction General procedure: Before reaction, each catalyst was dried at 200 °C to remove residual solvent molecules; catalytic reactions were carried out in 10 ml glass crimp cap vials loaded with 20-30 mg catalyst and a magnetic stirring bar. A solution of the substrate in 3.3 mL isopropanol (IPA) was added; n-tetradecane was added as internal standard. For each catalyst, a substrate to Zr ratio of 7.8 was used as to compare the activity of each catalyst. After introduction of the reaction mixture, the vials were placed in an aluminium heating block (at 120 °C) and stirred. Reaction samples were filtered through a 0.2 μm filter and analysed with gas chromatography (Shimadzu 2010 GC, CP-Sil 8, FID detector). Reaction products were identified using GC-MS. Reactions were performed in duplo, and the results shown are averaged.
	With hydrogen In neat (no solvent) at 110℃; for 12h; chemoselective reaction;
	With isopropanol at 160℃; for 48h; Inert atmosphere; Sealed tube;
	With C₃₉H₅₁AlN₆; isopropanol In toluene at 110℃; for 2h; Inert atmosphere; Schlenk technique;	2.5. Typical procedure employed for the Meerwein-Ponndorf-Verley(MPV) reduction General procedure: To a solution of catalyst (0.4 mmol) in toluene (10 mL) wasadded 2-propanol (8.0 mmol), followed by the addition of the aldehyde(4.0 mmol). The reaction mixture was then refluxed for therequired reaction time under an atmosphere of nitrogen. The reactionwas then cooled to room temperature and the conversionyield was determined by 1H NMR spectroscopic study based onthe integration in the methylene and the CHO region.
94 %Chromat.	With isopropanol at 120℃; for 6h;
70.2 %Spectr.	With C₄₀H₈₆Li₂Mg₂N₄O₂; isopropanol In neat (no solvent) for 4h; Inert atmosphere; Schlenk technique; Reflux;
89 %Spectr.	With [{(C₅H₁₀N)C(NCy)₂}AlMe(μ-OMe)]2; isopropanol In toluene at 110℃; for 8h; Reflux; Inert atmosphere; Schlenk technique;	2.6 General procedure employed for the MPV reaction General procedure: To a solution of catalyst in toluene was added aldehyde or ketone, followed by the addition of 2-propanol. The reaction mixture was then refluxed for the required reaction time under an atmosphere of nitrogen. The reaction was then cooled to room temperature and the conversion yield was determined by 1H NMR spectroscopic study based on the integration in the methylene and the CHO region.
	With hydrogen In isopropanol at 149.84℃; for 0.75h; Autoclave; chemoselective reaction;
	Multi-step reaction with 2 steps 1: 3-bromo-2-(tert-butyl)-4H-5-(2-pyridyl)-1,2,4,3-triazaphospholene / acetonitrile / 16 h / 20 °C / Glovebox 2: potassium hydroxide / dichloromethane / 0.5 h / 20 °C / Glovebox
	With nanocrystalline copper oxide supported on magnesia; cyclohexanol at 180℃; Autoclave; chemoselective reaction;
97 %Chromat.	With Ru(NNS<SUP>Me</SUP>)(PPh<SUB>3</SUB>)Cl₂; potassium-t-butoxide; hydrogen In tetrahydrofuran; isopropanol at 80℃; for 16h; Inert atmosphere;	17a Example 17: hydrogenation of different aldehydes/ketones General procedure: 4 mL glass reaction vials and stirring bars were dried overnight at 1 10°C, closed with PTFE/rubber septa, placed in a multiple reactor inlet suitable for a pressure vessel, and brought under argon atmosphere by three vacuum-argon cycles. With a syringe the reaction vessels were charged with the catalyst as stock solution in /PrOH (1 mL, 0.0005 mol/L, 0.05 mol%), followed by a solution of the compound A, B or C in /PrOH (1 mL, 1 mol/L, 1 mmol). After that a solution of freshly sublimed the base in THF (12.5 μ, 1 mol/L, 0.0125 mmol, 1 .25 mol%) was added with a Hamilton syringe. The reaction mixtures were transferred to an argon-filled pressure vessel, which was im- mediately flushed with three nitrogen and three hydrogen cycles, then pressurized to 30 bar hydrogen, heated to 80°C and stirred for 16h. After that the pressure vessel was cooled down to room temperature and depressurized. The reaction mixtures were filtered over silica and rinsed with ethanol (2 mL). The products are determined based on GC analysis retention time. The given values [%] are related to GC area%. The results are summarized in the following tables 4a, 4b and 4c.
	With Co₃O₄/mesoporous carbon In isopropanol at 120℃; for 48h; Inert atmosphere;	Transfer hvdroqenation of substrates For a typical run, 1 mmol of substrates, 10 mL of 2-propanol, 50 mg of Co3O4 MC and a magnet bar were placed in a glass vial (20 mL). The vial was flushed with argon and then tightly closed. The experiment was performed at 120 °C under magnetic stirring of 800 rpm in a stainless steel heating block. A small volume of sample (-0.1 mL) was periodically withdrawn and analyzed by GC-MS. 1 ,6- hexandiol was chosen as internal standard for FAL and HMF system, while n- decane was used as internal standard for cinnamaldehyde and citral. When increasing reaction temperature to 140 °C and 160 °C, the experiments were carried out in a stainless steel autoclave reactor with volume of 20 mL. The rest of experimental conditions remained the same.
	With C₂₄H₃₇IrN₂O₂P₂; C₄₄H₆₈Ir₂N₂O₄P₄; hydrogen In tetrahydrofuran at 21.84℃; for 5h; chemoselective reaction;
	With Ru(H)<SUB>2</SUB>(CO)(triphos); hydrogen In neat (no solvent) at 100℃; for 16h; chemoselective reaction;
90 %Chromat.	With isopropanol at 140℃; for 5h;
	With isopropanol at 160℃; for 6h; Autoclave; Inert atmosphere; Sealed tube;
76 %Spectr.	With C₂₀H₃₉BrFeN₃OP₂; water monomer; anhydrous sodium formate at 80℃; for 1h; chemoselective reaction;	General procedure for the catalytic transferhydrogenation of aldehydes General procedure: In a typical experiment, a vial containing a magnetic stirringbar was charged with catalyst 1 and the substrate(2.0 mmol) inside a glovebox. The vial was sealed with aseptum screw cap, taken out from the glovebox and asolution of sodium formate in degassed water (1.0 cm3,2.5 M) was added through the septum. The reaction mixturewas stirred at 80 C for the specified time after whichit was quickly cooled to room temperature and the reactionwas quenched by exposure to air. A sample was taken fromthe organic phase, diluted in CDCl3, and analyzed by NMRspectroscopy. For the isolation of the reaction products,1 cm3 diethyl ether was added and the phases were separated.The aqueous phase was washed with diethyl etherand the combined extracts were filtered over a short plug ofsilica to remove the catalyst. The solution was dried overMgSO4 and the solvent removed under reduced pressure.
	With bis(tricyclohexylphosphine)-3-phenyl-1H-inden-1-ylidene ruthenium(II)dichloride; anhydrous sodium formate; n-dodecyltrimethylammonium chloride In water monomer at 85℃; Schlenk technique;
	With activated carbon supported CoOx-shell/Co-core structured nanoparticle calcined at 500°C In isopropanol at 120℃; for 13h; Inert atmosphere;
	With potassium-t-butoxide; C₅₅H₄₄ClFeN₂OP₂⁽¹⁺⁾*BF₄^(1-); isopropanol at 25℃; for 0.05h; Inert atmosphere; chemoselective reaction;
91 %Spectr.	With methanol; borane-ammonia complex at 20℃; for 0.5h; Inert atmosphere; Schlenk technique; Glovebox; Green chemistry;
	With naphthalene; MOF-808 In isopropanol at 82℃; for 1h;	Catalytic test and product analysis General procedure: The catalytic activity of Zr-MOFs in the transfer hydrogenation of flavoring compounds was evaluated at moderate reaction conditions. Before use, Zr and Hf-MOFs were dried in an oven at 100°C for 12 h. In a typical procedure, a known amount of dried catalyst (9.5 mol% on the metal basis) of the dried catalyst, 2.6 mmol of carbonyl substrate, 0.05 g of naphthalene as an internal slandered, and 20 ml of isopropanol were added into a two-neck round bottom flask of 50 mL capacity. The reaction mixture in RBF equipped with a rubber septum and reflux condenser was heated at the boiling point of isopropanol for the desired time. The catalyst was separated by centrifugation and washed thoroughly with methanol and dried at 100°C. The filtrate was subjected to quantitative analysis using gas chromatography (GC, FID detector, and DB-624 column). Substrate conversion and the yield of products were determined using a single point internal standard calibration method.
	With Zr(OH)₄/CoFe₂O₄ core-shell magnetic nanoparticles; alcohol at 160℃; for 4h; Autoclave;
	With hydrogen; C₂₇H₄₁IrN₃P In 2-methyltetrahydrofuran at 25℃; for 24h; Inert atmosphere; Glovebox; chemoselective reaction;
	With Hf-MOF-808 catalyst In isopropanol at 82℃; for 2h;	Table 7 below shows an experiment for hydrogenation of the M-MOF-808 catalyst when the substrate is α,β-unsaturated carbonyl. The reaction condition of Table 7 below was the same as that of Table 6, except that the reaction temperature was 82° C. In the table below, the type of the central metal of MOF-808 was set to Zr or Hf.

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[51]He, Sina; Shao, Zheng-Jiang; Shu, Yijin; Shi, Zhangping; Cao, Xiao-Ming; Gao, Qingsheng; Hu, Peijun; Tang, Yi [Chemistry - A European Journal, 2016, vol. 22, # 16, p. 5698 - 5704]
[52]Gorgas, Nikolaus; Stöger, Berthold; Veiros, Luis F.; Kirchner, Karl [ACS Catalysis, 2016, vol. 6, # 4, p. 2664 - 2672]
[53]Plessers, Eva; De Vos, Dirk E.; Roeffaers, Maarten B.J. [Journal of Catalysis, 2016, vol. 340, p. 136 - 143]
[54]Ye, Tian-Nan; Li, Jiang; Kitano, Masaaki; Sasase, Masato; Hosono, Hideo [Chemical Science, 2016, vol. 7, # 9, p. 5969 - 5975]
[55]Wang, Guang -Hui; Deng, Xiaohui; Gu, Dong; Chen, Kun; Tüysüz, Harun; Spliethoff, Bernd; Bongard, Hans -Josef; Weidenthaler, Claudia; Schmidt, Wolfgang; Schüth, Ferdi [Angewandte Chemie - International Edition, 2016, vol. 55, # 37, p. 11101 - 11105][Angew. Chem., 2016, vol. 128, p. 11267 - 11271,5]
[56]Han, Hong-Fei; Zhang, Shao-Feng; Guo, Zhi-Qiang; Tong, Hong-Bo; Wei, Xue-Hong [Polyhedron, 2015, vol. 99, p. 71 - 76]
[57]Li, Hu; Fang, Zhen; He, Jian; Yang, Song [ChemSusChem, 2017, vol. 10, # 4, p. 681 - 686]
[58]Hua, Yupeng; Guo, Zhiqiang; Han, Hongfei; Wei, Xuehong [Organometallics, 2017, vol. 36, # 4, p. 877 - 883]
[59]Han, Hongfei; Guo, Zhiqiang; Zhang, Shaofeng; Hua, Yupeng; Wei, Xuehong [Polyhedron, 2017, vol. 126, p. 214 - 219]
[60]Putro, Wahyu S.; Kojima, Takashi; Hara, Takayoshi; Ichikuni, Nobuyuki; Shimazu, Shogo [Catalysis science and technology, 2017, vol. 7, # 16, p. 3637 - 3646]
[61]Tien, Chieh-Hung; Adams, Matt R.; Ferguson, Michael J.; Johnson, Erin R.; Speed, Alexander W. H. [Organic Letters, 2017, vol. 19, # 20, p. 5565 - 5568]
[62]Siddqui, Nazia; Sarkar, Bipul; Pendem, Chandrashekar; Khatun, Rubina; Sivakumar Konthala; Sasaki, Takehiko; Bordoloi, Ankur; Bal, Rajaram [Catalysis science and technology, 2017, vol. 7, # 13, p. 2828 - 2837]
[63]Current Patent Assignee: KONINKLIJKE DSM N.V. - WO2017/194662, 2017, A1 Location in patent: Page/Page column 46; 47
[64]Current Patent Assignee: EVONIK INDUSTRIES AG - WO2017/207555, 2017, A1 Location in patent: Page/Page column 12; 14
[65]Cano, Israel; Martínez-Prieto, Luis M.; Vendier, Laure; Van Leeuwen, Piet W. N. M. [Catalysis science and technology, 2018, vol. 8, # 1, p. 221 - 228]
[66]Christie, Francesca; Zanotti-Gerosa, Antonio; Grainger, Damian [ChemCatChem, 2018, vol. 10, # 5, p. 1012 - 1018]
[67]Li, Hu; He, Jian; Riisager, Anders; Saravanamurugan, Shunmugavel; Song, Baoan; Yang, Song [ACS Catalysis, 2016, vol. 6, # 11, p. 7722 - 7727]
[68]Zhou, Shenghui; Chen, Guixian; Feng, Xiao; Wang, Ming; Song, Tao; Liu, Detao; Lu, Fachuang; Qi, Haisong [Green Chemistry, 2018, vol. 20, # 15, p. 3593 - 3603]
[69]Gorgas, Nikolaus; Ilic, Aleksandra; Kirchner, Karl [Monatshefte fur Chemie, 2019, vol. 150, # 1, p. 121 - 126]
[70]Öztürk, Bengi Özgün; Öztürk, Sinem [Molecular catalysis, 2020, vol. 480]
[71]Gong, Wanbing; Han, Miaomiao; Chen, Chun; Lin, Yue; Wang, Guozhong; Zhang, Haimin; Zhao, Huijun [ChemCatChem, 2020, vol. 12, # 4, p. 1019 - 1024]
[72]Huo, Shangfei; Wang, Qingwei; Zuo, Weiwei [Dalton Transactions, 2020, vol. 49, # 23, p. 7959 - 7967]
[73]Meier, Sebastian; Riisager, Anders; Yang, Song; Zhao, Wenfeng [Green Chemistry, 2020, vol. 22, # 18, p. 5972 - 5977]
[74]Valekar, Anil H.; Oh, Kyung-Ryul; Hwang, Young Kyu [Bulletin of the Korean Chemical Society, 2021, vol. 42, # 3, p. 467 - 470]
[75]Hou, Pan; Ma, Mingwei; Zhang, Peng; Cao, Jingjie; Liu, Hui; Xu, Xingliang; Yue, Huijuan; Tian, Ge; Feng, Shouhua [New Journal of Chemistry, 2021, vol. 45, # 5, p. 2715 - 2722]
[76]Álvarez, Eleuterio; Hernández-Juárez, Martín; López-Serrano, Joaquín; Paneque, Margarita; Rendón, Nuria; Sánchez, Práxedes; Suárez, Andrés [Organometallics, 2021, vol. 40, # 9, p. 1314 - 1327]
[77]Current Patent Assignee: KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY - US2022/62880, 2022, A1 Location in patent: Paragraph 0202; 0210

23
[ 5392-40-5 ]
[ 5146-66-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With bismuth(lll) trifluoromethanesulfonate; acetylhydroxamic acid In acetonitrile for 14h; Reflux;	13 A typical method for preparation of nitrile from aldehyde using AHA: General procedure: 4-Isopropylbenzaldehyde 1a (0.50 g, 3.37 mmol), acetohydroxamic acid (0.30 g, 4.05 mmol), acetonitrile (5 ml), and Bi(OTf)3 (0.11 g, 0.17 mmol) were taken into a 25 ml round-bottomed flask fitted with a condenser and calcium chloride guard tube. The mixture was refluxed for 14 h and after completion of the reaction (GC, 10% SE-30 on Chromosorb, 10' × 1/8 column), the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. The crude product obtained was purified by normal column chromatography(silica gel 100-200 mesh, ethyl acetate/hexane = 1:20) to obtain 4-isopropylbenzonitrile 3a (0.47 g, 97%).
87%	With ammonium hydroxide; dihydrogen peroxide In isopropyl alcohol at 17 - 30℃;
87%	With O-(4-(trifluoromethyl)benzoyl)hydroxylamine; trifluoroacetic acid In 1,2-dimethoxyethane at 80℃; for 14h;

80%	With 1-methyl-pyrrolidin-2-one; hydroxylamine hydrochloride at 100℃; for 0.25h; microwave irradiation;
80%	With hydroxylamine hydrochloride In 1-methyl-pyrrolidin-2-one at 100℃; for 0.25h;

Reference： [1]Location in patent: experimental part Sridhar, Madabhushi; Reddy, Mallu Kishore Kumar; Sairam, Vangipuram Venkata; Raveendra, Jillella; Godala, Kondal Reddy; Narsaiah, Chinthala; Ramanaiah, Beeram China; Reddy, Cirandur Suresh [Tetrahedron Letters, 2012, vol. 53, # 27, p. 3421 - 3424]
[2]Erman; Snow; Williams [Tetrahedron Letters, 2000, vol. 41, # 35, p. 6749 - 6752]
[3]An, Xiao-De; Yu, Shouyun [Organic Letters, 2015, vol. 17, # 20, p. 5064 - 5067]
[4]Chakraborti, Asit K.; Kaur, Gurmeet [Tetrahedron, 1999, vol. 55, # 46, p. 13265 - 13268]
[5]Chakraborti; Kaur; Roy [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2001, vol. 40, # 10, p. 1000 - 1006]

24
[ 5392-40-5 ]
[ 106-22-9 ]
[ 624-15-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 88% 2: 10%	With hydrogen; silver In tetrahydrofuran at 150℃; for 72h;	13 (Selective Hydrogenation of Aldehyde Group) Catalysts E to G for Examples obtained in Production Example 4 were each 0.008 mmol in terms of metal equivalent of silver, incidentally, as a substrate having a carbon-carbon double bond and an aldehyde group, 0.25 mmol of citral (a mixture of cis-trans isomers geranial and neral 2: 1), solvent 5 ml of tetrahydrofuran (THF), hydrogen pressure 1.5 MPa, Hydrogenation reduction treatment was carried out at a reaction temperature of 150 ° C reaction time is In each of Examples 11 to 13, it was 72 hours, by using gas chromatograph, yield, selectivity was measured. The results are shown in Table 5.
1: 54% 2: 46%	With sodium cyanoborohydride at 20℃; for 0.05h;
	With (triphenylphosphine)copper(I) hydride hexamer; hydrogen; Dimethyl(phenyl)phosphine In <i>tert</i>-butyl alcohol; benzene at 20℃; for 15h; Title compound not separated from byproducts;

	With hydrogen In isopropyl alcohol at 119.84℃;
	With [Ru(H)(CO)(CH₃CN)(TPPMS)3][BF₄]; hydrogen In water; toluene at 100℃; for 24h; chemoselective reaction;
	With hydrogen In tetrahydrofuran at 150℃; for 3h; Autoclave; chemoselective reaction;

Reference： [1]Current Patent Assignee: BASF SE; N.E. Chemcat (in: BASF and Sumitomo Metal Mining); SUMITOMO METAL MINING CO., LTD.; OSAKA UNIVERSITY - JP6018928, 2016, B2 Location in patent: Paragraph 0085; 0087-0088
[2]Zeynizadeh, Behzad; Kouhkan, Mehri [Journal of the Chinese Chemical Society, 2018, vol. 65, # 12, p. 1521 - 1528]
[3]Chen, Jian-Xin; Daeuble, John F.; Brestensky, Donna M.; Stryker, Jeffrey M. [Tetrahedron, 2000, vol. 56, # 15, p. 2153 - 2166]
[4]Trasarti; Marchi; Apesteguia [Journal of Catalysis, 2007, vol. 247, # 2, p. 155 - 165]
[5]Location in patent: scheme or table Melean, Luis G.; Rodriguez, Mariandry; Gonzalez, Angel; Gonzalez, Beatriz; Rosales, Merlin; Baricelli, Pablo J. [Catalysis Letters, 2011, vol. 141, # 5, p. 709 - 716]
[6]Mitsudome, Takato; Matoba, Motoshi; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi [Chemistry - A European Journal, 2013, vol. 19, # 17, p. 5255 - 5258]

25
[ 64-17-5 ]
[ 4540-33-4 ]
[ 123-73-9 ]
[ 5392-40-5 ]
silica gel [ No CAS ]
[ 6790-23-4 ]

Reference： [1]Journal of the Chemical Society,1939,p. 1552

26
[ 4540-33-4 ]
[ 123-73-9 ]
[ 5392-40-5 ]
silica gel [ No CAS ]
acetate ethanol [ No CAS ]
[ 6790-23-4 ]

Reference： [1]Journal of the Chemical Society,1939,p. 1552

27
[ 624-15-7 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	With triphenyl(2,6-dimethylphenyl)bismuthonium tetrafluoroborate; N,N,N',N'-tetramethylguanidine In dichloromethane at 20℃; for 0.5h;
99%	Stage #1: geraniol With oxalyl dichloride; 3-methyl-1-[6-(methanesulfinyl)hexan-1-yl]-1H-imidazolium p-toluenesulfonate In dichloromethane at -70℃; for 0.5h; Stage #2: With triethylamine In dichloromethane at -70 - 20℃; for 5.5h;	4.7. General procedure for the Swern oxidation using ion-supported methyl sulfoxide A-1 or B-1 General procedure: Oxalyl chloride (0.34 mL) was added dropwise to a solution of ion-supported methyl sulfoxide A-1 (C6) (1.60 g, 4.0 mmol) in CH2Cl2 (6 mL) at -70 °C and the mixture was stirred for 30 min at the same temperature. Then, a solution of alcohol (2.0 mmol) in CH2Cl2 (3 mL) was added dropwise at -70 °C and the obtained mixture was stirred for 30 min. Triethylamine (1.66 mL, 12 mmol) was added dropwise at -70 °C and the mixture was stirred for 1 h at the same temperature. The resulting mixture was warmed to -60 °C and stirred for 1.5 h at the same temperature. Then, the mixture was warmed to -50 °C and stirred for 1 h at the same temperature. Finally, the mixture was warmed to room temperature and stirred for 2 h at the same temperature. The reaction mixture was quenched with water (10 mL), neutralized (pH=6-7) with aq 1 M HCl solution, and extracted with diethyl ether (40 mL×2). The organic layer was washed with water (10 mL), dried over Na2SO4, and filtered. After removal of the solvent, aldehyde or ketone was obtained. The purity was estimated by 1H NMR measurements.
97%	With hexaammonium heptamolybdate tetrahydrate; dihydrogen peroxide In water; methyl cyclohexane at 50℃; for 2h; Ionic liquid; Green chemistry;

97%	With di-tert-butyl-diazodicarboxylate; bathophenanthroline; oxygen; caesium carbonate; copper(l) chloride In toluene at 20℃; for 1h;
96%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper (II) dichloro(N,N,N',N'-tetramethylethylenediamine) In acetonitrile at 25℃; for 2h; chemoselective reaction;	2.3. Typical procedure for the Aerobic oxidation of alcohols using CuCl2/TMEDA/TEMPO2.3. Typical procedure for the Aerobic oxidation of alcohols using CuCl2/TMEDA/TEMPO General procedure: Method A: A 20-mm culture tube with capacity to 15 mL andequipped with a magnetic stirrer was loaded with MeCN (2 mL), CuCl2(3.0 × 10 3 mmol, 0.4 mg) and TMEDA (3.0 × 10 3 mmol, 0.45 μL). Tothis slightly greenish blue solution, alcohol 1b (3 mmol, 320 μL) andTEMPO (3.0 × 10-2 mmol, 4.7 mg, 1.0 mol%) were added at roomtemperature (25 C). The opened flask reaction was stirred at 25 Cunder bubbled air (see apparatus on SI) where within 2 h, the totalconversion of 1b was confirmed by GC/FID. Then, the crude was filteredoff in a minimal amount of silica gel (ca. 10 mg) furnishing 353 mg ofthe pure p-tolualdehyde (2b) in 98 % of yield.Method B: Into a 20-mm culture tube with capacity to 15 mL andcharged with a solution of the alcohol 1b (3 mmol, 320 μL) in MeCN(2 mL), were sequentially added TEMPO (300 μL of a 0.1 M solution inacetonitrile, 1.0 mol%) and CuCl2/TMEDA (15 μL of a 0.1 M solution inacetonitrile, 0.1 mol%) via syringe in one portion. The reaction wasstirred at 25 C under bubbled atmospheric air in an opened flask andmonitored by GC/FID, where within 2 h, the total conversion of 1b wasconfirmed. Finally, the crude material was filtered off in a minimalamount of silica gel (ca. 10 mg) furnishing 2b in 98 % of yield. Thereactions using either Method A or Method B were able to produce 2bwith the same yield. A detailed solvent effect study and a scalable procedurecan be found in S.I. Moreover, the values of TON/TOF/E-factorare given in the Table 2.
94%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 6,8-di(tert-butyl)-3-[2-(1H-imidazol-4-yl)ethyl]-3,4-dihydro-2H-1,3-benzoxazine; oxygen; copper(I) triflate In dichloromethane at 25℃; for 6h;	Typical procedure for the oxidation of primary alcohols. General procedure: A 5-mL two-necked, round-bottom flask equipped with a magnetic stirrer and an oxygen balloon was charged in succession with 0.0106 g(0.05 mmol) of Cu(OTf), 0.0078 g (0.05 mmol) of TEMPO, 0.0136 g (0.04 mmol) of benzoxazine ligand L, and 1 mL of methylene chloride. The corresponding alcohol, 1 mmol, was then added at 25°C under stirring, and oxygen from the balloon was introduced through a three-way valve. The progress of the reaction was monitored by GLC using a suitable column.
93%	With Dess-Martin periodane In dichloromethane at 23℃; for 2h; Inert atmosphere;
92%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen In dibutyl ether at 65℃; for 15h;
91%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; dimethyl 3-methyl-9-oxo-7-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)-2,4-di(pyridin-2-yl)-3,7-diazabicyclo-[3.3.1]nonane-1,5-dicarboxylate; copper(I) bromide In water at 20℃; for 9h; Green chemistry;
90%	With manganese(IV) oxide In pentane
89%	With rhodium(III) chloride hydrate; oxygen; C₂₅H₄₄NO₂PS In 1,2-dichloro-ethane at 60℃; for 54h;
88%	With titanium(IV) oxide; oxygen at 29.84℃; for 6h; Sealed tube; Irradiation;
88%	With oxygen In 1,3,5-trimethyl-benzene at 60℃; for 4h;	8.16 Example 8 Application of this method in the reaction of other alcohols to aldehydes and ketones The typical reaction steps are as follows:1 mmol of the starting alcohol of the reactant column shown in Table 2,OH - Ni3In-LDH 14 mg,Mesitylene 5mL were added to the reactor,Into the oxygen,Atmospheric reaction,The reaction was stirred at 60 for a certain period of time.The solid catalyst was removed by filtration,Using gas chromatography internal standard method (chlorobenzene as internal standard) to analyze the content of liquid products,Calculate yield.
87%	With 1-hydroxy-1.oxo-1H-1λ5-benzo[d][1,2]iodoxol-3-one pyridinium salt In N,N-dimethyl-formamide at 24 - 28℃; for 2.5h;
82%	With 3,4,5,6-tetramethyl-2-iodoxybenzoic acid In dichloromethane at 25 - 30℃; for 0.2h;
81%	With 2-(2-iodylphenyl)-2-methylpropanoic acid In dichloromethane at 25 - 30℃;
80%	With copper(l) iodide; TEMPOL; N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine In acetonitrile at 20℃; for 2h; Inert atmosphere;	2.3. Typical procedure for oxidation of alcohols General procedure: The copper salt and the ligand (each 0.025 mmol) were added to CH3CN (1 mL) in an Ar atmosphere and stirred for 30min. Then 4-OH-TEMPO (0.025 mmol) and substrate (0.5mmol) were added successively, and the mixture was stirred at room temperature. The reaction progress was checked using thin-layer chromatography. The reaction conversion and yield were obtained from GC measurements using nitrobenzene or nonane as an internal standard, or by column chromatography.
78%	With cyclohexenone; C₄₄H₆₆O₈P₄Pd₂ In water; toluene at 105℃; for 16h; Inert atmosphere; chemoselective reaction;
76%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene In dichloromethane at 35℃; for 0.075h; Flow reactor; chemoselective reaction;
75%	With manganese(IV) oxide In dichloromethane at 20℃;
66%	With tert.-butylhydroperoxide; oxygen In toluene at 80℃; for 16h;
61%	With oxygen In toluene at 110℃; for 24h;
36%	With manganese(IV) oxide; oxygen In toluene at 110℃; Green chemistry;	3.1. Oxidation of benzhydrol 1a in the presence of substoichiometric amounts of activated MnO2: preparation of benzophenone 2 (Table 1, entry 6). General procedure General procedure: Benzhydrol 1 (0.3831 g, 2.08 mmol) was dissolved in toluene (15 mL) and activated MnO2 (purchased from Aldrich, 0.106 g, 1.92 mmol, 50 mg/mmol) was added to the solution. The reaction mixture was heated at 110 °C under oxygen atmosphere for 4 h. Supernatant of the reaction mixture was scooped by pipet. Additional toluene (5 mL) was added to solid residue and washed the solid then the supernatant was scooped by pipet. This washing procedure was repeated for four times. All of toluene solution was combined and concentrated. Crude product was purified by flash chromatography (silica gel/hexane-EtOAc 3:1) to give 2 in 98% yield (0.373 g, 2.05 mmol). MnO2 residue was examined for the recycling use of the oxidant (Scheme 4, see below).
17%	With oxygen; 2,3-dicyano-5,6-dichloro-p-benzoquinone; sodium nitrite In dichloromethane; acetic acid at 20℃; for 20h;
82 % Chromat.	With benzyldimethyltelluronium dichromate In acetonitrile for 10h; Heating;
	With 2,2,6,6-tetramethyl-piperidine-N-oxyl; deposited on ITO-coated glass (working electrode) In water; acetonitrile for 100h; Electrochemical reaction; 1.4 V vs. Ag/AgCl (reference electrode), Pt wire (counter electrode);
	With Pd-SiO₂-Al₂O₃-H₂; oxygen In trifluorotoluene at 79.84℃; for 24h;
16 %Chromat.	With C₇₇H₆₀Cl₂N₄O₄PRu₂; 4-methylmorpholine N-oxide In dichloromethane for 12h; Reflux;
	With [Cu₂(5-bpyT)2Br₄](CH₃CN)2; potassium <i>tert</i>-butylate; oxygen In water; acetonitrile at 50℃; for 10h;
59 %Chromat.	With NiZn-Pd(0.02) nanocomposite catalyst In α,α,α-trifluorotoluene at 79.84℃; for 10h;
95 %Chromat.	With potassium <i>tert</i>-butylate; oxygen; copper dichloride; 4-methyl-2-((pyridin-2-ylmethylene)amino)phenol In water; acetonitrile at 20℃; for 8h;
	With potassium phosphate; recombinant rat brain aldo-keto reductase R₁B₁₀; nicotinamide adenine dinucleotide phosphate In methanol Enzymatic reaction;
91 %Chromat.	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; potassium <i>tert</i>-butylate; copper(ll) bromide In water; acetonitrile for 4h; air;
60 %Chromat.	With 6-methyl-2-pyridinecarboxylic acid; dihydrogen peroxide; iron(II) acetate In water; acetonitrile at 25℃; for 0.25h; chemoselective reaction;
	With air, Pd⁽⁰⁾[2(L^py)+2(HL^py(OTs)], L^py=MeO(CH₂CH₂O)₁₁₆CH₂CH_2-O-CH₂-4-Pyridyl In water at 60℃; for 2h; Autoclave; chemoselective reaction;
	With 1-methyl-1H-imidazole; [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [(2,2’-bipyridine)Cu(II)(OH)]₂(trifluoromethanesulfonate)₂; oxygen In acetonitrile at 20℃; Flow reactor;
	With oxygen In toluene at 90℃; for 14h;	2.3.1 Aerobic alcohol oxidation General procedure: The oxidation reaction of alcohol was performed according to the following sequence: PdOSNP (40mg, Pd=3.3mol% of substrate) with toluene (2mL) and alcohol (0.2mmol) was charged in the glass tube reactor. The mixture was stirred at 1000rpm using magnetic stirrer bar under atmospheric pressure of molecular oxygen at 90°C. The conversion and yield were obtained by taking the sample from a mixture at regular intervals and analyzing them with gas chromatography (GC, Younglin GC-6500) and at the end by GC-mass spectroscopy (GC-MS, JEOL GCMS-BU20) to compare with the standard samples. GC analyses were carried out using a flame ionization detector (FID) equipped with a DB-WAX capillary column. GC-MS were recorded at an ionization voltage of 70eV equipped with a DB-WAX capillary column (internal diameter=0.25mm, length=30m).
	With 1-methyl-1H-imidazole; tetrakis(acetonitrile)copper(I) trifluoromethanesulfonate; C₃₄H₄₀N₇O₄; oxygen In acetonitrile at 20℃; for 3h;
	With oxygen at 25℃; for 16h;
> 99 %Chromat.	With 1-methyl-1H-imidazole; copper(l) iodide; C₂₀H₂₅N₄O₂ In acetonitrile at 25℃; for 3.5h;
	With C₃₄H₃₇N₄O₆Ru₂⁽¹⁺⁾*Cl^(1-); potassium hydroxide In toluene at 70℃; for 24h; Schlenk technique; Inert atmosphere;
	With oxygen In hexane at 19.84℃; for 10h; Green chemistry;
	With oxygen In toluene at 80℃; for 3h; chemoselective reaction;
99 %Chromat.	With sodium hypochlorite; (Et₄N)₂[Fe^III(Cl)(biuret-TAML)] In aq. phosphate buffer; acetonitrile at 20℃; for 4h; chemoselective reaction;	3.1.1. Procedure for reactions at pH 7 General procedure: To a reaction vial containing a magnetic stir bar, unsubstituted Fe-bTAML catalyst, 1 (0.2-0.8mM, 0.5-2mol %), substrate (40mM, 0.04mmol, 1.0equiv.) and pH 7 phosphate buffer (100mM, 300μL aqueous solution) in 700μL acetonitrile were added. An aqueous solution of sodium hypochlorite (2equiv.) was added via syringe pump with continuous stirring over a period of 2-6h at room temperature. The reaction was monitored by TLC and GC. After completion of the reaction, the solvent (CH3CN) was removed under reduced pressure. Saturated aqueous solution of sodium bicarbonate was added to the residual portion and extracted with dichloromethane (2times). The organic part was dried with anhydrous sodium sulphate, analysed by GC-MS to estimate the product GC yield.
	With 2,2'-azinobis(3-ethylbenzthiazolinesulfonate); horse-radish peroxidase; choline oxidase from Arthrobacter cholorphenolicus, mutant S₁₀₁A/D₂₅₀G/F₂₅₃R/V₃₅₅T/F₃₅₇R/M₃₅₉R In aq. phosphate buffer at 30℃; for 24h; Enzymatic reaction;
	With 2,2,6,6-tetramethyl-piperidine-N-oxyl; 1-methyl-3-(propyl-3-sulfonic acid)imidazole chloride salt; oxygen; sodium nitrite In water; acetonitrile at 45℃; for 5h;	General catalytic procedures General procedure: TEMPO (5 mol%), NaNO2 (8 mol%), and the IL (20 mol%)were added successively into a 5-mL round-bottom flaskthat was purged with oxygen five times. Subsequently, benzylalcohol (2 mmol) and CH3CN/H2O (10:1; 2.2 mL) wereadded in turn via a syringe. Then, the mixture was stirred at45 °C in an oil bath under atmospheric oxygen. When thebenzyl alcohol had been consumed (monitored by TLC),o-phenylenediamine (2.2 mmol) was added. The mixturewas further stirred at 55 °C under atmospheric oxygen untilcompletion of the reaction (monitored by TLC). The reactionmixture was extracted with dichloromethane(4 × 15 mL), and the combined extract was evaporatedunder vacuum. The crude product was purified by columnchromatography on silica gel to afford product 3
	With dihydrogen peroxide; C₁₁H₁₈Br₂FeN₄⁽¹⁺⁾*Br^(1-) In acetonitrile at 30℃; for 24h;

Reference： [1]Location in patent: experimental part Matano, Yoshihiro; Suzuki, Takeshi; Iwata, Takaharu; Shinokura, Tomonori; Imahori, Hiroshi [Bulletin of the Chemical Society of Japan, 2008, vol. 81, # 12, p. 1621 - 1628]
[2]Location in patent: experimental part Tsuchiya, Daisuke; Tabata, Masayuki; Moriyama, Katsuhiko; Togo, Hideo [Tetrahedron, 2012, vol. 68, # 34, p. 6849 - 6855]
[3]Hu, Yu-Lin; Lu, Ming; Ge, Xiu-Tao [Journal of the Iranian Chemical Society, 2013, vol. 10, # 3, p. 453 - 460]
[4]Nishii, Takeshi; Ouchi, Tomomi; Matsuda, Aya; Matsubara, Yuka; Haraguchi, Yuuko; Kawano, Tomomi; Kaku, Hiroto; Horikawa, Mitsuyo; Tsunoda, Tetsuto [Tetrahedron Letters, 2012, vol. 53, # 44, p. 5880 - 5882,3]
[5]Alves, Otávio A. L.; Chagas, Rafael C. R.; Princival, Jefferson L.; Ribeiro, RogérioT.; Silva, Emmanuel D.; Villar, José A. F. P. [Applied Catalysis A: General, 2021, vol. 623]
[6]Zhang; Huang; Lü; Cao; Zhao [Russian Journal of General Chemistry, 2015, vol. 85, # 8, p. 1965 - 1972][Zh. Obshch. Khim.]
[7]Huynh, Khoi Q.; Seizert, Curtis A.; Ozumerzifon, Tarik J.; Allegretti, Paul A.; Ferreira, Eric M. [Organic Letters, 2017, vol. 19, # 1, p. 294 - 297]
[8]Location in patent: experimental part Chrobok, Anna; Baj, Stefan; Pudło, Wojciech; Jarzȩbski, Andrzej [Applied Catalysis A: General, 2010, vol. 389, # 1-2, p. 179 - 185]
[9]Ang, Wei Jie; Chng, Yong Sheng; Lam, Yulin [RSC Advances, 2015, vol. 5, # 99, p. 81415 - 81428]
[10]Valla, Alain; Cartier, Dominique; Laurent, Alain; Valla, Benoist; Labia, Roger; Potier, Pierre [Synthetic Communications, 2003, vol. 33, # 7, p. 1195 - 1201]
[11]Hu, Rong-Bin; Lam, Ying-Pong; Ng, Wing-Hin; Wong, Chun-Yuen; Yeung, Ying-Yeung [ACS Catalysis, 2021, vol. 11, # 6, p. 3498 - 3506]
[12]Vadakkekara, Raji; Biswas, Abul Kalam; Sahoo, Tapan; Pal, Provas; Ganguly, Bishwajit; Ghosh, Subhash Chandra; Panda, Asit Baran [Chemistry - An Asian Journal, 2016, vol. 11, # 21, p. 3084 - 3089]
[13]Current Patent Assignee: CHANGZHOU UNIVERSITY - CN107176898, 2017, A Location in patent: Paragraph 0036; 0037; 0038; 0039; 0041
[14]Location in patent: experimental part Kumanyaev, Ivan M.; Lapitskaya, Margarita A.; Vasiljeva, Ljudmila L.; Pivnitsky, Kasimir K. [Mendeleev Communications, 2012, vol. 22, # 3, p. 129 - 131]
[15]Location in patent: experimental part Moorthy, Jarugu Narasimha; Senapati, Kalyan; Parida, Keshaba Nanda; Jhulki, Samik; Sooraj, Kunnikuruvan; Nair, Nisanth N. [Journal of Organic Chemistry, 2011, vol. 76, # 23, p. 9593 - 9601]
[16]Moorthy, Jarugu Narasimha; Senapati, Kalyan; Parida, Keshaba Nanda [Journal of Organic Chemistry, 2010, vol. 75, # 24, p. 8416 - 8421]
[17]Zhang, Shufang; Miao, Chengxia; Xu, Daqian; Sun, Wei; Xia, Chungu [Chinese Journal of Catalysis, 2014, vol. 35, # 11, p. 1864 - 1873]
[18]Vasseur, Alexandre; Membrat, Romain; Gatineau, David; Tenaglia, Alphonse; Nuel, Didier; Giordano, Laurent [ChemCatChem, 2017, vol. 9, # 5, p. 728 - 732]
[19]Ambreen, Nida; Kumar, Ravi; Wirth, Thomas [Beilstein Journal of Organic Chemistry, 2013, vol. 9, p. 1437 - 1442]
[20]Location in patent: scheme or table Sugiyama, Sakae; Fuse, Shinichiro; Takahashi, Takashi [Tetrahedron, 2011, vol. 67, # 35, p. 6654 - 6658]
[21]Giorgi, Pascal D.; Miedziak, Peter J.; Edwards, Jennifer K.; Hutchings, Graham J.; Antoniotti, Sylvain [ChemCatChem, 2017, vol. 9, # 1, p. 70 - 75]
[22]Kamimura, Akio; Nozaki, Yuichiro; Nishiyama, Mai; Nakayama, Masaharu [RSC Advances, 2013, vol. 3, # 2, p. 468 - 472]
[23]Kamimura, Akio; Komatsu, Hiroyuki; Moriyama, Takaaki; Nozaki, Yuichiro [Tetrahedron, 2013, vol. 69, # 29, p. 5968 - 5972]
[24]Location in patent: experimental part Wang, Lianyue; Li, Jun; Yang, Hua; Lv, Ying; Gao, Shuang [Journal of Organic Chemistry, 2012, vol. 77, # 1, p. 790 - 794]
[25]Song, Yang-Heon [Synthetic Communications, 2006, vol. 36, # 5, p. 631 - 635]
[26]Palmisano, Giovanni; Ciriminna, Rosaria; Pagliaro, Mario [Advanced Synthesis and Catalysis, 2006, vol. 348, # 15, p. 2033 - 2037]
[27]Location in patent: scheme or table Chen, Jing; Zhang, Qinghong; Wang, Ye; Wan, Huilin [Advanced Synthesis and Catalysis, 2008, vol. 350, # 3, p. 453 - 464]
[28]Location in patent: experimental part Venkatachalam; Raja; Pandiarajan; Ramesh [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2008, vol. 71, # 3, p. 884 - 891]
[29]Location in patent: scheme or table Lu, Zhengliang; Ladrak, Tim; Roubeau, Olivier; Van Der Toorn, John; Teat, Simon J.; Massera, Chiara; Gamez, Patrick; Reedijk, Jan [Dalton Transactions, 2009, # 18, p. 3559 - 3570]
[30]Location in patent: scheme or table Hara, Takayoshi; Ishikawa, Masakazu; Sawada, Junya; Ichikuni, Nobuyuki; Shimazu, Shogo [Green Chemistry, 2009, vol. 11, # 12, p. 2034 - 2040]
[31]Location in patent: experimental part Uma Maheswari, Palanisamy; Hartl, František; Quesada, Manuel; Buda, Francesco; Lutz, Martin; Spek, Anthony L.; Gamez, Patrick; Reedijk, Jan [Inorganica Chimica Acta, 2011, vol. 374, # 1, p. 406 - 414]
[32]Location in patent: experimental part Endo, Satoshi; Matsunaga, Toshiyuki; Kuragano, Tsukasa; Ohno, Satoshi; Kitade, Yukio; Tajima, Kazuo; El-Kabbani, Ossama; Hara, Akira [Archives of Biochemistry and Biophysics, 2010, vol. 503, # 2, p. 230 - 237]
[33]Location in patent: experimental part Hu, Zhenzhong; Kerton, Francesca M. [Applied Catalysis A: General, 2012, vol. 413-414, p. 332 - 339]
[34]Tanaka, Shinji; Kon, Yoshihiro; Nakashima, Takuya; Sato, Kazuhiko [RSC Advances, 2014, vol. 4, # 71, p. 37674 - 37678] Tanaka, Shinji; Kon, Yoshihiro; Nakashima, Takuya; Sato, Kazuhiko [RSC Advances, 2014, vol. 40, # 71, p. 37674 - 37678]
[35]Giachi, Guido; Oberhauser, Werner; Frediani, Marco; Passaglia, Elisa; Capozzoli, Laura; Rosi, Luca [Journal of Polymer Science, Part A: Polymer Chemistry, 2013, vol. 51, # 11, p. 2518 - 2526]
[36]Vanoye, Laurent; Pablos, Mertxe; De Bellefon, Claude; Favre-Réguillon, Alain [Advanced Synthesis and Catalysis, 2015, vol. 357, # 4, p. 739 - 746]
[37]Seok, Seunghwan; Hussain, Muhammad Asif; Park, Kyun Joo; Kim, Jung Won; Kim, Do Hyun [Ultrasonics Sonochemistry, 2016, vol. 28, p. 178 - 184]
[38]Prathap, Kaniraj Jeya; Maayan, Galia [Chemical Communications, 2015, vol. 51, # 55, p. 11096 - 11099]
[39]Martínez-Prieto; Ferry; Rakers; Richter; Lecante; Philippot; Chaudret; Glorius [Chemical Communications, 2016, vol. 52, # 26, p. 4768 - 4771]
[40]Wang, Lianyue; Bie, Zhixing; Shang, Sensen; Lv, Ying; Li, Guosong; Niu, Jingyang; Gao, Shuang [RSC Advances, 2016, vol. 6, # 41, p. 35008 - 35013]
[41]Dutta, Indranil; Sarbajna, Abir; Pandey, Pragati; Rahaman, S. M. Wahidur; Singh, Kuldeep; Bera, Jitendra K. [Organometallics, 2016, vol. 35, # 10, p. 1505 - 1513]
[42]Current Patent Assignee: LEE DOCK ROK - KR2016/9439, 2016, A Location in patent: Paragraph 0021; 0022
[43]Sun, Fuan; Zhou, Jiacheng; Zhou, Weiyou; Pan, Jiugao; Qian, Junfeng; He, Mingyang; Chen, Qun [New Journal of Chemistry, 2018, vol. 42, # 6, p. 4029 - 4035]
[44]Jana, Sandipan; Thomas, Jithin; Sen Gupta, Sayam [Inorganica Chimica Acta, 2019, vol. 486, p. 476 - 482]
[45]Heath, Rachel S.; Birmingham, William R.; Thompson, Matthew P.; Taglieber, Andreas; Daviet, Laurent; Turner, Nicholas J. [ChemBioChem, 2019, vol. 20, # 2, p. 276 - 281]
[46]Geng, Zhenzhen; Zhang, Hong-Yu; Yin, Guohui; Zhang, Yuecheng; Zhao, Jiquan [Journal of Chemical Research, 2020, vol. 44, # 9-10, p. 557 - 565]
[47]Caselli, Alessandro; Gallo, Emma; Panza, Nicola; Rizzato, Silvia; Tseberlidis, Giorgio; di Biase, Armando [European Journal of Organic Chemistry, 2020, vol. 2020, # 42, p. 6635 - 6644]

28
[ 5392-40-5 ]
[ 26489-02-1 ]
3,7-dimethyl-1-octanal [ No CAS ]
3,7-dimethyl-2-octenal [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogen In hexane at 40℃; Title compound not separated from byproducts;
	With hydrogen at 49.84℃; for 2h; sealed reactor;
	With hydrogen In hexane at 100℃;	2.2 Hydrogenation experiments General procedure: The supported ionic liquid catalysts were used in the hydrogenation of citral (Aldrich, 95%). Hydrogenation experiments were performed in a semi-batch reactor (Parr Instrument Company). The total volume of the reactor was 600 ml whereas the effective liquid volume was 250 ml. The temperature and stirring rate were controlled by a Parr 4843 control unit (Watlow control series 982). All experiments were performed at a constant pressure and temperature. Approximately 3 g of citral (0.02 mol) was dissolved in 250 ml of n-hexane (Merck, >99%). In the beginning of each experiment, the reactor was heated to a desired temperature and, at the same time, the hydrogen pressure was also adjusted to desired level. After the citral solution was injected to the reactor, the stirring was commenced and this was considered as the starting point for the reaction. (0006) Citral hydrogenation products were identified by means of gas chromatography (Hewlett Packard 6890 GC with FI detector). In addition, a gas chromatograph coupled to a mass-spectrometer (Agilent 6980N GC with Agilent 5973 MS detector) was used to identify the peaks of citral hydrogenation products. The peaks in the chromatogram were identified with the following reference substances: (±)-citronellal (Fluka, 80-90%), nerol (Fluka, >90%), geraniol (Alfa Aesar, 97%), (+)-neomenthol (Fluka, 98.5%), (-)-isopulegol (Aldrich, 99%), tetrahydrogeraniol (Aldrich, 99%), menthol (Aldrich, 99%), (+)-isomenthol (Fluka, >99%), and (±)-β-citronellol (90-95%, Fluka). The progress of citral hydrogenation reaction was monitored by taking samples from the reactor and analyzing them by means of gas chromatography. In the case of standard samples and samples taken from reactor, 500 μl of internal standard (0.02 M cyclohexanone in cyclohexane) was added into a 500 μl of sample. The GC column used was an Agilent DB-5 with a length of 60 m, inner diameter of 0.32 mm and a film thickness of 1 μm. The following temperature program was applied: 10 min at 100 °C, then raised 5 °C/min to 160 °C. Temperature was then held 10 min at 160 °C. At the end the temperature was increased 13 °C/min to 200 °C and kept constant for 1 min.

With crosslinked Pd-chitosan catalyst In ethanol at 50℃;

Reference： [1]Burgener, Marco; Wirz, Ronny; Mallat, Tamas; Baiker, Alfons [Journal of Catalysis, 2004, vol. 228, # 1, p. 152 - 161]
[2]Hu, Baoji; Ding, Kunlun; Wu, Tianbin; Zhou, Xiaosi; Fan, Honglei; Jiang, Tao; Wang, Qian; Han, Buxing [Chemical Communications, 2010, vol. 46, # 45, p. 8552 - 8554]
[3]Salminen, Eero; Virtanen, Pasi; Kordás, Krisztián; Mikkola, Jyri-Pekka [Catalysis Today, 2012, vol. 196, # 1, p. 126 - 131]
[4]Schüßler, Stefan; Blaubach, Nico; Stolle, Achim; Cravotto, Giancarlo; Ondruschka, Bernd [Applied Catalysis A: General, 2012, vol. 445-446, p. 231 - 238]

29
[ 2524-37-0 ]
[ 5392-40-5 ]
[ 705260-27-1 ]

Reference： [1]Angewandte Chemie - International Edition,2012,vol. 51,p. 10329 - 10332,4
Angewandte Chemie,2012,vol. 124,p. 10475 - 10478,4
[2]Tetrahedron Letters,2005,vol. 46,p. 7539 - 7543

30
[ 504-02-9 ]
[ 5392-40-5 ]
[ 58134-00-2 ]

Yield	Reaction Conditions	Operation in experiment
90%	With 2,4,8,10-tetra-tert-butyl-6-hydroxydibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide; sodium sulfate In toluene at 60℃; Inert atmosphere; regioselective reaction;
88%	With ethylenediaminediacetic acid; zinc dibromide In tetrahydrofuran at 40℃; for 0.166667h;
75.4%	With ethylenediamine diacetic acid at 20℃; for 1h;

67%	With ethylenediamine diacetic acid
66%	With ethylenediamine diacetic acid

Reference： [1]Moreau, Julie; Hubert, Claudie; Batany, Jessika; Toupet, Loic; Roisnel, Thierry; Hurvois, Jean-Pierre; Renaudz, Jean-Luc [Journal of Organic Chemistry, 2009, vol. 74, # 23, p. 8963 - 8973]
[2]Garcia, Angie; Borchardt, Dan; Chang, Chia-En A.; Marsella, Michael J. [Journal of the American Chemical Society, 2009, vol. 131, # 46, p. 16640 - 16641]
[3]Fernandes, Sylvia; Rajakannu; Bhat, Sujata V. [RSC Advances, 2015, vol. 5, # 83, p. 67706 - 67711]
[4]Lee, Yong; Wang, Xue; Kim, Byung [Synthetic Communications, 2006, vol. 36, # 14, p. 2017 - 2025]
[5]Lee, Yong Rok; Lee, Won Kyong; Noh, Seok Kyun; Lyoo, Won Seok [Synthesis, 2006, # 5, p. 853 - 859]

31
[ 83-72-7 ]
[ 5392-40-5 ]
[ 77566-45-1 ]

Yield	Reaction Conditions	Operation in experiment
72%	With water at 80℃; for 6h;
70%	With formic acid In ethanol; water at 80℃; for 5.5h; Microwave irradiation;	General procedure for preparing 5f-k under microwave heating General procedure: A 10 mL microwave tube was loaded with 4 (11.5 mmol), the corresponding aldehyde (11.5 mmol), formic acid (17.3 mmol), and 5 mL of a 1:1 ethanol/water mixture (v/v), and the resulting mixture was irradiated from 1 to 5.5 h. The internal temperature reached 80 °C. The solvent was evaporated under reduced pressure, and the crude mixture was extracted with ethyl acetate (30 mL). The organic layer was washed with water (3×20 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residual solid product was purified by column chromatography using silica gel and a gradient of hexane/EtOAc as the eluent. The products were obtained in yields ranging from 10 to 73%.
64%	With ethylenediamine diacetic acid In benzene Heating;

Reference： [1]Location in patent: experimental part Jung, Ene Jin; Park, Byung Ho; Lee, Yong Rok [Green Chemistry, 2010, vol. 12, # 11, p. 2003 - 2011]
[2]Da Rocha, David R.; Mota, Kelly; Da Silva, Illana M.C.B.; Ferreira, Vitor F.; Ferreira, Sabrina B.; Da Silva, Fernando De C. [Tetrahedron, 2014, vol. 70, # 20, p. 3266 - 3270]
[3]Lee, Yong Rok; Choi, Jung Hyun; Trinh, Dinh Thi Lan; Kim, Nam Woo [Synthesis, 2005, # 18, p. 3026 - 3034]

32
[ 6666-75-7 ]
[ 5392-40-5 ]
(4E,6E)-2-cyano-3,7,11-trimethyldodeca-2,4,6,10-tetraenoic acid [ No CAS ]

Reference： [1]Helvetica Chimica Acta,2007,vol. 90,p. 512 - 520

33
[ 2732-18-5 ]
[ 5392-40-5 ]
deoxybruceol [ No CAS ]

Reference： [1]Synlett,2007,p. 2232 - 2236

34
[ 2295-58-1 ]
[ 5392-40-5 ]
C₁₉H₂₄O₄ [ No CAS ]

Reference： [1]Synlett,2007,p. 2232 - 2236

35
[ 727-71-9 ]
[ 5392-40-5 ]
C₂₄H₂₆O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With ethylenediamine diacetic acid In N,N-dimethyl-formamide at 100℃; for 10h;

Reference： [1]Yong, Rok Lee; Jung, Hee Kim [Synlett, 2007, # 14, p. 2232 - 2236]

36
PdSO₄ [ No CAS ]
Li₂ MoO₄ [ No CAS ]
[ 123-35-3 ]
[ 629-50-5 ]
[ 7732-18-5 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
	With 1-methyl-pyrrolidin-2-one; nitrogen; p-benzoquinone; lithium chloride; sodium chloride	6 EXAMPLE 6 EXAMPLE 6 To a solution of N-methylpyrrolidone (0.75 ml) and Li2 MoO4 (0.11 gm) was added PdSO4 (0.024 gm), LiCl (0.0054 gm), benzoquinone (0.03 gm) and H2 O (0.075 ml). The solution was gently but continuously stirred for about 5 minutes using nitrogen as an inert purging gas. Myrcene (0.066 ml) was added and the solution was heated to about 90° C., for about 2.5 hrs, with gentle and continuous stirring. Tridecane (0.013 gm) was then added to the mixture as an internal standard, and the solution was transferred to a separation funnel, rinsed with toluene (1.5 ml) and extracted five times using a NaCl/H2 O solution. The organic phase was then dried over K2 CO3, and the resulting product analyzed substantially as described in Example 1. The resulting yield of citral was 34%, with a selectivity of 17%.

Reference： [1]Current Patent Assignee: INTERNATIONAL PAPER CO - US4978804, 1990, A

37
PdCl₂ (CH₃ CN)2 [ No CAS ]
Li₂ MoO₄ [ No CAS ]
[ 123-35-3 ]
[ 629-50-5 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
	With 1-methyl-pyrrolidin-2-one; sodium chloride In water; toluene	1 EXAMPLE 1 EXAMPLE 1 To a solution of N-methylpyrrolidone (0.75 ml) and Li2 MoO4 (0.11 gm) was added PdCl2 (CH3 CN)2 (0.03 gm) and water (0.075 ml). The solution was gently but continuously stirred using a magnetic stirrer for about 5 minutes while nitrogen was employed as an inert purging gas. Myrcene (0.066 ml) was then added to the solution and the mixture was heated to about 90° C. for about 2.5 hrs, with gentle and continuous stirring. Tridecane (0.014 gm) was then added to the mixture as an internal standard, and the solution was transferred to a separation funnel. Toluene (1.5 ml) was added, and the solution was extracted five times using a NaCl/H2 O mixture. The organic phase was then dried over K2 CO3. The resulting yield of citral was 44%, with a selectivity of 26%.

Reference： [1]Current Patent Assignee: INTERNATIONAL PAPER CO - US4978804, 1990, A

38
[ 123-35-3 ]
[ 123-03-5 ]
[ 71-36-3 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
	With carbon dioxide;	To the solution was then added myrcene (3 ml), n-butanol (7.5 ml) and <strong>[123-03-5]cetylpyridinium chloride</strong> (0.3586 g). Carbon dioxide was bubbled through for about 20 min, the solution was heated to about 90 C. for about 2.5 hrs, and product recovered. The resulting yield of citral was 66%.

Reference： [1]Patent: US5093538,1992,A

39
[ 123-35-3 ]
[ 112-02-7 ]
[ 71-36-3 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
	With carbon dioxide;	To the solution was then added myrcene (0.66 ml), n-butanol (7.5 ml) and <strong>[112-02-7]cetyltrimethylammonium chloride</strong> (1.32 ml). Carbon dioxide was bubbled through for about 20 min, the solution was heated to about 90 C. for about 2.5 hrs, and product recovered. The resulting yield of citral was 46%.
	With oxygen;	To the solution was then added myrcene (3 ml), n-butanol (7.5 ml) and <strong>[112-02-7]cetyltrimethylammonium chloride</strong> (1.32 ml), and O2 was bubbled through the solution for about 15 min. The solution was heated to about 90 C. for about 6 hrs, while continuing to introduce O2 into the reaction vessel. Product was then recovered. The resulting yield of citral was 43%.
	With oxygen;	To the solution was then added myrcene (3 ml), n-butanol (7.5 ml) and <strong>[112-02-7]cetyltrimethylammonium chloride</strong> (1.32 ml), and O2 was bubbled through the solution for about 15 min. The solution was heated to about 90 C. for overnight, while continuing to introduce O2 into the reaction vessel. Product was then recovered. The resulting yield of citral was 66%.

Reference： [1]Patent: US5093538,1992,A
[2]Patent: US5093538,1992,A
[3]Patent: US5093538,1992,A

40
[ 123-35-3 ]
[ 112-02-7 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
	With carbon dioxide; In toluene;	To the solution was then added myrcene (0.66 ml), toluene (7.5 ml) and <strong>[112-02-7]cetyltrimethylammonium chloride</strong> (1.5 ml). Carbon dioxide was bubbled through for about 20 min, the solution was heated to about 90 C. for about 2.5 hrs, and product recovered. The resulting yield of citral was 27%.
	In toluene;	To the solution was then added myrcene (2.83 ml), toluene (7.5 ml) and <strong>[112-02-7]cetyltrimethylammonium chloride</strong> (1.32 ml). Oxygen was bubbled through for about 20 min, the solution was heated to about 90 C. for about 4 hrs, and product recovered. The resulting yield of citral, analyzed using external standard gas chromatography, was 20%.

Reference： [1]Patent: US5093538,1992,A
[2]Patent: US5093538,1992,A

41
[ 2754-11-2 ]
[ 5389-87-7 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
88%	With sulfuric acid; sodium sulfate In ethyl acetate; N,N-dimethyl-formamide	1 EXAMPLE 1 STR13 EXAMPLE 1 STR13 346 mg (2 mmols) of geranyl chloride and 787 mg (6 mmols) of N-ethylmorpholine N-oxide were placed in a flask, to which was further added 3 ml of N,N-dimethylformamide. The mixture was agitated at room temperature for 1 hour and at 50° C. for 4 hours. To the reaction mixture was added 10 ml of 2.5% sulfuric acid and 10 ml of ethyl acetate for phase separation. The resultant organic phase was washed with 5 ml of 2.5% sulfuric acid, 5 ml of a saturated sodium hydrogen carbonate aqueous solution and 5 ml of a 10% sodium sulfate aqueous solution successively, after which it was dried with magnesium sulfate. After the drying, the solvent was distilled off from the solution and the residue was subjected to distillation by the use of Kugel-rohr distillation apparatus (bath temperature 93° C./3 Torr.) to obtain 268 mg (1.76 mmols) of citral. The yield was 88%.

Reference： [1]Current Patent Assignee: KURARAY CO LTD - US4745229, 1988, A

42
[ 471-10-3 ]
[ 629-59-4 ]
[ 2687-45-8 ]
[ 5389-87-7 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
67%	With sulfuric acid In ethyl acetate; N,N-dimethyl-formamide	23 EXAMPLE 23 STR27 EXAMPLE 23 STR27 330 mg (1.9 mmols) of a mixture of gernayl chloride, neryl chloride and linalyl chloride (ratios=61:32:7), 24.3 mg (0.25 mmols) of copper(I) chloride, 0.82 g (6.0 mmols) of triethylamine N-oxide (water content of 14%), and 3 ml of N,N-dimethylformamide were mixed and agitated at 45° C. for 2 hours. 15 ml of ethyl acetate and 8 ml of 2% sulfuric acid were added to the mixture and shaked sufficiently to extract an organic matter. The organic phase was collected, to which 145 mg of n-tetradecane was added, followed by subjecting to gas chromatography. As a result, it was found that starting geranyl chloride, neryl chloride and linalyl chloride disappeared with citral being formed at a yield of 67%.

Reference： [1]Current Patent Assignee: KURARAY CO LTD - US4745229, 1988, A

43
[ 500-66-3 ]
[ 5392-40-5 ]
[ 4993-99-1 ]

Yield	Reaction Conditions	Operation in experiment
75%	With ammonium chloride In water for 24h; Inert atmosphere; Reflux;
74.5%	With <i>tert</i>-butylamine In toluene for 5h; Reflux; Dean-Stark;	2.1.1. Preparation of phytocannabinoids Cannabichromene (CBC) [17] A 100 mL round-bottom flaskequipped with a Dean-Stark trap was charged with 3.00 g (16.64 mmol)of olivetol, 2.99 mL (17.48 mmol) of citral, 1.76 mL (16.64 mmol) oftert-butylamine, and 33 mL of toluene. The reaction mixture wasrefluxed for 5 hours. After completion, the solvent was removed underreduced pressure. Flash chromatography using PE/EtOAc (95:5) provided3.90 g (12.40 mmol, 74.5%) of CBC as a yellow oil (99% purity).NMR spectra were in accordance with published data [18].
61%	With <i>tert</i>-butylamine In toluene for 18h; Inert atmosphere; Reflux;	1; 3; 4; 5; 6; 7; 8; 9 0079] EXAMPLE 1 : To a three-necked round bottomed flask, fitted with a dropping funnel and a condenser, under nitrogen atmosphere was added 0.5 g olivetol (2.78 mmol) and 0.2 g (0.36 mL, 2.78 mmol) t-butyl amine in 5 mL toluene and 0.42 g (0.48 mL, 2.78 mmol) of citral was then added dropwise. The mixture was refluxed for 18 hours, after which time it was cooled to room temperature. The reaction mixture was extracted with at least 0.5 MEq of 10% aqueous citric acid solution followed by water. The solution was then dried over anhydrous sodium sulfate, and concentrated by evaporation at reduced pressure to give the crude reaction mixture. The solution was then purified by normal phase silica flash chromatography with a methyl tert-butyl ether/heptane gradient. Analysis of the crude reaction mixture by HPLC (Fig. 1) showed CBC as the major product with a yield in the crude reaction mixture of 61 %.

50%	Stage #1: (E/Z)-3,7-dimethyl-2,6-octadienal With piperidine; acetic anhydride In ethyl acetate for 1h; Inert atmosphere; Sealed tube; Heating; Stage #2: Olivetol In ethyl acetate; toluene at 130℃; for 40h; Inert atmosphere;
38%	With acetic acid; ethylenediamine In toluene for 6h; Reflux;
35%	With ethylenediamine diacetic acid In toluene at 110℃; for 6h; Inert atmosphere;
	With propylamine In toluene	V (Preparation of Cannabichromene) EXAMPLE V (Preparation of Cannabichromene) The reaction of 5 g. olivetol (27.8 mmole), 1.652 g. n-propylamine (2.3 ml., 27.8 mmole) and 4.6 ml. citral (27.8 mmole) in 55 ml. toluene was carried out in the same manner as described under Example 1. The refluxing time was 7 hours. Gas chromatographic analysis of the reaction mixture showed 61.62% CBC, 4.01% Cannabicitran and trace amount of iso-CBC. Purification and chromatography of CBC were carried out as described under Example II.
	Stage #1: Olivetol; (E/Z)-3,7-dimethyl-2,6-octadienal With N-butylamine In toluene Reflux; Stage #2: In toluene at 20℃; for 0.166667h;
	Stage #1: (E/Z)-3,7-dimethyl-2,6-octadienal With piperidine; acetic anhydride In ethyl acetate at 0 - 90℃; for 1h; Stage #2: Olivetol In ethyl acetate; toluene at 139℃; for 65h; Inert atmosphere;	7 EXAMPLE 7: To a round bottomed flask with a stopcocked side arm (100 ml capacity), was charged with 640 pL citral, 800 pL piperdine and 7.5 mL ethyl acetate. The resulting mixture was cooled to 0°C and 800 pL acetic anhydride was added dropwise. The resulting mixture was heated at 90°C for 1 hour, before adding a 15 mL solution toluene containing 1 g olivetol. The reaction mixture was stirred at 130°C for 65 hours under nitrogen, after which time it was cooled to room temperature. The solvent was removed by evaporation to yield 3.1 g of crude product. Analysis by HPLC (FIG. 5) showed CBC as the major product with a yield of 30% w/w, however no CBL was observed. Replacement of 7.5 mL ethyl acetate with 15 mL toluene and 0.8 mL acetic anhydride produced no significant CBC and no observable CBL. An alternative reaction mixture of: 0.30 mL citral, 300 mg olivetol, 0.25 mL acetic anhydride, 1 .8 mL toluene, and a single drop of formic acid at room temp temperature under N2 gas for 24 hours produced no significant CBC and no observable CBL.
	With <i>tert</i>-butylamine In toluene at 50 - 60℃; for 9h; Reflux;	I EXAMPLE I: Preparation of Cannabichromene To a three-necked round bottomed flask (100 ml capacity), fitted with a dropping funnel and a condenser is added 5 g olivetol (27.8 mmole) and 2.03 g (2.96 ml, 27.8 mmole) t-butyl amine in 55 ml toluene and the mixture is heated to 50°-60°C, 4.23 g (4.76 ml, 27.8 mmole) of citral is then added dropwise. The mixture is refluxed for 9 hours, after which time it is cooled to room temperature and the solvent evaporated to give a crude reaction mixture.
	Stage #1: Olivetol With ethylenediamine In toluene at 100℃; Inert atmosphere; Reflux; Stage #2: (E/Z)-3,7-dimethyl-2,6-octadienal In toluene at 100℃; Inert atmosphere;	1; 3; 4; 5; 6; 7; 8; 9; 10; 11; 12; 14 Procedure: A EasyMax reactor (50 mL) equipped with a reflux condenser was loaded with olivetol (2.70 g, 15.0 mmol, 1.00 equiv.), Toluene (33 mL), and ethylenediamine ( 200 μL, 3.00 mmol, 20 mol%). Then the solution was heated to 100 °C. (Note: The reaction turned cloudy when ethylenediamine was added. The solution turned clear while heating to 100 °C.) Next, citral (2.80 mL, 16.35 mmol, 1.09 equiv.) in Toluene (8.17 mL) was added over a ten minute period. (Note: The reaction bubbled during this time.) The reaction mixture was stirred at 100 °C for 30 minutes (Note: The reaction was no longer bubbling after ~5 minutes.). After the allotted time, the reaction mixture was cooled to 20 °C. Conversion: 88.15%

Reference： [1]Quílez Del Moral, José F.; Ruiz Martínez, Cristina; Pérez Del Pulgar, Helena; Martín González, Juan Eduardo; Fernández, Ignacio; López-Pérez, José Luis; Fernández-Arteaga, Alejandro; Barrero, Alejandro F. [Journal of Organic Chemistry, 2021, vol. 86, # 4, p. 3344 - 3355]
[2]Vacek, Jan; Vostalova, Jitka; Papouskova, Barbora; Skarupova, Denisa; Kos, Martin; Kabelac, Martin; Storch, Jan [Free Radical Biology and Medicine, 2021, vol. 164, p. 258 - 270]
[3]Current Patent Assignee: CANOPY GROWTH CORPORATION - WO2021/127786, 2021, A1 Location in patent: Paragraph 0079; 0081; 0082; 0083; 0084-0087
[4]Yeom, Hyun-Suk; Li, Hui; Tang; Hsung, Richard P. [Organic Letters, 2013, vol. 15, # 12, p. 3130 - 3133]
[5]Udoh, Michael; Santiago, Marina; Devenish, Steven; McGregor, Iain S.; Connor, Mark [British Journal of Pharmacology, 2019, vol. 176, # 23, p. 4537 - 4547]
[6]Anderson, Lyndsey L.; Ametovski, Adam; Lin Luo, Jia; Everett-Morgan, Declan; McGregor, Iain S.; Banister, Samuel D.; Arnold, Jonathon C. [ACS Chemical Neuroscience, 2021, vol. 12, # 2, p. 330 - 339]
[7]Current Patent Assignee: THE UNIVERSITY OF MISSISSIPPI - US4315862, 1982, A
[8]Caprioglio, Diego; Mattoteia, Daiana; Minassi, Alberto; Pollastro, Federica; Lopatriello, Annalisa; Muňoz, Eduardo; Taglialatela-Scafati, Orazio; Appendino, Giovanni [Organic Letters, 2019, vol. 21, # 15, p. 6122 - 6125]
[9]Current Patent Assignee: CANOPY GROWTH CORPORATION - WO2021/127788, 2021, A1 Location in patent: Paragraph 00171
[10]Current Patent Assignee: LYGOS INC - WO2021/163042, 2021, A1 Location in patent: Page/Page column 28
[11]Current Patent Assignee: PURISYS - WO2021/222609, 2021, A1 Location in patent: Paragraph 00158-00159; 00169-00170; 00173; 00176; 00179; ...

44
[ 107-86-8 ]
[ 1191-16-8 ]
[ 5392-40-5 ]

Yield	Reaction Conditions	Operation in experiment
48%	With benzoic acid	17 EXAMPLE 17 EXAMPLE 17 60 parts of prenyl acetate, 40 parts of 3,3-dimethylacrolein and 2parts of benzoic acid are heated together for five hours thirty minutes at 140°C and the product is worked up. 11.1 parts of citral is obtained having a boiling point of 104°C at 12 mm in a yield of 48% at a conversion of 32% (based on 3,3-dimethylacrolein).

Reference： [1]Current Patent Assignee: BASF SE - US3965193, 1976, A

45
[ 3602-54-8 ]
[ 5392-40-5 ]
[ 60715-04-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With ethylenediamine diacetic acid In xylene for 10h; Heating;
87%	With ethylenediamine diacetic acid In 5,5-dimethyl-1,3-cyclohexadiene at 170℃; for 1h; Microwave irradiation;
62%	With ethylenediamine diacetic acid In N,N-dimethyl-formamide at 100℃; for 12h; Inert atmosphere;

Reference： [1]Yong, Rok Lee; Xia, Likai [Synthesis, 2007, # 20, p. 3240 - 3246]
[2]Aigner, Ludwig; Bieler, Lara; Couillard-Despres, Sebastien; Priglinger, Eleni; Riepl, Herbert M.; Urmann, Corinna [Journal of Natural Products, 2021, vol. 84, # 10, p. 2675 - 2682]
[3]Location in patent: experimental part Wang, Xue; Lee, Yong Rok [Tetrahedron, 2009, vol. 65, # 49, p. 10125 - 10133]

46
[ 90-02-8 ]
[ 5392-40-5 ]
[ 1178907-94-2 ]

Yield	Reaction Conditions	Operation in experiment
67%	With potassium carbonate In methanol; toluene at 80℃;
60%	In 1,4-dioxane; water at 55℃; for 72h; Inert atmosphere; Alkaline conditions;	Preparationof the precursor, 2-methyl-2-(4-methylpent-3-en-1-yl)-2H-chromene-3-carbaldehyde: A solution of sodium carbonate (14.08 mmol, 1.4 g) in water (5 mL) was stirred at 25 °C. After complete dissolution of sodium carbonate, a solution of salicylaldehyde (12.8 mmol, 2 g) in 1,4-dioxane (15 mL) was added at 0 °C. After 15 min, citral (38.4 mmol, 6.61 mL) was added at room temperature. The resulting mixture was stirred at 55 °C for 72 h. After completion, as monitored by TLC, the crude mixture was extracted with ethyl acetate and washed with brine solution. Removal of the solvent followed by purification on silica gel column chromatography using a gradient mixture of EtOAc/hexane (1:9) afforded the 2-methyl-2-(4-methylpent-3-enyl)-2H-chromene-3-carbaldehyde in 60% yield.
51%	With 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine at 30℃; for 48h; Sealed tube;

	With sodium carbonate In 1,4-dioxane; water at 55℃; for 72h;
	Stage #1: salicylaldehyde With sodium carbonate In 1,4-dioxane; water at 0℃; for 0.25h; Stage #2: (E/Z)-3,7-dimethyl-2,6-octadienal In 1,4-dioxane; water at 20 - 55℃; for 72h;	Preparation of 6-(chloro)-2-methyl-2-(4-methylpent-3-enyl)-2H-chromene-3-carbaldehyde from 5-chlorosalicylaldehyde General procedure: A solution of sodium carbonate (14.08 mmol, 1.4 g) in water (5 mL) was stirred at 25 °C. After complete dissolution of sodium carbonate, a solution of 5-chlorosalicylaldehyde (12.8 mmol, 2 g) in 1,4-dioxane (15 mL) was added at 0 °C. After 15 min, citral (38.4 mmol, 6.61 mL) was added at room temperature. The resulting mixture was stirred at 55 °C for 72 h. After the completion, as monitored by TLC, the crude product (1b) was extracted with ethyl acetate and washed with brine solution. Removal of solvent followed by purification on silica gel column chromatography using a gradient mixture of EtOAc/hexane (1:9) afforded the 6-(chloro)-2-methyl-2-(4-methylpent-3-enyl)-2H-chromene-3-carbaldehyde in 60% yield.

Reference： [1]Giorgi, Pascal D.; Miedziak, Peter J.; Edwards, Jennifer K.; Hutchings, Graham J.; Antoniotti, Sylvain [ChemCatChem, 2017, vol. 9, # 1, p. 70 - 75]
[2]Rao, Y. Jayaprakash; Reddy, E. Pravardhan; Sridhar; Lakshmi; Reddy, B.V. Subba [Tetrahedron Letters, 2016, vol. 57, # 26, p. 2853 - 2856]
[3]Ballarotto, Marco; Solinas, Mario; Temperini, Andrea [Organic and Biomolecular Chemistry, 2021, vol. 19, # 47, p. 10359 - 10375]
[4]Location in patent: scheme or table Bröhmer, Manuel C.; Volz, Nicole; Bräse, Stefan [Synlett, 2009, # 9, p. 1383 - 1386]
[5]Location in patent: experimental part Reddy, B.V. Subba; Divya, Baddula; Swain, Manisha; Rao, T. Prabhakar; Yadav; Vishnu Vardhan [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 5, p. 1995 - 1999]

47
[ 727-71-9 ]
[ 5392-40-5 ]
C₂₄H₂₆O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With ethylenediamine diacetic acid In N,N-dimethyl-formamide at 100℃; for 10h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Wang, Xue; Lee, Yong Rok [Tetrahedron, 2009, vol. 65, # 49, p. 10125 - 10133]

48
[ 2174-64-3 ]
[ 5392-40-5 ]
[ 89462-14-6 ]

Yield	Reaction Conditions	Operation in experiment
43%	With ethylenediamine diacetic acid In N,N-dimethyl-formamide at 100℃; for 12h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Wang, Xue; Lee, Yong Rok [Tetrahedron, 2009, vol. 65, # 49, p. 10125 - 10133]

49
[ 2295-58-1 ]
[ 5392-40-5 ]
C₁₉H₂₄O₄ [ No CAS ]

Reference： [1]Tetrahedron,2009,vol. 65,p. 10125 - 10133

50
[ 109-73-9 ]
[ 5392-40-5 ]
[ 63711-85-3 ]

Yield	Reaction Conditions	Operation in experiment
97.6%	With S₂O₈₂-/PIM-6 In cyclohexane at 10℃; for 2h;	4 15.2g of neral aldehyde was added to a 250ml flask,100 ml of cyclohexane was added, stirred well, and then 1.3 g of catalyst S2O82-/PIM-6 (molar ratio of covalent groups to ligands was 0.1) was added thereto at 10°C, and 7.3 g of n-butylamine was dropped thereon. The reaction solution was added to the reaction mixture, and the reaction was carried out with stirring for 2 hours. The reaction was filtered and separated to obtain a catalyst and a reaction solution. The reaction solution was washed three times with saturated brine, and the organic phase was collected. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The solvent was cyclohexane and the crude product was obtained. The crude product was purified by silica gel column chromatography. The silica gel column was first neutralized with n-butylamine and then eluted with n-hexane-ethyl acetate=2:10 (v/v). Corresponding purificationN-n-butyl-Nerol Aldimine,The yield was 97.6% and the purity was 99.0%.
	With potassium hydroxide
	With zirconium(IV) tetraisopropoxide In methanol at 20℃; for 4h; Inert atmosphere;	General Procedure for the zirconium-mediated reductive amination reaction of carbonyl compounds General procedure: A mixture of aldehyde or ketone (2 mmol), zirconium(IV) isopropoxide (567 mg, 2 mmol) and the desired amine (6 mmol) in absolute methanol (5 mL) was stirred under argon at room temperature for 4 hours. Sodium borohydride (75 mg, 2 mmol) was then added at 0 °C and the resulting mixture was stirred for an additional 2 hours. The reaction was then quenched by adding water (1 mL). After filtration over a path of celite, washing with methanol and ethyl acetate, the solvents were removed in vacuo to afford the expected crude amine which was purified by flash chromatography on silicagel.

19.8 g

With boron trifluoride diethyl etherate; sodium sulfate In cyclohexane at -5℃; for 6h;

2 15.2 g (0.1 mol) of the above-obtained citral was added to a 250 ml flask,And 130 ml of cyclohexane was added, And 5 g of anhydrous sodium sulfate to form a reaction solution,Cooled to -5 ° C,Then, 0. l ml of boron trifluoride ether solution was added to the reaction solution as a catalyst,And 7.3 g of n-butylamine was added dropwise to the reaction solution,And the mixture was stirred for 6 hours while stirring. The reaction solution was washed three times with saturated brine,And the organic phase was collected and the organic phase was dried over anhydrous sodium sulfate,Concentrated under reduced pressure to remove the solvent cyclohexane in crude product,The crude product was purified by silica gel column chromatography,First with n-butylamine on the silica column to neutralize,And eluted with n-hexane-ethyl acetate = 2: 10 (ν / ν)To give the corresponding purified N-n-butyl-citral imine 19.8 g,Purity 94%

Reference： [1]Current Patent Assignee: NAN AN CHUANGYOU DAILY CHEMICAL - CN106565501, 2017, A Location in patent: Paragraph 0013; 0015; 0017; 0019; 0021; 0022; 0024
[2]Location in patent: scheme or table Metlushka, Kirill E.; Alfonsov, Vladimir A.; Bolshakova, Olga V.; Nizamov, Il'yas S.; Nizamov, Il'nar D.; Voloshina, Alexandra D.; Sergeenko, Gulnur G. [Phosphorus, Sulfur and Silicon and the Related Elements, 2011, vol. 186, # 4, p. 806 - 808]
[3]Pieri, Cyril; Brunel, Jean Michel [Letters in drug design and discovery, 2015, vol. 12, # 6, p. 448 - 456]
[4]Current Patent Assignee: CHINESE ACADEMY OF FORESTRY - CN104387278, 2017, B Location in patent: Paragraph 0017; 0039

51
[ 183143-90-0 ]
[ 5392-40-5 ]
C₃₃H₄₆O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With ethylenediamine diacetic acid In N,N-dimethyl-formamide at 100℃; for 12h; Inert atmosphere; regioselective reaction;	3.2. Typical procedure for compounds 12 and 18-24 General procedure: To a solution of substituted trihydroxybenzenes (1.0 mmol) and citral or trans,trans-farnesal (1.2 mmol) in DMF (10 mL) was added ethylenediamine diacetate (36 mg, 0.2 mmol) at room temperature. The reaction mixture was stirred at 100 °C for 10-12 h and then cooled to room temperature. After completion of reaction as indicated by TLC, the reaction mixture was quenched with water (30 mL) and extracted with ethyl acetate (50 mL×3). The combined organic layer was dried over MgSO4 and concentrated, and the crude product was purified by column chromatography on silica gel (hexane/ethyl acetate, 20:1) to afford products.