16355-00-3Relevant articles and documents
One Pot Asymmetric Synthesis of (R)-Phenylglycinol from Racemic Styrene Oxide via Cascade Biocatalysis
Sun, Zai-Bao,Zhang, Zhi-Jun,Li, Fu-Long,Nie, Yao,Yu, Hui-Lei,Xu, Jian-He
, p. 3802 - 3807 (2019)
(R)-Phenylglycinol is an important chiral building block for pharmaceutical and fine chemical industry, and its efficient synthesis from cheap and commercially available starting materials is challenging and highly desirable. Herein, a new three-step one-pot cascade system employing epoxide hydrolase, glycerol dehydrogenase, and ω-transaminase was designed for the asymmetric synthesis of (R)-phenylglycinol from racemic styrene oxide. A cofactor self-sufficient system employing AlaDH/L?Ala was utilized for the regeneration of expensive cofactor NAD+ and removal of by-product pyruvate. Furthermore, in situ product removal by cation resin adsorption was used to drive the thermodynamic equilibrium of the cascade reaction to the direction of product generation. Finally, optically pure (R)-phenylglycinol was successfully produced from racemic styrene oxide with high yield (81.9 %) and excellent enantioselectivity (99 % ee).
A Comparison of Ligands Proposed for the Asymmetric Dihydroxylation
Crispino, Gerard A.,Makita, Atsushi,Wang, Zhi-Min,Sharpless, K. Barry
, p. 543 - 546 (1994)
Comparative data for several ligands proposed recently for use in the osmium-catalyzed asymmetric dihydroxylation (AD) are presented.
Stereochemistry of the Spontaneous, Acid-Catalyzed and Base Catalyzed Hydrolyses of Styrene Oxide
Lin, Bin,Whalen, Dale L.
, p. 1638 - 1641 (1994)
The stereochemical courses of the spontaneous, hydronium ion-catalyzed and hydroxide ion-catalyzed hydrolyses of (R)-styrene oxide have been determined by 1H NMR analysis of the bis-(+)-α-(methoxy-α-trifluoromethyl)phenylacetate diesters of the styrene glycol products from each reaction.The glycol product from the spontaneous reaction of chiral styrene oxide is the result of 93percent inversion and 7percent retention.This result, coupled with published results of 18O-labeling experiments, indicates that essentially all of the styrene oxide that reacts with cleavage of the benzyl C-O bond yields glycol with inversion of stereochemistry at the benzyl carbon.A mechanism involving addition of neutral water concerted with benzyl C-O bond breaking is proposed for this reaction.The glycol product from the acid-catalyzed reaction was determined to be the result of 67percent inversion and 33percent retention at the benzyl carbon.This result, which agrees with one previous publication and contradicts that of another, reflects the stereochemistry of addition of solvent to the benzyl carbon.Consistent with a recent report that 18O-hydroxide attacks the α- and β-carbons of styrene oxide at almost equal rates, styrene glycol from the reaction of chiral styrene oxide with sodium hydroxide was found to be, within experimental error, completely racemic.
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Jensen,Kiskis
, p. 5825,5826 (1975)
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Highly enantioselective conversion of racemic 1-phenyl-1,2-ethanediol by stereoinversion involving a novel cofactor-dependent oxidoreduction system of Candida parapsilosis CCTCC M203011
Nie, Yao,Xu, Yan,Mu, Xiao Qing
, p. 246 - 251 (2004)
An economical and convenient biocatalytic process was developed for the preparation of (S)-1-phenyl-1,2-ethanediol (PED), which is a valuable chiral building block for pharmaceuticals and liquid crystals, by stereoselective microbial conversion from the corresponding racemate. As a result of screening bacteria, yeasts, and molds, the enantioselective conversion of racemic PED by Candida parapsilosis CCTCC M203011 was found to be the most efficient process to produce (S)-PED with high optical purity of 98% ee and yield of 92%. By detecting the intermediate produced in the reaction by GC-MS, it was suggested that (S)-enantiomer was produced from the intermediate identified as β-hydroxyacetophenone by asymmetric reduction after stereoselective oxidation of (R)-enantiomer to β-hydroxyacetophenone. After investigating the cofactor requirement and stereospecificity of the reaction catalyzed by the cell-free extract from C. parapsilosis CCTCC M203011, it was found that the stereoselective conversion involved the oxidation of (R)-PED to the intermediate with NADP+ as the cofactor and the reduction reaction that formed the product used NADH as the cofactor, which was catalyzed by a novel cofactor-dependent oxidoreduction system. The NADP+-dependent (R)-specific alcohol dehydrogenase involved in stereoinversion was purified from C. parapsilosis CCTCC M203011, which has a relative molecular mass of 45kD.
Rhodium catalysed enantioselective hydroboration of alkenylboronic esters with catecholborane
Wiesauer, Christian,Weissensteiner, Walter
, p. 5 - 8 (1996)
Alkenylboronic esters such as (E)-2-(2-phenylethenyl)-1,3,2-dioxaborolane were subjected to catalytic hydroboration with catecholborane and with use of neutral and cationic rhodium complexes modified by various diphosphine ligands. The resulting 1,2-diboryl intermediate was oxidised with alkaline hydrogen peroxide to give the corresponding 1,2-diol with enantioselectivities up to 79% e.e.
Microbiological Transformations. 28. Enantiocomplementary Epoxide Hydrolyses as a Preparative Access to Both Enantiomers of Styrene Oxide
Pedragosa-Moreau, S.,Archelas, A.,Furstoss, R.
, p. 5533 - 5536 (1993)
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Asymmetric dihydroxylation with silica-anchored alkaloids
Bolm, Carsten,Maischak, Astrid,Gerlach, Arne
, p. 2353 - 2354 (1997)
Diols with excellent enantiomeric excesses are obtained from unfunctionalised alkenes in high yields by osmium-catalysed dihydroxylationsusingsilica-boundpyrimidineandpyrazino-pyridazine ligands.
Enantioselective hydrolysis of styrene oxide with the epoxide hydrolase of Sphingomonas sp. HXN-200
Liu, Zeya,Michel, Johannes,Wang, Zunsheng,Witholt, Bernard,Li, Zhi
, p. 47 - 52 (2006)
The soluble bacterial epoxide hydrolase (EH) from Sphingomonas sp. HXN-200 catalyzed the enantioselective hydrolysis of racemic styrene oxide to give (S)-styrene oxide with an enantiomeric ratio (E) of 21-23 in aqueous buffer, better than any reported native EHs. The ring opening of the styrene oxide with this EH was only at the terminal position for the (S)-enantiomer and at the terminal and benzylic position in an 87:13 ratio for the (R)-enantiomer. Enzymatic hydrolysis of the styrene oxide in a two-liquid phase system significantly reduced autohydrolysis, thus improving the E to 26-29. Hydrolysis of 160 mM styrene oxide with cell-free extract (CFE) of Sphingomonas sp. HXN-200 (10 mg protein/mL) in aqueous buffer and n-hexane (1:1) for 30.7 h afforded 39.2% (62.7 mM) of (S)-styrene oxide in >99.9% ee. The lyophilized CFE was proven to be stable, while the rehydrated lyophilized CFE powder was successfully used for the hydrolysis of 320 mM styrene oxide in the two-liquid phase system, yielding 40.2% (128.6 mM) of (S)-styrene oxide in >99.9% ee after 13.8 h. No inhibitory effect of the diol product on the hydrolysis was observed when the diol concentration was lower than 476 mM, suggesting a straightforward process for the hydrolysis of up to 1 M styrene oxide.
Using deep eutectic solvents to improve the biocatalytic reduction of 2-hydroxyacetophenone to (R)-1-phenyl-1,2-ethanediol by Kurthia gibsonii SC0312
Peng, Fei,Chen, Qing-Sheng,Li, Fang-Zhou,Ou, Xiao-Yang,Zong, Min-Hua,Lou, Wen-Yong
, (2020)
The effects of five deep eutectic solvents (DESs) on the production of (R)-1-phenyl-1,2-ethanediol from 2-hydroxyacetophenone catalyzed by Kurthia gibsonii SC0312 were investigated in this study. Of these, choline chloride/1,4-butanediol (ChCl/Bd) showed excellent biocompatibility and suitably increased the cell membrane permeability while having a little impact on the structure of DNA. Indeed, ChCl/Bd at the concentration of 2 % increased the catalytic rate of the cells by 22 %. The other DESs did not stimulate the catalytic capacity of the cells, despite some increases in the cell membrane permeability. Additionally, the conformation of DNA was visibly changed when adding the other examined DESs except for choline chloride/triethylene glycol. The DESs modified the fatty acid composition of cellular membrane, decreased the relative amount of iso-C14:0 and increased the relative amount of normal C15:0. Meanwhile, the DESs were able to improve the relative ratio of normal fatty acids to branched fatty acids. Finally, a highly efficient reduction of 80 mM 2-hydroxyacetophenone by K. gibsonii SC0312 in the ChCl/Bd-containing system was established, affording (R)-1-phenyl-1,2-ethanediol in 80 % yield and optical purity >99 % at 30 mg/mL wet cells. This work offers a promising approach for the preparation of (R)-1-phenyl-1,2-ethanediol from 2-hydroxyacetophenone using K. gibsonii SC0312.
Stereoselective 1,2-additions of α-alkoxymethyllithiums to aldehydes
Smyj, Robert P.,Chong, J. Michael
, p. 2903 - 2906 (2001)
(equation presented) A chiral derivative of tributylstannymethanol, readily prepared from L-valine, undergoes Sn-Li exhange to provide an α-alkoxyorganolithium that adds to aldehydes with up to 91:9 dr. The diastereoselectivity depends on the solvent and alkyllithium used for transmetalation. Treatment of adducts with acid allowed recovery of the chiral auxiliary and diol with complete stereochemical integrity.
Resolution of 1,2-diols by enzyme-catalyzed oxidation with anodic, mediated cofactor regeneration in the extractive membrane reactor: Gaining insight by adaptive simulation
Degenring, Daniela,Schroeder, Iris,Wandrey, Christian,Liese, Andreas,Greiner, Lasse
, p. 213 - 218 (2004)
Oxidative racemic resolution of 1,2-diols is a method for the synthesis of enantiopure diols not easily accessed by reduction. The constraints generally found for oxidation to hydroxy ketones can be overcome by coupling various techniques. To circumvent product inhibition, a membrane reactor with solvent extraction of the lipophilic product was chosen. For the oxidative regeneration of NAD+ from NADH anodic oxidation mediated by ABTS was used. The kinetic characteristics of the system were determined independently for each significant system step. However, it proved difficult to simulate the coupled process completely with the kinetic data obtained independently, as true reaction conditions are not covered by kinetic experiments. A mixed approach using a system of ordinary differential equations corrected with data from the process (e.g. enzyme activity) leads to a satisfactory description. This model was applied as a starting point for identifying the relevant process parameters.
Directed Evolution of Alcohol Dehydrogenase for Improved Stereoselective Redox Transformations of 1-Phenylethane-1,2-diol and Its Corresponding Acyloin
Hamnevik, Emil,Maurer, Dirk,Enugala, Thilak Reddy,Chu, Thao,L?fgren, Robin,Dobritzsch, Doreen,Widersten, Mikael
, p. 1059 - 1062 (2018)
Laboratory evolution of alcohol dehydrogenase produced enzyme variants with improved turnover numbers with a vicinal 1,2-diol and its corresponding hydroxyketone. Crystal structure and transient kinetics analysis aids in rationalizing the new functions of these variants.
In defense of the catalytic asymmetric cis dihydroxylation of olefins utilizing insoluble polymeric ligands [6]
Salvadori,Pini,Petri
, p. 6929 - 6930 (1997)
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Tridentate nitrogen phosphine ligand containing arylamine NH as well as preparation method and application thereof
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Paragraph 0117-0120, (2021/06/26)
The invention discloses a tridentate nitrogen phosphine ligand containing arylamine NH as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. The tridentate nitrogen phosphine ligand disclosed by the invention is the first case of tridentate nitrogen phosphine ligand containing not only a quinoline amine structure but also chiral ferrocene at present, a noble metal complex of the type of ligand shows good selectivity and extremely high catalytic activity in an asymmetric hydrogenation reaction, meanwhile, a cheap metal complex of the ligand can also show good selectivity and catalytic activity in the asymmetric hydrogenation reaction, and is very easy to modify in the aspects of electronic effect and space structure, so that the ligand has huge potential application value. A catalyst formed by the ligand and a transition metal complex can be used for catalyzing various reactions, can be used for synthesizing various drugs, and has important industrial application value.
An easy and low-cost method of embedding chiral molecules in metal-organic frameworks for enantioseparation
Cao, Rong,Fang, Zhi-Bin,Hu, Xiao-Jing,Huang, Ge,Liu, Tian-Fu,Zhang, Shuo
supporting information, p. 7459 - 7462 (2020/07/15)
A facile method, post-synthetic exchange of modulators (PSEm), has been demonstrated here to prepare chiral metal-organic frameworks for enantioseparation. Based on this method, three chiral porous Zr-based metal-organic frameworks have been prepared through exchanging the coordinated modulators on metal clusters of MOFs with commercially available chiral carboxylic acid molecules. In addition, the obtained materials show enantioselectivity toward three different enantiomers, which presents a proof of concept for the design of MOF materials for enantioseparation by an easy and low-cost method. This journal is