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CAS No. : | 135145-34-5 | MDL No. : | MFCD08458908 |
Formula : | C8H9ClO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | QYUQVBHGBPRDKN-LURJTMIESA-N |
M.W : | 156.61 | Pubchem ID : | 6950741 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501 | UN#: | |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate; dihydrogen peroxide; (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl; benzo[1,3,2]dioxaborole 1.) DME, -78 deg C, 2 h, 2.) DME, RT, 3 h; Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts; | ||
With sodium hydroxide; dihydrogen peroxide; benzo[1,3,2]dioxaborole 1.) DME, - 78 deg C, 2 h; 2.) room temp., 3 h; Yield given. Multistep reaction. Title compound not separated from byproducts; | ||
With potassium fluoride; trichlorosilane; dihydrogen peroxide; potassium hydrogencarbonate 1) 0 deg C, 36 h; Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts; |
With bis(norbornadiene)rhodium(l)tetrafluoroborate; C67H63N2O7P; C67H63N2O7P; diethylzinc; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In tetrahydrofuran at 0 - 20℃; Inert atmosphere; optical yield given as %ee; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In tetrahydrofuran at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With bis(1,5-cyclooctadiene)diiridium(I) dichloride; C37H35FeN2P; hydrogen; potassium carbonate In methanol at 20℃; for 12h; Glovebox; Autoclave; enantioselective reaction; | General procedure for asymmetric hydrogenation of ketones General procedure: In a nitrogen-filled glovebox, a stainless steel autoclave was charged with [Ir(COD)Cl]2(3.4 mg, 0.005 mmol) andL2(6.6 mg, 0.11 mmol) in 1.0 mL of dry MeOH. After stirring for 1h at room temperature, a solution of the substrates1(1.0 mmol) andK2CO3(6.9 mg, 0.05 mmol) in 2.0 mL of MeOH was added to the reaction mixture, and then the hydrogenation was performed at room temperature under an H2pressure of 20 bar for 12 h. The solvent was then evaporated and the residue was purified by flash column chromatography to give the corresponding hydrogenation product which was analyzed by chiral HPLC to determine the enantiomeric excesses. |
With borane; 1,1-diphenyl-L-valinol In tetrahydrofuran Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With potassium hydroxide; RuCl2<(S)-TolBINAP>; hydrogen; (S)-1-isopropyl-2,2-bis(4-methoxyphenyl)ethylenediamine In isopropyl alcohol at 11 - 30℃; for 1h; Yield given. Yields of byproduct given. Title compound not separated from byproducts; |
With dimethylsulfide borane complex; (4R,5R)-2-methyl-4-phenyl-5-methoxymethyl-1,3,2-oxazaborolidine In tetrahydrofuran; toluene at 22℃; for 0.166667h; Title compound not separated from byproducts; | ||
With potassium isopropoxide; isopropyl alcohol at 82℃; for 22h; Title compound not separated from byproducts; | ||
With potassium hydroxide; polymerised rhodium In isopropyl alcohol for 3h; Title compound not separated from byproducts; | ||
Stage #1: 3'-Chloroacetophenone With aluminum isopropoxide; (Ra)-5,6,7,8,5',6',7',8'-octahydro-[1,1']binaphthalenyl-2,2'-diol In dichloromethane at 20℃; for 0.5h; Stage #2: With dimethylsulfide borane complex In dichloromethane at 40℃; for 0.166667h; Title compound not separated from byproducts; | ||
With copper (II)-fluoride; phenylsilane; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) In toluene at 20℃; for 24h; Title compound not separated from byproducts; | ||
With sodium hydroxide; isopropyl alcohol for 1h; Heating; Title compound not separated from byproducts; | ||
With isopropyl alcohol at 20℃; for 76h; Title compound not separated from byproducts; | ||
With (R,R,R,R)-N,N,N',N'-(2-OH-2-(Ph)ethyl)4-1,3-xylylenediamine; SmI(η8-cyclooctatetraene)(thf); isopropyl alcohol at 25℃; for 24h; Title compound not separated from byproducts; | ||
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; sodium formate; ephedrine hydrochloride at 20℃; Title compound not separated from byproducts; | ||
With potassium <i>tert</i>-butylate; hydrogen In propan-1-ol at 25℃; for 10h; Title compound not separated from byproducts; | ||
With potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 0℃; for 8h; Title compound not separated from byproducts; | ||
With Cyanidioschyzon merolae 10D cultured cells In water at 42℃; for 72h; Irradiation; Title compound not separated from byproducts; | ||
With potassium <i>tert</i>-butylate; isopropyl alcohol at 20℃; for 3h; Title compound not separated from byproducts; | ||
With potassium <i>tert</i>-butylate; hydrogen In dichloromethane; isopropyl alcohol for 8h; cooling; Title compound not separated from byproducts; | ||
With (1R,2R)-PhCH(NH2)CH(Ph)NH-p-SO2-C6H4-CH2CH2-silica gel; tetrabutylammomium bromide; sodium formate at 40℃; Title compound not separated from byproducts; | ||
Stage #1: 3'-Chloroacetophenone With copper (II)-fluoride; phenylsilane; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) In toluene at 20℃; for 8h; Stage #2: With hydrogenchloride Further stages. Title compound not separated from byproducts.; | ||
With potassium hydroxide; isopropyl alcohol at 25℃; for 1.3h; Title compound not separated from byproducts.; | ||
With potassium hydroxide In isopropyl alcohol at 25℃; for 5h; Title compound not separated from byproducts.; | ||
With trichlorosilane In toluene at -20℃; for 16h; Title compound not separated from byproducts.; | ||
With potassium hydroxide; Butane-1,4-diol at 40℃; for 24h; Title compound not separated from byproducts.; | ||
With triethylamine In formic acid at 25℃; for 1h; Title compound not separated from byproducts.; | ||
With formic acid; N-{2-[(biphenyl-2-ylmethyl)amino]-1R,2R-diphenylethyl}-4-methylbenzenesulfonamide chloro ruthenium; triethylamine In formic acid; triethylamine at 28℃; for 24h; Inert atmosphere; optical yield given as %ee; | ||
Stage #1: 3'-Chloroacetophenone With polymethylhydrosiloxane; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) In toluene at 20℃; for 24h; Inert atmosphere; Stage #2: With tetrabutyl ammonium fluoride; water In tetrahydrofuran; diethyl ether for 0.5h; optical yield given as %ee; enantioselective reaction; | ||
With lithium hydroxide; hydrogen; triphenylphosphine; iridium; (8R,9R)-9-amino(9-deoxy)epicinchonin In methanol at 40℃; for 10h; optical yield given as %ee; enantioselective reaction; | ||
Stage #1: 3'-Chloroacetophenone With aluminum(III) nitrate nonahydrate; sodium hydroxide; polymethylhydrosiloxane; copper(II) nitrate trihydrate; sodium carbonate; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) In toluene at 20℃; Inert atmosphere; Stage #2: With tetrabutyl ammonium fluoride In tetrahydrofuran; diethyl ether for 0.5h; | ||
With trans-(R, R)-[Fe(Ph2PCH2CH=NCH(Ph)CH(Ph)N=CHCH2PPh2)(CH3CN)(CO)][BPh4]2; potassium <i>tert</i>-butylate In isopropyl alcohol at 22℃; for 0.216667h; Inert atmosphere; optical yield given as %ee; | ||
With C64H60Cl2N2O2P2Ru; potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 25 - 28℃; for 10h; optical yield given as %ee; enantioselective reaction; | ||
With sodium hexaflorophosphate; bis(1,5-cyclooctadiene)diiridium(I) dichloride; (αS,αS)-1,1'-bis[α-(dimethylamino)benzyl]-(R,R)-2,2'-bis(dicyclohexylphosphino)ferrocene; isopropyl alcohol; sodium t-butanolate at 40℃; for 3h; Inert atmosphere; | ||
Stage #1: 3'-Chloroacetophenone With polymethylhydrosiloxane; copper(II) ferrite; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) In toluene at 20℃; for 8h; Stage #2: With tetrabutyl ammonium fluoride; water In tetrahydrofuran; diethyl ether; toluene for 0.5h; optical yield given as %ee; enantioselective reaction; | ||
With Aspergillus terreus SSP 1498 In glycerol at 32℃; for 48h; aq. phosphate buffer; Microbiological reaction; optical yield given as %ee; enantioselective reaction; | ||
With trans-(R,R)-[Fe(NCMe)(CO)(diph-ethP2N2)][BF4]2; potassium <i>tert</i>-butylate; isopropyl alcohol at 20℃; for 0.5h; Inert atmosphere; optical yield given as %ee; | ||
With C32H12BF24(1-)*C41H57IrN3O(1+); potassium <i>tert</i>-butylate; isopropyl alcohol at 20℃; for 20h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 20℃; for 15h; optical yield given as %ee; enantioselective reaction; | ||
Stage #1: 3'-Chloroacetophenone With (BOPA-dpm)H; iron(II) acetate In tetrahydrofuran at 65℃; Inert atmosphere; Stage #2: With diethoxymethylane In tetrahydrofuran at 65℃; optical yield given as %ee; | ||
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; Butane-1,4-diol; N-[(1S,2S)-2-amino-1,2-diphenylethyl]-4-methylbenzenesulfonamide; potassium hydroxide at 40℃; for 72h; optical yield given as %ee; | ||
With C40H58Cl2FeN4O6P2; potassium <i>tert</i>-butylate; isopropyl alcohol at 22 - 24℃; for 1h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With hydrogen; potassium hydroxide; 9-amino-9-deoxyepicinchonine In isopropyl alcohol at 40℃; for 5h; Autoclave; optical yield given as %ee; enantioselective reaction; | ||
With potassium <i>tert</i>-butylate; hydrogen In isopropyl alcohol at 20℃; for 24h; Autoclave; optical yield given as %ee; enantioselective reaction; | ||
Stage #1: 3'-Chloroacetophenone With (S,S)-(BOPA-dpm)FeCl2; zinc In tetrahydrofuran at 65℃; for 1h; Inert atmosphere; Stage #2: With Triethoxysilane In tetrahydrofuran at 65℃; for 48h; Inert atmosphere; Stage #3: With potassium fluoride; tetrabutyl ammonium fluoride In tetrahydrofuran; methanol Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
Stage #1: 3'-Chloroacetophenone With copper acetylacetonate; (S)-Xyl-P-Phos In toluene at -20℃; for 12h; Stage #2: With sodium hydroxide In water; toluene for 3h; optical yield given as %ee; stereoselective reaction; | ||
Multi-step reaction with 2 steps 1: sodium tetrahydroborate / ethanol / Inert atmosphere 2: bis(1,5-cyclooctadiene)diiridium(I) dichloride; bis(triphenylphosphine)iminium chloride; acetone; potassium hydroxide; N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane / dichloromethane; water; isopropyl alcohol / 6 h / 18 °C / Resolution of racemate; Inert atmosphere | ||
With bis(triphenylphosphine)carbonyliridium(I) chloride; (R)-N,N'-bis[2-(piperidin-1-yl)benzylidene]propane-1,2-diamine; potassium hydroxide In isopropyl alcohol at 75℃; for 5h; optical yield given as %ee; enantioselective reaction; | ||
With chlorobis(cyclooctene)-iridium(I) dimer; (S)-N-(2-(tert-butylsulfinyl)benzyl)-1-(pyridin-2-yl)methanamine; potassium <i>tert</i>-butylate; isopropyl alcohol In dichloromethane at 20℃; for 3h; optical yield given as %ee; stereoselective reaction; | ||
With dichloro(benzene)ruthenium(II) dimer; (1<i>Ξ</i>,4<i>R</i>)-1-benzylamino-<i>p</i>-menth-8-en-2-one oxime; potassium hydroxide In isopropyl alcohol at 80℃; for 3h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With (S,S)-DPENDS; C36H24Cl2O18P2RuS6(6-)*6Na(1+); hydrogen; potassium hydroxide In water at 30℃; for 3h; Autoclave; optical yield given as %ee; enantioselective reaction; | 4.2. Typical procedure for asymmetric hydrogenation of aromatic ketones General procedure: To a 60 mL stainless autoclave with a glass liner and magnetic stirrer were added PEG-400, H2O, RuCl2(TPPTS)2, (S,S)-DPENDS, KOH, and reactant. Hydrogen was introduced to the desired pressure after the reaction mixture had been purged with H2 five times. The products were extracted by n-hexane and analyzed by GC-960 with a FID detector and β-DEX120 capillary column (30 m × 0.25 mm, 0.25 μm film) at 115 °C. The enantiomeric excess (ee value) was calculated from the equation: ee (%) = 100 × (R - S)/(R + S). | |
79 % ee | With formic acid; C23H32ClN2O2RuS; triethylamine In acetonitrile at 20℃; for 96h; enantioselective reaction; | 4.1.7 General procedure for ketones reduction using catalysts 5-7 General procedure: To a ketone (2.4 mmol) placed in a vial 1 mL of CH3CN solution of the preformed ruthenium catalyst (24 μmol) and formic acid/triethylamine azeotropic mixture (1 mL) were added. The mixture was then stirred at room temperature and the progress of the reaction was monitored by TLC until the specified conversion was achieved. After evaporation of the solvents, 4 mL of CH2Cl2 and 1.5 mL of 10% aqueous HCl solution were added to the residue. The layers were separated and the water layer was extracted twice with 2 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and the solvent was evaporated in vacuo. The residual oil was purified by column chromatography on silica gel using chloroform (dried over CaCl2) as eluent to afford the appropriate alcohol. The enantiomeric excess was determined by GC analysis using a Supelco cyclodextrin β-DEX 120 capillary column (20 m × 0.25 mm ID and 0.25 μm film thickness). The results of the reduction are summarized in Table 1. |
82 % ee | With formic acid; C23H30ClN2O2RuS; triethylamine In acetonitrile at 20℃; for 18h; | General procedure for ketone reduction using catalysts 12-18 General procedure: To a ketone (2.4 mmol) placed in a vial, 1 mL of CH3CN solution of preformed ruthenium catalyst (24 lmol) and formic acid/triethylamine azeotropic mixture (1 mL) were added. The mixture was then stirred at room temperature and the progress of the reaction was monitored by TLC until the specified conversion was achieved. After evaporation of the solvents, 4 mL of CH2Cl2 and 1.5 mL of 10% aqueous HCl solution were added to the residue. The layers were separated and the water layer was extracted twice with 2 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and the solvent was evaporated in vacuo. The oily residue was purified by column chromatography on silica gel using chloroform (dried over CaCl2) as eluent to afford the appropriate ketone. The enantiomeric excess was determined by GC analysis using a Supelco cyclodextrinb-DEX 120 capillary column (20 m 0.25 mm I.D. and 0.25 lm film thickness). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With borane-THF In tetrahydrofuran; toluene at 20℃; for 0.666667h; | |
99% | With formic acid; triethylamine at 28 - 40℃; enantioselective reaction; | |
98% | With AMBERLITE XAD-7; Geotrichum candidum IFO 4597 In lithium hydroxide monohydrate at 30℃; for 24h; |
98% | With sodium tertiary butoxide; <i>tert</i>-butyl alcohol; (S)-2,2',6,6'-tetramethoxy-4,4'-bis(di(3,5-xylyl)phosphino)-3,3'-bipyridine In toluene at 20℃; for 14h; enantioselective reaction; | |
98% | With di-μ-chlorobis[(1,2,5,6-η)-1,5-cyclooctadiene]diiridium; hydrogen; C41H44N3O3P; barium(II) hydroxide In ethanol at 40℃; for 1h; Autoclave; enantioselective reaction; | |
97% | With bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride; hydrogen; C41H43N2O4P; barium(II) hydroxide In methanol at 30℃; for 2h; enantioselective reaction; | |
96% | With dodecacarbonyltri-iron; C52H58N4P2; hydrogen; potassium hydroxide In methanol at 45℃; for 5h; enantioselective reaction; | |
95% | With potassium hydroxide; <RuCl2(mesitylene)>2 (1S,2S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine In isopropanol for 8h; Ambient temperature; | |
93% | With Debaryomyces hansenii P1 at 30℃; for 48h; Microbiological reaction; enantioselective reaction; | |
91% | With 2-(N-morpholino)ethanesulfonic acid buffer; nadide; isopropanol for 24h; Ambient temperature; acetone powder of Geotrichum candidum IFO4597(APG4); in the dark; | |
91% | With 2-(N-morpholino)ethanesulfonic acidbuffer; nadide; isopropanol at 30℃; for 20h; acetone powder of Geotrichum candidum; | |
89% | With Lactobacillus paracasei BD101 In aq. buffer at 30℃; for 48h; Microbiological reaction; enantioselective reaction; | |
88% | With n-hexan-2-ol In hexane; lithium hydroxide monohydrate at 30℃; for 24h; immobilized Geotrichum candidum; | |
83% | In lithium hydroxide monohydrate at 30℃; for 5h; Geotrichum candidum IFO4597 on a diluted medium (glycerol, yeast extract, polypeptone); | |
82% | With nadide; Sodium hydrogenocarbonate; isopropanol In carbon dioxide at 35℃; for 5h; Supercritical conditions; MES buffer; Enzymatic reaction; optical yield given as %ee; enantioselective reaction; | |
80% | With D-glucose at 35℃; for 36h; Tris buffer; Microbiological reaction; Enzymatic reaction; optical yield given as %ee; enantioselective reaction; | 4.6. Preparative scale production General procedure: The preparative scale (large scale) production of (S)-1-phenylethanol 1b from acetophenone 1a by immobilized C. laurentii EBK-19 cells was also achieved. The reduction of 1a was carried out in a 1000-mL Erlenmeyer flask using beads prepared as described in Section 4.4. The cells were activated by suspending the beads in 300 mL tris buffer containing 4% glucose. After cell activation (3 h), acetophenone 1a (6 mM) was directly added to the mixture. During the 36 h reaction period, the beads were regularly separated by filtration, resuspended in tris buffer and glucose and reused for the same reaction without washing. At regular time intervals (36 h), the conversion and enantiomeric excess (ee) of the product were determined and the yields calculated. The run time of the beads was optimized for the production of 1b and found to be 27 days. |
80% | With Lactobacillus kefiri P2 at 25℃; for 64h; Green chemistry; Enzymatic reaction; enantioselective reaction; | General asymmetric bioreduction process General procedure: Lactobacillus kefiri P2 was added from its glycerol stock by inoculation to 10mL MRS mixture (MgSO4.7H2O 11.5% (w/v), K2HPO4 2 g/L, pepton [Oxoid] 10 g/L, yeast extract 2% glucose, [Difco] 5 g/L, C2H3NaO2.3H2O 5 g/L, salt solution [MgSO4.7H2O 11.5% (w/v), triamonium citrate 2 g/L], Tween 80 1 mL/L) followed by 48 h growth at 37 °C. From this mixture, overnight grown bacterial cells were inoculated to 100m LMRS mixture at 10% concentration. Then, pH of medium was adjusted to 4.5 with 1M HCI. This mixture was shaken for 2 hours, and then 1 mmol of substrate (1-16) was directly added to this mixture and incubated on an orbital shaker at 150 rpm with an incubation temperature of 25 °C for 64 h incubation period. After the catalytic reaction was complete, the supernatant was separated. The aqueous phase was saturated with NaCI and extracted with dichloromethane. After the organic phases were combined, they were dried over anhydrous Na2SO4 and filtered to remove the salt. The liquid was removed in a vacuum to remove dichloromethane and the crude product was characterizedby NMR analysis. After the crude product was purified using column chromatography, ee was determined using chiral HPLC. The absolute configurations of the alcohols were determined by comparing the literature values of the specific rotation. |
79% | With D-glucose In lithium hydroxide monohydrate at 32℃; for 24h; Microbiological reaction; optical yield given as %ee; enantioselective reaction; | |
77% | With acetophenone reductase from Geotrichum candidum NBRC 4597; nadide; isopropanol In aq. buffer at 30℃; for 14h; Enzymatic reaction; enantioselective reaction; | 1.6 Preparative scale reduction of 2a-13a by GcAPRD wild type and Trp288Ala General procedure: Reductions were performed in 50 mL of 100 mM HEPES-NaOH buffer (pH 7.2) consisting of1.4 mM NAD+, 0.23-0.39 mmol of 2a-13a, cofactor regeneration reagent written in Table S1, and purified GcAPRD with the amount written in Table S1. Reactions were done for 14 h at 30°C with a rotational speed of 130 rpm. The product was extracted with diethyl ether, dried over MgSO4, and evaporated under reduced pressure. Silica gel column chromatography (hexane:ethyl acetate 4:1) were performed to give the corresponding chiral alcohols 2b-13b. |
75% | With n-hexan-2-ol; Geotrichum candidum IFO 4597 cells on BL-100 polymer In hexane at 30℃; for 24h; | |
75% | With C23H31ClN2O2RuS; potassium hydroxide In isopropanol at 24 - 25℃; for 24h; | |
74% | Stage #1: 1-(3-chlorophenyl)ethan-1-one With (1R,2R)-N,N’-bis(3,5-di-tert-butylbenzyl)-1,2-diphenylethane-1,2-diamine; methyldiethoxysilane; Zinc acetate In tetrahydrofuran at 25℃; for 24h; Inert atmosphere; Stage #2: With hydrogenchloride; lithium hydroxide monohydrate In tetrahydrofuran for 1h; enantioselective reaction; | |
73% | With Alternaria alternata EBK-4 In various solvent(s) at 28℃; for 24h; Microbiological reaction; | |
66% | With D-(+)-glucose In aq. phosphate buffer at 25℃; for 24h; Sealed tube; enantioselective reaction; | 3.4. Reduction of Ketones General procedure: Reactions were all performed in 50-mL screw-capped plastic vials to prevent evaporation ofketones/alcohols. The reaction mixture contained 3 g of free resting cells (0.3 g/mL) or 4.5 gof immobilized cells (0.45 g/mL), 0.5 g of glucose in 10 mL Na2HPO4-KH2PO4 buffer (100 mM,pH 7.0), with the substrates of the final concentration of 10 mM. The solution was shaken at 25 Cfor 24 h. After separating from the cells by centrifugation, 2 mL of the obtained supernatant wassaturated with NaCl, and extracted with n-hexane/i-PrOH (95/5, v/v, 2 1 mL). The obtained organiclayer was dried over Na2SO4 and injected into HPLC for yield and ee measurement. |
64% | With (S)-selective alcohol dehydrogenase whole-cell lyophilisate In aq. buffer enantioselective reaction; | |
44% | With seeds of Bauhinia variegata L. (Fabaceae) In lithium hydroxide monohydrate; dimethyl sulfoxide at 40℃; for 48h; Green chemistry; enantioselective reaction; | |
37% | With Synechococcus sp. PCC 7942 at 20℃; for 72h; Irradiation; | |
26% | With fruits of Ligustrum lucidum (glossy privet) In aq. phosphate buffer; dimethyl sulfoxide at 20℃; for 144h; enantioselective reaction; | |
With [N-[(1S,2S)-2-(amino-κN)-1,2-diphenylethyl]-4-methylbenzenesulfonamidato-κN]chloro[(1,2,3,4,5,6-η)-1-methyl-4-(1-methylethyl)benzene]ruthenium; formic acid; triethylamine at 28℃; for 21h; Yield given; | ||
With D-glucose; D-glucose dehydrogense; Pyrococcus furiosus alcohol dehydrogenase In dimethyl sulfoxide at 37℃; | ||
With 1,4-dihydronicotinamide adenine dinucleotide; (S)-alcohol dehydrogenase; formate dehydrogenase from C. boidini; Rhodococcus erythropolis (E.coli) In phosphate buffer Enzymatic reaction; | ||
With 1,4-dihydronicotinamide adenine dinucleotide; (S)-alcohol dehydrogenase from Rhodococcus erythropolis In phosphate buffer at 30℃; | ||
With D-glucose; D-glucose dehydrogenase; NADPH In dimethyl sulfoxide at 20℃; | ||
With C49H57ClFeN2OsP2; potassium-t-butoxide; hydrogen In methanol at 60℃; for 1h; optical yield given as %ee; enantioselective reaction; | ||
With Aspergillus terreus SSP 1498 at 32℃; for 48h; aq. phosphate buffer; Microbiological reaction; optical yield given as %ee; enantioselective reaction; | ||
With carrot (Daucus carota L.) In ethanol; lithium hydroxide monohydrate at 33℃; for 28h; Enzymatic reaction; optical yield given as %ee; enantioselective reaction; | ||
With phenylsilane; copper (II) acetate; (S)-2,2',6,6'-tetramethoxy-4,4'-bis(di(3,5-xylyl)phosphino)-3,3'-bipyridine In toluene at -20℃; for 12h; stereoselective reaction; | ||
With ADH-A from Rhodococcus ruber; NAD<SUP>+</SUP> In aq. phosphate buffer; isopropanol at 30℃; for 72h; enantioselective reaction; | ||
99.9 % ee | With 5'-GGTATTGAGGGTCGCGCGGGCGCGGGCGCGATGTCAATTCCATCAAGCCAGTACGGATT-3'; nicotinamide adenine dinucleotide; anhydrous zinc chloride In aq. phosphate buffer at 30℃; for 0.05h; stereoselective reaction; | |
> 99.9 % ee | With tripotassium phosphate tribasic; Candida parapsilosis aldo-keto reductase CPAR4; NADPH at 30℃; for 8h; Enzymatic reaction; enantioselective reaction; | 2.7 Asymmetric reduction of carbonyl compounds General procedure: Asymmetric reductions of various carbonyl compounds by the purified enzymes were carried out at 30°C for 8h with mild shaking in a reaction mixture containing 0.1M potassium phosphate buffer (pH 6.5), 1gL-1 substrate, 10mM NADPH, and the purified enzyme of appropriate amount in a total volume of 2mL. In order to determine the absolute configuration of chiral alcohols, the reaction products were extracted with ethyl acetate or hexane and the organic layer was used for analysis. The optical purity of the reaction products were determined by chiral HPLC (HP 1100, Agilent, USA) equipped with Chiralcel OB-H column (4.6mm×250mm; Daicel Chemical Ind. Ltd., Japan) or chiral GC (7890A, Agilent, USA) equipped with FID detector and Chrompack Chirasil-Dex CB chiral capillary column (25m×0.25mm; Varian, USA) [21]. |
99 %Chromat. | With alcohol dehydrogenase from Escherichia coli In isopropanol at 30℃; for 24h; Enzymatic reaction; stereoselective reaction; | |
>99% ee | With glucose; glucose dehydrogenase from Bacillus subtilis CGMCC 1.1398; medium-chain dehydrogenase from Kuraishia capsulate CBS1993; nadide In aq. phosphate buffer for 16h; Enzymatic reaction; enantioselective reaction; | Substrate scope and enantioselectivity determination General procedure: Substrate scope and enantioselectivity determination The relative activities of 26 substrates were measured using thepreviously described assay protocol with adjusted ratio of enzymeand substrate concentration. The a-chloroacetophenone activitywas assumed 100%.Enantioselectivity was determined by examining the reductionof aromatic ketones using an NADH-regeneration system consist-ing of the puried KcDH and glucose dehydrogenase (GDH) fromBacillus subtilis CGMCC 1.1398. The 1-mL reaction mixture con-tained 0.5 mM NAD+, 10 mM ketone, 1 U KcDH, 50 mg glucoseand 2 U GDH in 50 mM potassium phosphate buffer (pH 7.0). After16 h, the reaction sample was equally separated into two parts,with one terminated by adding an equal volume of methanol, fol-lowed by HPLC analysis to determine the conversion ratio, and theother extracted with ethyl acetate, followed by ee analysis. Meth-ods used for analysing chiral products using HPLC or GC aredescribed in Supplementary Table S1. |
Multi-step reaction with 2 steps 1: (1R,2R)-N,N’-bis(3,5-di-tert-butylbenzyl)-1,2-diphenylethane-1,2-diamine; Zinc acetate / neat (no solvent) / 6 h / 25 °C / Inert atmosphere; Sealed tube 2: N,N,N-tributylbutan-1-aminium fluoride / tetrahydrofuran / 0.08 h / 0 °C / Inert atmosphere | ||
95 % ee | With N,N'-((1S,2S)-cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)benzamide); ruthenium(III) trichloride hydrate; hydrogen; anhydrous sodium carbonate In methanol at 20℃; for 22h; Autoclave; enantioselective reaction; | |
98 %Chromat. | With C50H47Cl2N6O5PRuS2; potassium isopropoxide; isopropanol at 28℃; for 0.0333333h; Inert atmosphere; enantioselective reaction; | |
With D-glucose; NADH In aq. phosphate buffer; dimethyl sulfoxide at 30℃; Enzymatic reaction; | 1.A Step A: (S)-1-(3-chlorophenyl)ethanol A stock solution of 9 g Glucose (25 g/L), 1.10 g ADH-RE (3 g/L), 360 mg NAD (1 g/L), 720 mg GDH (2 g/L), and 360 mg LDH (1 g/L) in 360 mL 0.1M phosphate buffer was prepared beforehand. 90 mL of the stock solution was quickly added to a solution of 1-(3-chlorophenyl)ethanone (1.0 g, 6.5 mmol) in 10 mL of DMSO, and stirred overnight at 30° C. The reaction showed >98% conversion and >99% e.e. by HPLC [ZORBAX Eclipse Plus C18 50×4.6 mm, 1.8 uM, 10% to 95% B (A=0.1% phosphoric acid, B=acetonitrile), 1.5 mL/min., 210 nM, 25C, 8 min. run time]; therefore, 100 mL of MTBE was added followed by 2 mL of 5N NaOH. The reaction was agitated, centrifuged, and separated. The aqueous layer was re-extracted with 50 mL of MTBE followed by agitation, centrifuge, and separation. The MTBE layers were combined and washed with 50 mL of brine, dried with Na2SO4, filtered, and concentrated in vacuo. The residue was purified by ISCO COMBIFLASH chromatography (12 g silica gel, 30 mL/min, 254 nM, 0% to 100% EtOAc/hexane over 24 CV. The desired product elutes at 22% EtOAc/hexane). | |
96 % ee | With di-μ-chlorobis[(1,2,5,6-η)-1,5-cyclooctadiene]diiridium; C49H67FeN2O2PS; hydrogen; lithium tert-butylate In isopropanol at 20℃; for 12h; Inert atmosphere; Autoclave; | 10 Preparation of 1-m-chlorophenylethanol from m-chloroacetophenone (S/C=10000) In a high-purity argon atmosphere, [Ir(COD)Cl]2 (3.4 mg, 0.005 mmol)The chiral ligand L6 (9.2 mg, 0.011 mmol) was dissolved in isopropanol (1 mL).Stirring for 3 hours at room temperature gives an orange clear solution. 20 μL (0.001 mol %) of the orange solution was taken with a micro syringe and added to m-chloroacetophenone (2 mmol),In a mixed system of isopropanol (2 mL) and lithium t-butoxide (1 mol %). Place the reaction system in an autoclaveStir at room temperature under H2 (20 atm) for 12 hours. Remove the solvent under reduced pressureColumn chromatography (silica gel column, eluent: ethyl acetate) to give pure 1-chlorobenzene-ethanol,The product was analyzed by HPLC and found to have an ee value of 96%. |
96 % ee | With di-μ-chlorobis[(1,2,5,6-η)-1,5-cyclooctadiene]diiridium; C49H67FeN2O2PS; hydrogen; lithium tert-butylate In isopropanol at 25 - 30℃; for 12h; Autoclave; enantioselective reaction; | |
88 %Chromat. | With tris-(dibenzylideneacetone)dipalladium(0); copper(I) thiophene-2-carboxylate; triethyl phosphite In isopropanol at 30℃; for 24h; | |
95 % ee | With hydrogen; C32H12BF24(1-)*C39H43IrN2P(1+) In isopropanol at 20℃; for 0.5h; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With C45H32I4O6; 1,1,1,3,3,3-hexamethyl-disilazane; In dichloromethane; at -30℃; for 2h; | The racemic alcohol (1s) at -30 C1.0 mmol as a catalyst was dissolved in 5 ml dichloromethane (wherein, R I andn is 2; and pharmaceutically acceptable salts thereof) compound of the formula(2) the addition of 0.01 mol% of potassium and fluoro one equivalent offluoride, a carboxylic acid group and the ion exchange resin 80 mg silylatingagent of formula (5), including (in the formula, R is methyl) wasadded to 0.7 equivalents, and then the mixture was stirred for 1 hour. Filteringthe mixture was concentrated and then to recover the potassium fluoride and theion exchange resin. The residue was purified by flash chromatography (acetone /hexane / triethylamine = 1: 5: 0.025) to give the chiral alcohol; to give the(2s, 46% yield 97% ee, (S) -form). |
46% | With potassium fluoride; C46H34I4O6; 1,1,1,3,3,3-hexamethyl-disilazane; In dichloromethane; at -30℃; | At -30C, racemic alcohol (1s) 1.0 mmol was dissolved in 5 ml dichloromethane, the compound of formula 2(wherein, R is I and n is 2; and pharmaceutically acceptable salts) 0.01 mol% as a catalyst and the addition of 0.7 eq., of silylating agent formula (5) (in the formula, R4 is methyl)and 1 equivalent of potassium fluoride and 80 mg of carboxylic acid group ion exchange resin was added and stirred for 1 hour. The mixture was filtered then concentrated to recover potassium fluoride and the ion exchange resin. The residue was purified by flash chromatography (acetone /hexane / triethylamine = 1: 5: 0.025) to give the chiral alcohol (2s, 46% yield 97% ee, (S)-form). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Geotrichum candidum IFO 4597 cells In water Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ox. m. Tl(III)-Acetat; | ||
Ox. m. Tl(III)-Acetat; | ||
Ox. m. Tl(III)-Acetat; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: Racemic secondary alcohols (0.25 mmol), catalyst (1.5 mol% of substrate), and KBr (0.02 mmol, 0.0024 g) were added to H2O(1.5 mL). The mixture was stirred for 10 min at room temperature, and then PhI(OAc)2 (0.175 mmol, 0.056 g) was added in four equal parts. The reaction progress was monitored by gas chromatography (GC). After achieving the desired oxidation level, the reaction mixture was heated to 40 ?C. The catalyst was precipitated out of the reaction system, washed with diethyl ether(3× 5 mL), dried in a vacuum, and finally recharged with fresh substrate, additive, and oxidant for the next catalytic cycle. The supernatants separated from the reaction system were extractedwith ether three times. The collected organic phase was driedover sodium sulfate and concentrated in a vacuum. The resultantmixture was purified by column chromatography on silica gel athe stationary phase (petroleum ether/ethyl acetate, 90/10). Enantioselectivitywas determined by a Agilent Technologies 6890NGC system equipped with a 19091G-B213 chiral capillary column(30 m×0.32 mm×0.25 m) with an FID. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium fluoride; dihydrogen peroxide; potassium hydrogencarbonate In tetrahydrofuran; methanol at 20℃; for 11h; | ||
With potassium fluoride; dihydrogen peroxide; potassium hydrogencarbonate In tetrahydrofuran; methanol for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With (R)-2,2'-dihydroxy-3,3'-di[(Me2N)2P(O)]-1,1'-binaphthyl In tetrahydrofuran; toluene at 20℃; for 72h; Title compound not separated from byproducts; | ||
With (R)-3,3'-bis[(Me2N)2P(=O)-]-BINOL In tetrahydrofuran; toluene at 20℃; for 72h; Title compound not separated from byproducts.; | ||
With (S)-(N-(ferrocenylmethyl)azetidin-2-yl)(diphenyl)methanol In toluene at 30℃; for 48h; Title compound not separated from byproducts.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis(acetylacetonate)nickel(II); biarylidene di-O-isopropylidene-α-D-glucofuranose phosphite In tetrahydrofuran at -20℃; for 1h; Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With titanium(IV) isopropylate; zinc(II) chloride In toluene at -78 - -30℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With bis(norbornadiene)rhodium(l)tetrafluoroborate; C67H63N2O7P; C71H71N2O7P; diethylzinc; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In tetrahydrofuran at 0 - 20℃; Inert atmosphere; optical yield given as %ee; | |
Multi-step reaction with 2 steps 1: HSiCl3; (R)-2-diphenylphosphino-1,1'-binaphthyl; [PdCl(η3-C3H5)]2 / toluene / 0 °C 2: aq. H2O2; KF; KHCO3 / tetrahydrofuran; methanol / 11 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 13 percent Chromat. / Geotrichum candidum IFO 4597 cells on BL-100 polymer; cyclohexanone / hexane / 24 h / 30 °C 2: Geotrichum candidum IFO 4597 cells / H2O |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 85 percent / diethyl ether / 0 °C 2: 1.) lithium diisopropylamide / 1.) THF, -78 deg C, 15 min, 2.) -78 deg C, 30 min 3: 89 percent / tetrahydrofuran / 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 1.) lithium diisopropylamide / 1.) THF, -78 deg C, 15 min, 2.) -78 deg C, 30 min 2: 89 percent / tetrahydrofuran / 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: dimethyl zinc(II) With (2S)-1-(ferrocenylmethyl)aziridin-2-yl(diphenyl)methanol In toluene at 0 - 40℃; Inert atmosphere; Stage #2: m-Chlorobenzaldehyde In toluene at 0 - 30℃; Stage #3: With water; ammonium chloride In toluene optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium perborate; water In tetrahydrofuran at 22℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydride In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With di-isopropyl azodicarboxylate; triphenylphosphine |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran; toluene at 20 - 50℃; Inert atmosphere; | 10.A (10A) Ethyl 3-{4-[(1R)-1-(3-chlorophenyl)ethoxy]phenyl}-3-ethoxypropionate Ethyl 3-ethoxy-3-(4-hydroxyphenyl)propionate (100 mg, 0.420 mmol) produced in Example 1 (1C) and (1S)-1-(3-chlorophenyl)ethanol (99 mg, 0.630 mmol) were dissolved in tetrahydrofuran (10 mL), and triphenylphosphine (178 mg, 0.680 mmol) and a 40% diethyl azodicarboxylate toluene solution (309 μL, 0.680 mmol) were added thereto at room temperature, and then, the resulting mixture was stirred under a nitrogen atmosphere at 50° C. for 4 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0 to 95:5 (v/v)), whereby the objective title compound was obtained as a yellow oily substance (142 mg, yield: 90%). 1H NMR (CDCl3, 400 MHz): δ1.12 (3H, t, J=7.1 Hz), 1.21 (3H, td, J=4.6, 7.3 Hz), 1.61 (3H, d, J=6.3 Hz), 2.52 (1H, dd, J=5.0, 15.2 Hz), 2.76 (1H, dd, J=8.9, 14.4 Hz), 3.27-3.37 (2H, m), 4.11 (2H, qd, J=2.8, 7.1 Hz), 4.62-4.66 (1H, m), 5.25 (1H, q, J=6.6 Hz), 6.81 (2H, d, J=9.0 Hz), 7.17 (2H, d, J=9.0 Hz), 7.22-7.30 (3H, m), 7.37 (1H, s) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C32H31Cl2N4OPRu; potassium isopropoxide at 30℃; for 0.333333h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride In water at 0℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 61 % ee 2: 61 % ee | With alkylsulfatase Pisa1 from Pseudomonas sp. DSM 6611; water at 30℃; for 24h; Enzymatic reaction; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 93 % ee 2: 93 % ee | With alkylsulfatase Pisa1 from Pseudomonas sp. DSM 6611; water In dimethyl sulfoxide at 30℃; for 24h; Enzymatic reaction; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrabutyl ammonium fluoride In tetrahydrofuran at 0℃; for 0.0833333h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: With tetrafluoroboric acid diethyl ether complex In dichloromethane at 0 - 20℃; for 3h; Stage #2: With potassium fluoride; dihydrogen peroxide; potassium hydrogencarbonate In tetrahydrofuran; methanol at 20℃; for 15h; | 2 Example 2: Production of product Chiral alcohol compound (Application example) General procedure: 20 mL of the reaction tube,A solution of 1a (0.087 g, 0.3 mmol) in dichloromethane (15 mL) was added and stirred at 0 ° C and addedHBF4 · Et2O(0.35 g, 1.6 mmol, 40% Wt). For 3 h,Spin the solvent and add it in sequenceTetrahydrofuran (3 mL),Methanol (3 mL),Potassium fluoride (0.07 g, 1.2 mmol),Potassium bicarbonate (0.30 g, 3.0 mmol),H2O2 (1.5 mL, 30% wt).Room temperature stirring 15h, diluted with water,Extracted with ether, washed with saturated brine, dried over anhydrous sodium sulfate, dried and dried over PE / EtOAc = 4/1 to give 0.048 g (0.24 mmol, 81% yield) of the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: triethylamine / dichloromethane / 0.75 h / 0 - 20 °C 2: potassium carbonate / acetonitrile / 17 h / 80 °C / Microwave irradiation 3: hydrogenchloride / 1,4-dioxane / 1 h / 70 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 0.75 h / 0 - 20 °C 2: potassium carbonate / acetonitrile / 17 h / 80 °C / Microwave irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine In dichloromethane at 0 - 20℃; for 0.75h; | 1.B Step B: (S)-1-(3-chlorophenyl)ethyl methanesulfonate Triethylamine (0.254 ml, 1.821 mmol) was added to a solution of (S)-1-(3-chlorophenyl)ethanol (0.1426 g, 0.911 mmol) in CH2Cl2 (2 ml), followed by Ms-Cl (0.085 ml, 1.093 mmol) at 0° C. After the addition, the reaction was allowed to warm to ambient temperature. The resulting mixture was stirred for 45 minutes. 1H NMR of an aliquot showed complete conversion to the desired product. The reaction was partitioned between EtOAc and water/brine. The organic layer was collected, dried over MgSO4, and concentrated in vacuo to give an oil which was used as is without further purification. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.28-7.43 (m, 4H), 5.73 (q, 1H), 2.82 (s, 3H), 1.77 (d, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: gold(III) chloride; water / isopropyl alcohol / 24 h / 65 °C 2: (S)-selective alcohol dehydrogenase whole-cell lyophilisate / aq. buffer / pH 8 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26 % ee | With 1(4),8(11),15(18),22(25)-tetrakis-{(10R,20R)-2-hydroxy-10,20-diphenylethoxy}phthalocyaninato zinc(II) In dichloromethane at 20℃; for 24h; Inert atmosphere; Overall yield = 37 %; enantioselective reaction; | 2.2.8. General procedure for the enantioselective diethylzinc addition to aromatic aldehydes General procedure: Under an argon atmosphere, chiral ligand (0.1 mmol) was dissolvedin dry solvent, Ti(OiPr)4 (0.94 mmol) was added and stirredfor 1 h for the Ti-mediated reactions. Et2Zn (2 mmol, 1 M in hexane)was added, and the resulting yellow solution was stirred for20 min at rt. Aldehyde (1 mmol) was then added dropwise in 10min and the reaction was stirred for another 24 h at room temperature.After quenching with 1 mL saturated NH4Cl solution, 25 mLof H2O was added and then extracted with CH2Cl2 (3 25 mL). Thecombined organic phases were dried over Na2SO4 and evaporatedin vacuo. The crude product was purified by flash chromatographyto give the corresponding alcohol. Enantiomeric excesses weredetermined by GC analysis with chiral HP-CHIRAL-B20 column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: copper(I) thiophene-2-carboxylate; triethyl phosphite; tris-(dibenzylideneacetone)dipalladium(0) / water; isopropyl alcohol / 20 °C 2: copper(I) thiophene-2-carboxylate; triethyl phosphite; tris-(dibenzylideneacetone)dipalladium(0) / isopropyl alcohol / 24 h / 30 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: With C36H28FeMnN2O3P(1+)*Br(1-); potassium carbonate In ethanol at 20℃; for 0.0833333h; Glovebox; Stage #2: With hydrogen In ethanol at 50℃; for 16h; Glovebox; Autoclave; | 16 Example 11 Asymmetric hydrogenation of acetophenone with Mn-PNN catalyst General procedure: In the glove box, add Mn-Cat.1 catalyst (3.8mg, 0.005mmol) and substrate acetophenone (120mg, 1mmol) into a 5mL clear glass vial, then potassium carbonate (1.4 mg, 0.01 mmol) and absolute ethanol (3 mL) were added, and the mixture was stirred at room temperature for 5 min. Finally, the hydrogenation bottle was put into the autoclave, the hydrogen was replaced three times and then filled with 30 bar H2, and reacted at 50°C for 16h. After the reaction is completed, the hydrogen is released carefully, the solvent is spin-dried under reduced pressure, and the hydrogenated product (R)-1-phenylethanol is purified by silica gel column, a colorless and transparent liquid, >99% conversion, 95% yield, 77% ee, |
83 % ee | With bis(1,5-cyclooctadiene)diiridium(I) dichloride; C37H35FeN2P; hydrogen; potassium carbonate In methanol at 20℃; for 24h; Autoclave; Overall yield = 94 %; enantioselective reaction; | 31 Example 23-42 General procedure: Reaction substrate suitability[Ir(COD)Cl] 2 (0.34 mg, 0.0005 mmol) in a glove box filled with nitrogenAnd the chiral P, N, N ligand L1 (0.64 mg, 0.0011 mmol) was dissolved in anhydrous methanol (3.0 mL).Stir at room temperature for 1 hour. Substrate I-b~I-u,(120 mg, 1.0 mmol) and K2CO3 (5.6 mg, 0.05 mmol),Place it in an autoclave and replace it with hydrogen three times.Then pass hydrogen to 20 atmospheres and react at room temperature for 24 hours.The hydrogenated product II-b to II-u is obtained. The invention has wide substrate suitability,According to the above reaction conditions, many substrates can participate in the reaction.High yield and high enantioselectivity to obtain the alcohol product II of the chiral center,Its reaction formula is: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrabutyl ammonium fluoride In tetrahydrofuran; toluene; pentane at 20℃; for 0.5h; Sealed tube; Inert atmosphere; Glovebox; Overall yield = 0.0731 g; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
>99 % ee | With pseudozyma (Candida) antarctica lipase B In hexane at 20℃; for 0.5h; Enzymatic reaction; | 2.2 General procedure for CAL-B-catalyzed transesterification in organic solvents General procedure: The reaction was conducted with a similar method reported previously.1 Novozym 435 (10 mg) and vinyl acetate (0.20 mmol) were added to a solution of an alcohol (0.10 mmol) in an organic solvent (10 mL) at 50 °C. The reaction mixture was vigorously stirred with a magnetic bar for 0.50 h. An aliquot (20 μL) was withdrawn, filtered through EXtrelut and diluted with diethyl ether before being analyzed by GC. Conversion (c) was calculated as c = ees/(eep + ees) and was confirmed by GC molar response factor of acetate/alcohol using isoamyl alcohol as an internal standard. |
Tags: 135145-34-5 synthesis path| 135145-34-5 SDS| 135145-34-5 COA| 135145-34-5 purity| 135145-34-5 application| 135145-34-5 NMR| 135145-34-5 COA| 135145-34-5 structure
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P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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