10593-35-8

Basic information

• Product Name: (R)-1-(3-pyridyl)ethanol
• CAS NO: 10593-35-8
• Molecular Weight: 123.155
• Mol File: 10593-35-8.mol
• Article Data: 98

Chemical Properties

• CAS DataBase Reference: (R)-1-(3-pyridyl)ethanol(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-1-(3-pyridyl)ethanol(10593-35-8)
• EPA Substance Registry System: (R)-1-(3-pyridyl)ethanol(10593-35-8)

Safety Data

• Hazardous Substances Data: 10593-35-8(Hazardous Substances Data)

Upstream product

• 4754-27-2 1-(3-Pyridyl)ethanol 
• 97-72-3 2-Methylpropionic anhydride 
• 350-03-8 methyl-3-pyridylketone 
• 67-63-0 isopropyl alcohol 
• 108-05-4 vinyl acetate 
• 536-78-7 3-ethylpyridine 
• 67031-82-7 1-(3-Pyridyl)ethyl benzoate 
• 500-22-1 3-pyridinecarboxaldehyde 
• 544-97-8 dimethyl zinc(II) 
• 35692-86-5 1-(3-Pyridyl)ethyl acetate 
• 27854-86-0 (1R)-1-(3-pyridyl)ethyl acetate 
• 75-24-1 trimethylaluminum 

Downstream Products

• 72504-66-6 (1R)-1-(1-benzyl-1,2,5,6-tetrahydro-3-pyridyl)ethanol 
• 183866-66-2 (R)-3-Eth-(Z)-ylidene-4-(1H-indol-2-ylmethyl)-piperidine-1-carboxylic acid benzyl ester 
• 183866-63-9 (R,Z)-benzyl 3-ethylidene-4-(2-methoxy-2-oxoethyl)piperidine-1-carboxylate 
• 183866-61-7 5-((R)-1-Hydroxy-ethyl)-3,6-dihydro-2H-pyridine-1-carboxylic acid benzyl ester 

Relevant articles and documents

Efficient Asymmetric Synthesis of Ethyl (S)-4-Chloro-3-hydroxybutyrate Using Alcohol Dehydrogenase SmADH31 with High Tolerance of Substrate and Product in a Monophasic Aqueous System

Bioreductions catalyzed by alcohol dehydrogenases (ADHs) play an important role in the synthesis of chiral alcohols. However, the synthesis of ethyl (S)-4-chloro-3-hydroxybutyrate [(S)-CHBE], an important drug intermediate, has significant challenges concerning high substrate or product inhibition toward ADHs, which complicates its production. Herein, we evaluated a novel ADH, SmADH31, obtained from the Stenotrophomonas maltophilia genome, which can tolerate extremely high concentrations (6 M) of both substrate and product. The coexpression of SmADH31 and glucose dehydrogenase from Bacillus subtilis in Escherichia coli meant that as much as 660 g L-1 (4.0 M) ethyl 4-chloroacetoacetate was completely converted into (S)-CHBE in a monophasic aqueous system with a >99.9% ee value and a high space-time yield (2664 g L-1 d-1). Molecular dynamics simulation shed light on the high activity and stereoselectivity of SmADH31. Moreover, five other optically pure chiral alcohols were synthesized at high concentrations (100-462 g L-1) as a result of the broad substrate spectrum of SmADH31. All these compounds act as important drug intermediates, demonstrating the industrial potential of SmADH31-mediated bioreductions.

Novel dimethoxy(aminoalkoxy)borate derived from (S)-diphenylprolinol as highly efficient catalyst for the enantioselective boron-mediated reduction of prochiral ketones

The novel dimethoxyl(aminoalkoxy)borate 1 was isolated as a white crystalline dimer joined by H-bonding as evidenced by X-ray analysis, and demonstrated to be a highly effective catalyst for the asymmetric reduction of representative prochiral ketones with borane-DMS. Optically pure alcohols were obtained using only 1 mol % of catalyst 1 in up to 99% ee.

A solar light-driven, eco-friendly protocol for highly enantioselective synthesis of chiral alcohols via photocatalytic/biocatalytic cascades

The judicious utilization of solar light for the asymmetric synthesis of optically active compounds by imitating natural photosynthesis introduces a new concept that harnesses this renewable energy in vitro for ultimate transformation into chiral chemical bonds. Herein, we present a comprehensive description of such a biomimetic endeavor towards the design and construction of an asymmetric artificial photosynthesis system that comprises an efficient method of nicotinamide cofactor (NADPH) regeneration under visible light employing a graphene-based light harvesting photocatalyst and its subsequent utilization in an enzyme-catalyzed asymmetric reduction of prochiral ketones to expediently furnish the corresponding chiral secondary alcohols. A detailed optimization study revealed a major dependency of the reaction outcome on the amount of cofactor, photocatalyst and enzyme used, as well as the mode of their addition. A series of structurally diverse ketones bearing an array of (hetero)aryl/alkyl substituents proved to be highly suitable to our photocatalytic-biocatalytic cascade approach, providing (R/S)-1-(hetero)aryl/ alkylethanols in excellent enantioselectivities (ee ～ 95->99.9%) under mild and environmentally benign conditions. To the best of our knowledge, the synthesis of these enantiopure alcohols employing a visible-light-driven nicotinamide cofactor regeneration strategy has been reported for the first time. Such enantioenriched alcohols act as versatile chiral building blocks for the synthesis of compounds having industrial and pharmaceutical relevance. In addition, this solar-to-chiral chemicals prototype appears advantageous from ecological and economical perspectives. We describe mechanistic pathways to demonstrate how the present catalytic synthesis protocol functions through perfect orchestration between visible-light-driven photocatalysis and biocatalysis to be successively applied in inducing asymmetry in an achiral molecule for the ultimate goal of solar energy utilization in the synthesis of valuable chiral fine chemicals. This work highlights the potential advantages of a bioinspired system to the pertinence of solar energy in asymmetric transformations leading to enantioenriched alcohol precursors, and thus opens up a new field of research that might emerge as an important breakthrough with promising implications towards generating a sustainable and non-fossil/non- nuclear energy future. the Partner Organisations 2014.

Highly enantioselective transfer hydrogenation of ketones with chiral (NH)2P2 Macrocyclic Iron(II) complexes

Bis(isonitrile) iron(II) complexes bearing a C2-symmetric diamino (NH)2P2 macrocyclic ligand efficiently catalyze the hydrogenation of polar bonds of a broad scope of substrates (ketones, enones, and imines) in high yield (up to 99.5 %), excellent enantioselectivity (up to 99 % ee), and with low catalyst loading (generally 0.1 mol %). The catalyst can be easily tuned by modifying the substituents of the isonitrile ligand. Paying the iron price: Bis(isonitrile) iron(II) complexes with a C2-symmetric diamino (NH)2P2 macrocyclic ligand efficiently catalyze the hydrogenation of polar bonds of a broad scope of substrates (ketones, enones, imines) in high yield (up to 99.5 %), excellent enantioselectivity (up to 99 % ee), and with low catalyst loading (generally 0.1 mol %).

Chiral Cyclopentadienone iron complexes for the catalytic asymmetric hydrogenation of ketones

Three chiral (cyclopentadienone)iron complexes derived from (R)-BINOL (CK1-3) were synthesized and their structures unambiguously confirmed by X-ray analysis (CK3). Under suitable conditions for the in situ conversion into the corresponding (hydroxycyclopentadienyl)iron hydrides (Me3NO, H2), the new chiral complexes were tested in the catalytic asymmetric hydrogenation of ketones, showing moderate to good enantioselectivity. In particular, the complex bearing methoxy substituents at the 3,3-positions of the binaphthyl moiety (CK2) proved remarkably more enantioselective than the unsubstituted one (CK1) and reached the highest level of enantioselectivity (up to 77% ee) ever obtained with chiral (cyclopentadienone)iron complexes. Reducto! Chiral (cyclopentadienone)iron complexes were synthesized and tested, after in situ activation, in the catalytic asymmetric hydrogenation of ketones leading to the highest enantiomeric excesses ever obtained with this type of catalysts.

Highly enantioselective carbonyl reduction with borane catalyzed by chiral spiroborate esters derived from chiral 1,2-aminoalcohols

Novel spiroborate esters derived from nonracemic 1,2-amino alcohols were examined as chiral catalysts in the borane reduction of acetophenone and other aromatic ketones at room temperature. The optically active alcohols were obtained in excellent chemical yields and enantioselectivities up to 99% ee with 10% of catalyst.

Asymmetric synthesis of allo-heteroyohimbine alkaloids

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Chiral Pyridyl Alcohol-Promoted Highly Enantioselective and Rapid Addition of Dialkylzinc to Pyridinecarboxaldehydes

Optically active 1-(2-, 3-, and 4-pyridyl)propanols and 1-(3-pyridyl)ethanol were synthesized in good to high enantiomeric excesses (up to 88percent e.e.) and in a short reaction time by catalyzed asymmetric addition of dialkylzinc to pyridine-2-, 3- and 4-carboxaldehydes and 6-bromopyridine-2-carboxaldehyde in the presence of tridentate chiral 2--1,1-diarylethanols.

Enantioselective reduction of ketones catalysed by 1,3,2-oxazaborolidines prepared from phenylglycine

(R)-B-methyl-4,5,5-triphenyl-1,3,2-oxazaborolidine (1) and (R)-B-allyl- 4,5,5-triphenyl-1,3,2-oxazaborolidine (2), prepared from (R)-phenylglycine, catalyse the reduction of prochiral ketones with borane, to afford the corresponding secondary alcohols in good chemical yields and with moderate to high (61%-96%) enantiomeric excesses. These compounds gave the best results reported so far regarding the reduction of linear alkyl methyl ketones catalysed by oxazaborolidines.

Microbial enantioselective reduction of acetylpyridine derivatives

The microbial enantioselective reduction of acetylpyridine derivatives was studied. Many microorganisms were found to reduce 5-acetylfuro[2,3-c]pyridine (AFP) to (S)-5-(1-hydroxyethyl)furo[2,3-c]-pyridine (FPH). Candida maris IFO10003 reduced AFP to (R)-FPH with high enantioselectivity. The microbial reduction reaction was optimized. The aeration conditions and glucose concentration affected the yield and stereoselectivity. The cells accumulated 17.5 g/l (107 mM) of (R)-FPH with a 99% yield and 97% enantiomeric excess (e.e.). A cell-free extract of C. maris accumulated 91.5 g /l (559 mM) with over 99% e.e. with enzymatic NADH regeneration. (R)-FPH is an important intermediate for the synthesis of HIV reverse-transcriptase inhibitor, and other optically active 1-(pyridyl)ethanol derivatives are versatile chiral building blocks for asymmetric synthesis.

Remarkably improved stability and enhanced activity of a: Burkholderia cepacia lipase by coating with a triazolium alkyl-PEG sulfate ionic liquid

Three types of triazolium cetyl-PEG10 sulfate ionic liquid were synthesized and their activation of Burkholderia cepacia lipase was investigated; both the reaction rate and enantioselectivity depended on the cationic part of the coating ILs and 1-butyl-3-methyl-1,2,3-triazolium cetyl-PEG10 sulfate (Tz1)-coated lipase PS, which is especially suitable for the transesterification of 1-(pyridin-2-yl)ethanol, 1-(pyridin-3-yl)ethanol, and 1-(pyridin-4-yl)ethanol, among 12 types of tested secondary alcohol. The most important result was obtained when these enzymes were stored in an IL ([N221MEM][Tf2N]) solvent: Tz1-PS showed an amazing stability and it exhibited an excellent activity after 2 years when the enzyme was stored in [N221MEM][Tf2N].

Asymmetric anti-Prelog reduction of ketones catalysed by Paracoccus pantotrophus and Comamonas sp. cells via hydrogen transfer

A broad range of ketones including methyl-aryl-, methyl-alkyl-, cyclic and sterically hindered ketones were reduced to the corresponding anti-Prelog alcohols with moderate to excellent stereoselectivities by employing lyophilised cells of Paracoccus pantotrophus DSM 11072 and Comamonas sp. DSM 15091 via hydrogen transfer. The reduction equivalents were provided using 2-propanol as a hydride donor. For instance, acetophenone was reduced to the corresponding (R)-enantiomer with >99% ee.

Spiroborate esters in the borane-mediated asymmetric synthesis of pyridyl and related heterocyclic alcohols

The effectiveness of several spiroborate ester catalysts was investigated in the asymmetric borane reduction of 2-, 3-, and 4-acetylpyridines under different reaction conditions. Highly enantiomerically enriched 1-(2-, 3-, and 4-pyridyl)ethanols and 1-(heterocyclic)ethanols were obtained using 1-10% catalytic loads of the spiroborate 5 derived from diphenylprolinol and ethylene glycol.

Selective Reductions. 40. A Critical Examination of the Relative Effectiveness of Various Reducing Agents for the Asymmetric Reduction of Different Classes of Ketones

Among a wide variety of highly promising asymmetric reducing agents recently reported in the literature, 20 promising reagents were selected for critical examination.All of the data for the asymmetric reductions of prochiral ketones by these 20 reagents were compiled.The various ketones were organized into 10 distinct classes.However, direct comparison of the relative effectiveness of these 20 reagents for individual classes of ketones proved not possible because of the wide variation in the individual ketones used to test each reagent.In the hope of making possible such comparison, we selected one representative ketone for each of the 10 different classes of ketones.Then, six of the most promising reagents were selected: B-isopinocampheyl-9-borabicyclononane, B-Ipc-9-BBN (neat); diisopinocampheylchloroborane, Ipc2BCl; a mixed reagent of 2 equiv of BH3 with (S)-(-)-2-amino-3-methyl-1,1-diphenylbutan-1-ol, BH3-AMDPB (2:1); NB-Enantride; K-Glucoride; and Binal-H.These six reagents were applied to the 10 selected standard ketones.On the basis of results obtained for the six reagents and the 10 selected ketones, preferred reagents are suggested for the asymmetric reduction of individual classes of ketones.

I86A/C295A mutant secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus has broadened substrate specificity for aryl ketones

Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase (SADH) reduces aliphatic ketones according to Prelog's Rule, with binding pockets for small and large substituents. It was shown previously that the I86A mutant SADH reduces acetophenone, which is not a substrate of wild-type SADH, to give the anti-Prelog R-product (Musa, M. M.; Lott, N.; Laivenieks, M.; Watanabe, L.; Vieille, C.; Phillips, R. S. ChemCatChem 2009, 1, 89–93.). However, I86A SADH did not reduce aryl ketones with substituents larger than fluorine. We have now expanded the small pocket of the active site of I86A SADH by mutation of Cys-295 to alanine to allow reaction of substituted acetophenones. As predicted, the double mutant I86A/C295A SADH has broadened substrate specificity for meta-substituted, but not para-substituted, acetophenones. However, the increase of the substrate specificity of I86A/C295A SADH is accompanied by a decrease in the kcat/Km values of acetophenones, possibly due to the substrates fitting loosely inside the more open active site. Nevertheless, I86A/C295A SADH gives high conversions and very high enantiomeric excess of the anti-Prelog R-alcohols from the tested substrates.

Preparation of 1-Pyridinylethanols of High Enantiomeric Purity by Lipase Catalysed Transesterifications

Component B lipase of the Candida antarctica yeast displays high enantioselectivity in catalysing transesterification reactions in non-aqueous media with chiral secondary alcohols.This was exploited to resolve racemates of 1-(pyridinyl)-ethanols, 1-(6-bromopyridin-2-yl)ethanol, and 1-(6-bromopyridin-2-yl)-2,2-dimethylpropanol.The lipase esterified the (R)-alcohols of the first four substrates in equal or more than 99percent enantiomeric excess in less than three hours with 30-40percent isolated yield.Remaining (S)-enantiomers were isolated in similar yields and in 97-98percent ee. 1-(6-Bromopyridin-2-yl)-2,2-dimethylpropanol did not form any detectable ester in one week.

Stereochemical Control in Bakers' Yeast Redox Biotransformations of Aryl Methyl Ketones and Carbinols

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Catalytic Asymmetric Syntheses of Secondary Alcohols Using cis-1-Amino-2-indanols as Chiral Ligands

Both enantiomers of cis-1-amino-2-indanols (1a,b) have been used as chiral ligands in the catalytic asymmetric reduction of ketones with BH3*SMe2 affording secondary alcohols with enantiomeric excesses up to 95percent.Furthermore, some N,N-dialkyl derivatives of 1a,b catalyzed the enantioselective addition of diethylzinc to aldehydes.

Manganese catalyzed asymmetric transfer hydrogenation of ketones

The asymmetric transfer hydrogenation (ATH) of a wide range of ketones catalyzed by manganese complex as well as chiral PxNy-type ligand under mild conditions was investigated. Using 2-propanol as hydrogen source, various ketones could be enantioselectively hydrogenated by combining cheap, readily available [MnBr(CO)5] with chiral, 22-membered macrocyclic ligand (R,R,R',R')-CyP2N4 (L5) with 2 mol% of catalyst loading, affording highly valuable chiral alcohols with up to 95% ee.

RETRACTED ARTICLE: The Manganese(I)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones: Disclosing the Macrocylic Privilege

The bis(carbonyl) manganese(I) complex [Mn(CO)2(1)]Br (2) with a chiral (NH)2P2 macrocyclic ligand (1) catalyzes the asymmetric transfer hydrogenation of polar double bonds with 2-propanol as the hydrogen source. Ketones (43 substrates) are reduced to alcohols in high yields (up to >99 %) and with excellent enantioselectivities (90–99 % ee). A stereochemical model based on attractive CH–π interactions is proposed.