| 98% |
In isopropanol at 80℃; for 18h; also with other catalysts, various times; |
|
| 98% |
With isopropanol at 80℃; for 18h; also with Yb(Oi-Pr)3, Ce(Oi-Pr)3, Sm(Oi-Pr)3; |
|
| 97% |
With isopropanol; sodium hydroxide for 22.5h; Reflux; |
|
| 97% |
With sodium tetrahydridoborate In methanol at 20℃; for 4h; |
|
| 96% |
With sodium tetrahydridoborate at 60℃; for 3h; |
|
| 96% |
With hydrogenchloride; isopropanol for 0.55h; Heating; |
|
| 95% |
With di-n-butyltin dihydride In toluene at 20℃; for 3h; |
|
| 94% |
With lithium aluminium hydride; Methylephedrine; N-ethyl-N-phenylamine In diethyl ether at -78℃; for 3h; |
|
| 93% |
With isopropanol at 80℃; for 24h; Inert atmosphere; |
|
| 92% |
With hydrogen at 80℃; |
|
| 92% |
With zirconyl pyrophosphate; isopropanol at 150℃; for 10h; |
|
| 92% |
Stage #1: hexyl-methyl-ketone With (R)-(+)-3,3'-bis(4-fluorophenyl)-[1,1'-binaphthalene]-2,2'-diol; Di-n-butylmagnesium; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane; lithium chloride In n-heptane; toluene at -40℃; for 24h; Inert atmosphere; Sealed tube;
Stage #2: With methanol In n-heptane; toluene at -40 - 20℃; for 0.5h; Inert atmosphere; Sealed tube; |
|
| 91% |
With diphenylamine borane In tetrahydrofuran 1.) 0 deg C, 1 h, 2.) 20 deg C, 1 h; |
|
| 91% |
With LaNi5 hydride In tetrahydrofuran; methanol 1) 0 deg C, 4 h, 2) r.t., 37 h; |
|
| 90% |
With alumina-supported potassium hydroxide; isopropanol for 0.216667h; microwave irradiation; |
|
| 90% |
With isopropanol; lithium tert-butylate at 180℃; for 0.5h; |
|
| 90% |
With poly(1,4-butyl-bis-vinylpyridinium) borohydride In ethanol at 20℃; for 0.833333h; |
|
| 90% |
Stage #1: hexyl-methyl-ketone With C23H20BrMnNO3P In isopropanol for 0.166667h; Inert atmosphere; Schlenk technique;
Stage #2: With potassium-t-butoxide In isopropanol at 60℃; for 3h; Inert atmosphere; Schlenk technique; |
|
| 89% |
With sodium tetrahydridoborate In methanol at 0 - 20℃; |
General procedure for synthesis of alcohols 1a-6a
General procedure: To a solution of appropriated commercial ketone (50mmol) in methanol (50mL) at 0°C, NaBH4 (1.93g, 51mmol) was added in portions. In the sequence, the reaction was carried out under vigorous stirring at room temperature for 2-6h. Then the methanol was removed by simple distillation, distilled water was added to the white residue and the pH was adjusted to pH 6.0 with aqueous HCl solution 1molL-1. The organic phase was extracted with dichloromethane (3×20mL), dried over anhydrous magnesium sulphate, filtered off and concentrated by simple distillation, leading to racemic alcohols 1a-6a. |
| 89% |
With 1-hydrosilatrane; potassium-t-butoxide In tetrahydrofuran; N,N-dimethyl-formamide at 20℃; for 0.5h; |
|
| 88% |
With sodium tetrahydridoborate In benzene for 3h; Ambient temperature; other similar catalysts; |
|
| 88% |
With isopropanol; sodium hydroxide at 80℃; for 16h; |
|
| 87% |
With chloro-trimethyl-silane; calcium hydride; anhydrous zinc chloride In tetrahydrofuran at 40℃; for 0.3h; |
|
| 87% |
With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); hydrogen In tert-Amyl alcohol at 30℃; for 12h; Green chemistry; |
4.2. General procedure for catalytic hydrogenation of 2
General procedure: To an oven-dried 5 mL round-bottom flask were added ketone (1 mmol), cat. 7 (2.7 mg, 0.5 mol %) and tert-amyl alcohol (1 mL). Next, vacuum was applied to the flask followed by filling with H2 gas and keeping the flask attached to a balloon filled with H2 gas. The mixture was heated at 30 °C for 12 h. After completion of the reaction, the solvent was removed by evaporation under reduced pressure. The alcohols were isolated and purified by filtering a hexanes/ethyl acetate (5:1) solution of the crude product through a pad of silica gel, and then removing the solvent under reduced pressure. The conversion and purity of the alcohol products was assessed using NMR spectroscopy. |
| 86% |
With t-BuOSmI2; isopropanol In tetrahydrofuran at 65℃; for 24h; various ketones; |
|
| 86% |
With sodium tetrahydridoborate; nickel (II) chloride In tetrahydrofuran at 20℃; for 0.0833333h; |
|
| 85% |
In isopropanol at 80℃; for 2h; |
|
| 85% |
With lithium aluminium hydride |
|
| 85% |
With [Cp*Ir(2,2'-bpyO)(OH)][Na]; hydrogen In water monomer at 30℃; for 12h; Green chemistry; |
4.1. General procedure for catalytic hydrogenation of ketones,aldehydes or unsaturated aldehydes
General procedure: To an oven-dried 5 mL round-bottom flask were added ketonesor aldehydes or unsaturated aldehydes (1 mmol), cat. 6 (5.5 mg,1 mol %) and H2O (1 mL). Next, vacuum was applied to the flask followedby filling with H2 gas and keeping the flask attached to a balloonfilled with H2 gas. The mixture was heated at 30 °C for 12 h.After completion of the reaction, the mixture was extracted withethyl acetate (5 mL x 3). Then, the ethyl acetate layers were combined, dried with anhydrous sodium sulfate, filtered, and concentratedby evaporation under reduced pressure. The alcohols wereisolated and purified by filtering a hexanes/ethyl acetate (8:1)solution of the crude product through a pad of silica gel. Thenthe solvent was removed under reduced pressure to afford the correspondingproducts. The purity of alcohol products was assessedusing 1H NMR spectroscopy. |
| 85% |
With [Cp*Ir(2,2'-bpyO)(OH)][Na]; hydrogen In water monomer at 30℃; for 12h; |
22 The method is:
2-Octanone (128 mg, 1.0 mmol), metal ruthenium complex [Cp*Ir(2,2'-bpyO)(OH)][Na] (4.6 mg, 0.01 mmol, 1 mol% ) and water (1 mL) sequentially added to 25 ml round bottom flasks. The reaction mixture was reacted at 30 °C, and the hydrogen atmosphere was reacted for 12 hours. The solvent is removed by sputum, then purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1), yield: 85%. |
| 83.8% |
With titanium isopropoxide; sodium tetrahydridoborate; copolyesteramide (from N,N'-bis(4-methoxycarbonylbenzoyl)hexamethylenediamine, 1,6-hexanediol, poly(ethylene glycol)) In dichloromethane for 6h; Ambient temperature; |
|
| 82.5% |
With methanol; nickel boride; BH3 for 0.5h; Ambient temperature; |
|
| 81% |
With trimethoxyhydrosilane; dilithium pinacolate In diethyl ether; hexane for 15h; Ambient temperature; |
|
| 81% |
With Poly(n-butyl-4-vinylpyridinium)borohydride In ethanol at 20℃; for 4.36667h; |
General procedure for the reduction of carbonylcompounds with P(BVP)BH4
General procedure: To a solution of the substrate (1 mmol) in ethanol as asolvent (5 mL) in a round-bottomed flask (25 mL) equippedwith a magnetic stirrer, P(BVP)BH4 (100 mg) was addedand stirred at room temperature. The progress of thereaction was monitored by TLC. On completion of thereaction, the mixture was filtered and the used reagent waswashed successively with HCl (1.0 M, 2 10 mL) andethanol (2 5 mL). The combined filtrates were evaporatedand the pure product was obtained in moderate to excellent yields. In a few cases in which the reaction wasnot complete, the crude product was purified on silica gelwith an appropriate eluent (Scheme 1). |
| 79% |
Stage #1: hexyl-methyl-ketone With bis(η5-cyclopentadienyl) titanium dichloride; sodium tetrahydridoborate In 1,2-dimethoxyethane at 20℃;
Stage #2: With sodium hydroxide In 1,2-dimethoxyethane |
|
| 75% |
With sodium hydroxide; ytterbium(III) tris(trifluoromethanesulfonate) In isopropanol for 0.5h; Heating; |
|
| 75% |
Stage #1: hexyl-methyl-ketone With diphenylsilane; Cs2CO3 at 80℃; for 5h; Schlenk technique;
Stage #2: With sodium hydroxide In methanol; water monomer at 70℃; Schlenk technique; chemoselective reaction; |
|
| 75% |
Stage #1: hexyl-methyl-ketone With 1,1,3,3-Tetramethyldisiloxane; [Mn(Si(SiMe3)3)2(tetrahydrofuran)2] at 80℃; for 6h;
Stage #2: With N,N,N-tributylbutan-1-aminium fluoride In water monomer |
|
| 72% |
With 2-pyrrolidinon; samarium diiodide Glovebox; |
|
| 68% |
With potassium hydroxide; isopropanol for 4h; Heating; |
|
| 68% |
With C33H34ClIrNS(1+)*F6P(1-) In isopropanol at 80℃; for 6h; |
|
| 67% |
Stage #1: hexyl-methyl-ketone With polyethylsiloxane at 100℃;
Stage #2: With sodium hydroxide In tetrahydrofuran Heating; |
|
| 62% |
With borane-THF; (3R,8R,13R)-3,8,13-triphenylhexahydrotris[1,3,2]-oxazaborolo[3,2-a:3′,2′-c:3′′,2′′-e][1,3,5,2,4,6]-triazatriborinine In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; enantioselective reaction; |
Asymmetric Reduction of Acetophenone with Catalyst 2;Typical Procedure
General procedure: A 100 mL, flame-dried, two-necked, round-bottomed flaskequipped with a magnetic stirrer bar was charged withcatalyst 2 (0.66 mmol) and anhyd THF (4 mL). PhCOMe (2mmol, 0.22 mL) was then added under argon from a syringe.Subsequently, BH3·THF (2.4 mmol, 1.2 equiv) was addeddropwise with the aid of a syringe pump at a rate of 1 mL/h,and the solution was then stirred at r.t. under argon for 18 h. When the reaction was complete, the mixture washydrolyzed by addition of MeOH (5 mL) and 1 M aq HCl (5mL). Workup as described in ref. 14 gave enantiomericallyenriched 1-phenylethanol as a colorless oil; yield: 0.19 g(78%). |
| 60% |
With C12H19ClCoN5(1+)*Cl(1-); sodium tertiary butoxide In isopropanol at 85℃; for 24h; Inert atmosphere; |
|
| 59% |
With LiPhInH3 In diethyl ether for 24h; Ambient temperature; |
|
| 50% |
With [2,2]bipyridinyl; sodium hypophosphite monohydrate; di-μ-chlorobis-[(η6-p-cymene)chlororuthenium(II)] In water monomer at 80℃; for 24h; Inert atmosphere; Sealed tube; |
|
| 31% |
With anhydrous silver tetrafluoroborate; diethoxymethylane; C26H29N3O2*Cl(1-)*Ir(1+)*C8H12 at 20℃; for 20h; stereoselective reaction; |
2.3.1. Procedure using [IrCl(cod)]2as an Ir catalyst precursor
General procedure: A flask was charged with azolium salt L12 (0.02 mmol, 9.1 mg),Ag2O (0.01 mmol, 2.4 mg) and CH2Cl2(1 mL). After stirring the resulting mixture at room temperature for 2 h in the dark, CH2Cl2 was removed in vacuo. Then, a THF (1 mL) solution of [IrCl(cod)]2(0.01 mmol, 6.9 mg) was added to the reaction vessel. The resulting mixture was stirred at room temperature for an additional 4 h in the dark, filtered through a membrane filter, and evaporated to dry-ness in vacuo. Subsequently, to the resulting flask containing yellow solid of the unpurified IrCl(cod)(NHC) complex, a solution of AgBF4(0.025 mmol, 4.9 mg) in CPME (2 mL) was added, and then stirred at room temperature for 1 h. Finally, propiophenone (0.5 mmol,66 mg) and (EtO)2MeSiH (2.25 mmol, 294 mg) were added to the resulting CPME solution (see Appendix A. Supplementary data fordetails). After stirring at room temperature for 20 h under open-air conditions, K2CO3(2 mg) and MeOH (2 mL) were added. Then, the resulting mixture was stirred at room temperature for 2 h. Afterevaporation of the solvents, the residue obtained was purified bycolumn chromatography on silica gel (Et2O/n-hexane = 3:7) to give(S)-1-phenyl-1-propanol (61 mg, 91% isolated yield). The ee was measured by chiral GLC. |
| 30% |
With 1-Methylpyrrolidine; C13H12MnN3O5; hydrogen In tetrahydrofuran at 100℃; for 24h; Autoclave; Glovebox; |
|
| 98.8 % Chromat. |
With tetrabutylammonium octahydrotriborate In chloroform for 20h; Heating; |
|
| 99 % Turnov. |
With sodium tetrahydridoborate In chlorobenzene at 60℃; for 38h; various cyclophosphazenic polypodant catalysts; reaction time, efficiency of the catalysts investigated; |
|
|
With sodium tetrahydridoborate In water monomer; toluene at 25℃; other polymer-supported crown ethers and cryptands as phase-transfer catalysts; |
|
|
With hydrogen; sodium 2-ethyl hexanoate In tetrahydrofuran at 60℃; for 1h; other catalysts, other alkali salts; hydrogenation rate; |
|
| 100 % Chromat. |
With PEG-400; sodium tetrahydridoborate In water monomer; benzene for 5h; Heating; other reagents (phase-transfer catalysts); |
|
|
With hydrogen; Trimethylacetic acid In tetrahydrofuran at 100℃; other temperature, other conc. of pivalic acid, other aditives, other pH object of study - optical yield; |
|
|
at 30℃; for 48h; microorganism, strain Lodderomyces elongisporus IFO 1676, agar plate; other microorganismen; |
|
| 92 % Chromat. |
With sodium tetrahydridoborate; hexakis<p-<<butoxytris(ethoxy)>methoxy>phenoxy>cyclophosphazene at 20℃; for 2h; further times and phase-transfer catalysts; |
|
|
With potassium hydroxide; phosphinerhodium; isopropanol at 82℃; for 41h; hydrogen transfer reduction using various chiral catalysts, various optical yields; |
|
|
With CuO containing mixed catalyst at 150 - 200℃; Hydrogenation; |
|
|
With nickel at 150 - 200℃; Hydrogenation; |
|
| 98 % Chromat. |
With sodium tetrahydridoborate; erbium(III) chloride In ethanol; water monomer The reaction was carried out in the presence of 1,2,5,6-tetrahydrobenzaldehyde. Condition used was described in ref. 3. (J. Am. Chem. Soc. (1979), 44, 4187).; |
|
| 99.4 % Chromat. |
With tetrabutylammonium octahydrotriborate; manganese (II) chloride In tetrahydrofuran Ambient temperature; |
|
| 74 % Chromat. |
With hydrogenchloride; 4(P(C6H5)3)*2Cu(1+)*2(BH3)*2(CN)(1-)={(P(C6H5)3)2CuBH3(CN)}2 In tetrahydrofuran for 3h; Ambient temperature; pH 3; |
|
|
With tetraethylammonium borohydride In dichloromethane at 25℃; for 20h; Yield given; |
|
|
With hydrogenchloride; lithium aluminium hydride; (S)-2-(2,6-xylidinomethyl)pyrrolidine In diethyl ether at -100℃; for 3h; Yield given; |
|
| 64 % Chromat. |
With samarium diiodide; water monomer In tetrahydrofuran for 24h; Ambient temperature; |
|
|
With hydrogen; Trimethylacetic acid In tetrahydrofuran at 100℃; |
|
|
With isopropanol for 6h; Heating; Yield given; |
|
|
With potassium phosphate buffer; pig testicular 20β-hydroxysteroid dehydrogenase; NADPH at 37℃; |
|
|
With sodium tetrahydridoborate |
|
| 95 % Chromat. |
With isopropanol at 89.85℃; for 24h; |
|
|
With sodium tetrahydridoborate |
|
|
With lithium aluminium hydride; aluminium chloride anhydrous; diethyl ether |
|
| 95 % Chromat. |
With (Ppyz)Zr(BH4)2Cl2 In diethyl ether for 2.5h; Heating; |
|
|
With 1,3-bis-(diphenylphosphino)propane; Cs2CO3; isopropanol In toluene at 80℃; for 15h; |
|
|
Multi-step reaction with 2 steps
1: [RhCl(C2H4)2]2; tris(2,2'',6,6''-tetramethyl-m-terphenyl-5'-yl)phosphane; tridecane / benzene / 6 h / 50 °C
2: HCl / methanol |
|
|
Multi-step reaction with 3 steps
1: 1.) lithium diisopropylamide / 1.) THF, -78 deg C
2: H2 / rhodium cationic complex with (R)-1-<(S)-1',2-bis(diphenylphosphino)ferrocenyl>ethanol <(R)-(S)-BPPFOH> / benzene / 170 h / 20 °C / 3800 Torr
3: 1.) MeLi 2.) H3O(1+) / 1.) ether |
|
| 92 %Chromat. |
With isopropanol at 89.84℃; for 2h; Inert atmosphere; |
|
|
With di-μ-chlorobis-[(η6-p-cymene)chlororuthenium(II)]; glycerol; potassium hydroxide at 70℃; for 20h; |
|
|
With sodium tetrahydridoborate In methanol at 20℃; |
|
| 67 %Chromat. |
With Lactobacillus brevis alcohol dehydrogenase; isopropanol; NADPH; magnesium(II) chloride In Tris-HCl buffer at 30℃; for 24h; Enzymatic reaction; |
|
|
With lithium aluminium hydride Inert atmosphere; |
General remarks
General procedure: All reactions were carried out using Schlenk techniques. Proline derived ligands 3a-3c and 3e-k were prepared from Boc-L-proline and the corresponding commercially available amines, as described in the literature[i]. [RuCl2 (p-cymene)]2 and (1R,2S)-(+)-cis-1-amino-indanol 3d were purchased. Racemic alcohols 2a-m were prepared by LiAlH4 reductions of the corresponding ketone. Other reagents are commercially available. Products were purified by preparative thin layer chromatography using plates prepared from silica gel. Bruker AM 250 spectrometer, operating at 250 MHz for 1H, and at 62.5 MHz for 13C, was used for the NMR spectra which are referenced to the solvent as internal standard. Infrared spectra were recorded in CHCl3 solution using CaF2 cells on a Perkin-Elmer 1000 FT-IR spectrometer. HRMS were measured with a Thermo-Finnigan-Mat 95 spectrometer. Optical rotations were determined using a Perkin-Elmer 241 Polarimeter at room temperature using a cell of 1 dm length and l = 589 nm. Data are reported as follows: [a]D20 (concentration in g/100 mL, solvent). Reactions were monitored by gas chromatography analysis on apparatus Fisons 8000 equipped with column β-P1. Enantiomeric excesses of alcohols were determined by gas chromatograph analysis on Fisons 9000 apparatus equipped with Chiraldex β-PM column. For the separation of the enantiomers of the mixture of alcohols 2a-g, the program was as follows: oven temperature was maintained at 50°C during 30 min, then heated to 100°C (5°C/min) maintained at 100°C during 65 min, then heated to 120°C (5°C/min) and maintained at 120°C during 100 min. |
| 64 %Chromat. |
With anhydrous sodium carbonate; isopropanol at 82℃; for 6h; Inert atmosphere; |
|
|
With glucose dehydrogenase; D-glucose; (R)-specific alcohol dehydrogenase from Candida maris IFO10003; NADH In dimethyl sulfoxide at 30℃; for 17h; aq. phosphate buffer; Enzymatic reaction; |
|
|
With Thermoanaerobacterethanolicus alcohol dehydrogenase; NADH at 30℃; for 0.0166667h; Enzymatic reaction; |
|
|
With bis[1-butyl-2-(diphenylphosphanyl)-3-methylimidazolium]tetrachloridoruthenium(III) hexafluorophosphate; potassium-t-butoxide; isopropanol at 100℃; for 2h; Inert atmosphere; Autoclave; |
|
|
With [{(CH3)2C3HN2-C5H3N-C3H3N2}RuCl2(PPh3)]; potassium isopropoxide; isopropanol at 82℃; for 0.00277778h; Inert atmosphere; |
|
| 100 %Chromat. |
With formic acid; C25H26ClIrN2; anhydrous sodium formate In water monomer at 80℃; for 12h; Inert atmosphere; |
|
|
With Yarrowia lipolytica short chain dehydrogenase/reductase; NADPH; magnesium(II) chloride In aq. buffer at 28℃; for 0.166667h; Enzymatic reaction; |
General procedure: Unless otherwise stated, purified tagged YlSDR (1-10μM) was assayed in 50mM Tris-HCl containing 2mM MgCl2, pH 8.0, 10mM substrate (for lipophilic substrates, additional 0.15% Tween 20) and 0.75mM NADPH. The decrease of absorbance at 340nm was monitored at 28°C for 10min. The reported values represent the average of at least four measurements with appropriate blanks substracted. One activity unit is defined as the amount of enzyme catalyzing the oxidation of 1μM of NADPH per minute. Kinetic parameters for reduction were determined at pH 5.0. |
|
With potassium-t-butoxide; isopropanol at 100℃; for 8h; Autoclave; Inert atmosphere; Green chemistry; |
|
|
With [ruthenium(II)(η6-benzene)(chloride)(NC5H4CH2SeC6H5)](hexafluorophosphate); potassium hydroxide In isopropanol at 80℃; for 2h; Reflux; |
|
| 98 %Chromat. |
Stage #1: hexyl-methyl-ketone With methanol; Octanal; Ru<SUB>nano</SUB>HAP at 30℃; for 0.5h; Flow reactor; Inert atmosphere;
Stage #2: With hydrogen at 40℃; Flow reactor;
Stage #3: With water monomer at 80℃; for 1h; Flow reactor; Inert atmosphere; chemoselective reaction; |
|
|
With C24H29ClRhSe2(1+)*F6P(1-); potassium hydroxide In isopropanol; acetonitrile at 80℃; for 5h; |
|
|
With diphenyl sulfide; isopropanol at 90℃; Inert atmosphere; |
|
| 98 %Chromat. |
With sodium hydroxide In isopropanol at 82℃; for 1h; |
2.3. Transfer hydrogenation of carbonyl compounds
General procedure: In a typical procedure, a 5 mg (0.77 mol%) of RuO2/MWCNT and 80 mg (2 mmol) of NaOH were stirred with 5 mL of i-PrOH taken in an ace pressure tube equipped with a stirring bar. Then the substrate (1 mmol) was added to the stirring solution and then the mixture was heated at 82°C. The completion of the reaction was monitored by GC. After the reaction, the catalyst was separated out from the reaction mixture by simple centrifugation and the products and unconverted reactants were analyzed by GC without any purification. Selectivity of the product for each reaction was alsocalculated. Finally, the separated RuO2/MWCNT was washed well with diethyl ether followed by drying in an oven at 60°C for 5 h and it was reused for the subsequent transfer hydrogenation of carbonyl compounds to investigate the reusability of the RuO2/MWCNT. |
| 59 %Chromat. |
With platinum on activated charcoal; hydrogen In n-heptane at 120℃; for 1h; Autoclave; |
|
|
With potassium-t-butoxide In isopropanol at 90℃; for 0.533333h; Flow reactor; Inert atmosphere; |
|
| 96 %Spectr. |
With Cp*Ir(oF-BPI)Cl; potassium hydroxide In isopropanol at 80℃; for 7h; Schlenk technique; Inert atmosphere; |
|
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