100306-33-0Relevant articles and documents
Identification of key residues in Debaryomyces hansenii carbonyl reductase for highly productive preparation of (S)-aryl halohydrins
Xu, Guo-Chao,Shang, Yue-Peng,Yu, Hui-Lei,Xu, Jian-He
, p. 15728 - 15731 (2015)
Key residues of Debaryomyces hansenii carbonyl reductase in the determination of the reducing activity towards aryl haloketones were identified through combinatorial mutation of conserved residues. This study provides a green and efficient biocatalyst for the synthesis of (S)-aryl halohydrins.
Copper(ii)-catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl and heteroaryl ketones: Asymmetric synthesis of (R)-fluoxetine and (S)-duloxetine
Zhou, Ji-Ning,Fang, Qiang,Hu, Yi-Hu,Yang, Li-Yao,Wu, Fei-Fei,Xie, Lin-Jie,Wu, Jing,Li, Shijun
, p. 1009 - 1017 (2014)
A set of reaction conditions has been established to facilitate the non-precious copper-catalyzed enantioselective hydrosilylation of a number of structurally diverse β-, γ- or ε-halo-substituted alkyl aryl ketones and α-, β- or γ-halo-substituted alkyl heteroaryl ketones under air to afford a broad spectrum of halo alcohols in high yields and good to excellent enantioselectivities (up to 99% ee). The developed procedure has been successfully applied to the asymmetric synthesis of antidepressant drugs (R)-fluoxetine and (S)-duloxetine, which highlighted its synthetic utility.
PEG600-carboxylates as efficient reusable reaction media and acylating agents for the resolution of sec-alcohols
Monteiro, Carlos M.,Lourenco, Nuno M. T.,Ferreira, Frederico C.,Afonso, Carlos A. M.
, p. 42 - 46 (2015)
Herein is presented a simple, attractive, and reusable methodology for one-pot resolution/separation of free sec-alcohols with enantiomeric excess (ee) values over 90% by the combination of sustainable acylating agents/solvents (polyethylene glycol derivatives) and an easily available and common biocatalyst (Candida antarctica lipase B, or CAL B) under irreversible conditions, along with a separation process by extraction or distillation. A scale-up reaction was carried out with the Fluoxetine precursor with ee values close to 90% for the R enantiomer.
Iminophenyl Oxazolinylphenylamine for Enantioselective Cobalt-Catalyzed Hydrosilylation of Aryl Ketones
Chen, Xu,Lu, Zhan
, p. 4658 - 4661 (2016)
A new family of chiral iminophenyl oxazolinylphenylamines (IPOPA) was designed and synthesized through three steps from commercially available starting materials. An efficient cobalt-catalyzed asymmetric hydrosilylation of simple ketones with a low catalyst loading of CoCl2 and IPOPA was developed to afford chiral alcohols in good yields with high enantioselectivities.
A new catalytic enantioselective reducing reagent system from (-)-α,α-diphenylpyrrolidinemethanol and 9-borabicyclo[3.3.1]nonane, especially effective for hindered and substituted aralkylketones
Kanth, Josyula V.B.,Brown, Herbert C.
, p. 1069 - 1074 (2002)
New catalytic enantioselective reduction systems were prepared from aminoalcohols and dialkylboranes, for the enantioselective reductions of prochiral aromatic ketones. Among these, the system prepared from (-)-α,α-diphenylpyrrolidinemethanol with 9-borabicyclo[3.3.1]nonane proved especially promising for such reductions. This complex catalyzes the reduction of prochiral aralkyl ketones to the corresponding alcohols with BH3-THF, with enantioselectivities 82-99.2%. Also, this catalyst is particularly effective for the more hindered and substituted aralkyl ketones. Various modifications in this new catalytic reduction system, such as changing reaction conditions, reducing agent and dialkylborane, were also examined.
Chiral terpene auxiliaries III: Spiroborate esters from (1R,2S,3R,5R)-3-amino-apopinan-2-ol as highly effective catalysts for asymmetric reduction of ketones with borane
?wiklińska, Marta,Krzemiński, Marek P.,Tafelska-Kaczmarek, Agnieszka
, p. 1453 - 1458 (2015)
New spiroborate esters, derived from terpene amino alcohols, (S)-prolinol, and 2-aminoethanol, were employed as catalysts in the borane reduction of acetophenone and other aryl alkyl and halogenated ketones. The corresponding alcohols were obtained in high yields and with enantioselectivities up to 98% ee. The influence of the amino alcohol and the diol moieties of spiroborate on the reaction selectivity was examined. The catalyst load, the nature of the solvent, the borane source, and the reaction conditions were also investigated.
Pen G acylase catalyzed resolution of phenylacetate esters of secondary alcohols
Baldaro,D'Arrigo,Pedrocchi-Fantoni,Rosell,Tagliani,Terreni,Servi
, p. 1031 - 1034 (1993)
Penicillin G acylase from E. coli (E.C. 3.5.1.11) immobilized on Eupergit C is used for the kinetic resolution of phenyl acetate esters of secondary alcohols of pharmaceutical interest.
Efficient Synthesis of (R)-2-Chloro-1-(2,4-dichlorophenyl)ethanol with a Ketoreductase from Scheffersomyces stipitis CBS 6045
Shang, Yue-Peng,Chen, Qi,Kong, Xu-Dong,Zhang, Yu-Jun,Xu, Jian-He,Yu, Hui-Lei
, p. 426 - 431 (2017)
By enzyme screening, a ketoreductase cloned from Scheffersomyces stipitis CBS 6045 and named SsCR was identified that could catalyze the asymmetric hydrogenation of a variety of aromatic ketones. SsCR exhibited a specific activity of 65 U mg?1p
Chemoenzymatic synthesis of fluoxetine precursors. Reduction of β-substituted propiophenones
Coronel, Camila,Arce, Gabriel,Iglesias, Cesar,Noguera, Cynthia Magallanes,Bonnecarrere, Paula Rodriguez,Giordano, Sonia Rodriguez,Gonzalez, David
, p. 94 - 98 (2014)
Five endophytic yeast strains isolated from edible plants were tested in the reduction β-chloro- and β-azidopropiophenone for the preparation of optically active fluoxetine precursors. The biotransformation rendered not only the corresponding chiral γ-substituted alcohols, but also unsubstituted alcohols and ketones. The product profile was studied and a plausible mechanism for the reductive elimination of the β-functional group is proposed.
Enantioselective reduction of propiophenone formed from 3-chloropropiophenone and stereoinversion of the resulting alcohols in selected yeast cultures
Janeczko, Tomasz,Kostrzewa-Suslow, Edyta
, p. 1264 - 1269 (2014)
Biotransformation of 3-chloro-1-phenylpropan-1-one 1 in sixteen selected cultures of yeast strains has been carried out. For most of the biocatalysts studied the substrate was fully consumed after 1-9 h of transformation, with the exception of the culture of Saccharomyces brasiliensis KCh 905, in which after 24 h trace amounts of the substrate were still visible (2%). However, apart from the expected enantiospecific reduction of the substrate to 3-chloro-1-phenylpropan-1-ol 3, the main biotransformation products comprised of a dehalogenation product - propiophenone 2 and the product of its reduction - 1-phenylpropan-1-ol 4. It was only in the cultures of five strains: Saccharomyces brasiliensis KCh 905, Rhodotorula marina KCh 77, Candida parapsilosis KCh 909, Candida viswanathii KCh 120, and Saccharomyces cerevisiae KCh 464 that 3-chloro-1-phenylpropan-1-ol 3 was observed in amounts of more than 10% of the product mixture. (S)-3-Chloro-1-phenylpropan-1-ol with ee = 91% was identified after 9 h of biotransformation in the culture of Candida viswanathii KCh 120, whereas (R)-3-chloro-1-phenylpropan-1-ol with ee = 28% was found in the culture of Aphanocladium album KCh 417. 1-Day biotransformation of propiophenone 2 in the cultures of Rhodotorula strains gave (S)-1-phenylpropan-1-ol 4 with a very high ee (95-99%) and 85-99% of substrate conversion, whereas transformation of this substrate in the cultures of Candida viswanathii KCh 120 and Candida parapsilosis KCh 909 led to (R)-1-phenylpropan-1-ol with ee = 98% and 97%, respectively. During biotransformation of propiophenone the percent composition of the reaction mixtures changed with time. Employment of the racemic mixture of 1-phenylpropan-1-ol 4 as a substrate for biotransformations allowed us to observe that the biocatalysts tested were capable of enantioselective oxidation of (S)-1-phenylpropan-1-ol. An exception was the culture of Rhodotorula glutinis KCh 242, in which after one day of biotransformation (S)-1-phenylpropan-1-ol was obtained with ee = 96%.
