133082-13-0Relevant articles and documents
Highly Efficient Synthesis of Optically Pure (S)-1-phenyl-1,2-ethanediol by a Self-Sufficient Whole Cell Biocatalyst
Chen, Xi,Mei, Ting,Cui, Yunfeng,Chen, Qijia,Liu, Xiangtao,Feng, Jinhui,Wu, Qiaqing,Zhu, Dunming
, p. 483 - 488 (2015)
Terminal vicinal diols are important chiral building blocks and intermediates in organic synthesis. Reduction of α-hydroxy ketones provides a straightforward approach to access these important compounds. In this study, it has been found that asymmetric reduction of a series of α-hydroxy aromatic ketones and 1-hydroxy-2-pentanone, catalyzed by Candida magnolia carbonyl reductase (CMCR) with glucose dehydrogenase (GDH) from Bacillus subtilis for cofactor regeneration, afforded 1-aryl-1,2-ethanediols and pentane-1,2-diol, respectively, in up to 99 % ee. In order to evaluate the efficiency of the bioreduction, lyophilized recombinant Escherichia coli whole cells coexpressing CMCR and GDH genes were used as the biocatalyst and α-hydroxy acetophenone as the model substrate, and the reaction conditions, such as pH, cosolvent, the amount of biocatalyst and the presences of a cofactor (i.e., NADP+), were optimized. Under the optimized conditions (pH6, 16h), the bioreduction proceeded smoothly at 1.0 m substrate concentration without the external addition of cofactor, and the product (S)-1-phenyl-1,2-ethanediol was isolated with 90 % yield and 99 % ee. This offers a practical biocatalytic method for the preparation of these important vicinal diols. Self-sufficient catalysis! Lyophilized recombinant Escherichia coli coexpressing Candida magnolia carbonyl reductase (CMCR) and glucose dehydrogenase (GDH) genes served as an effective self-sufficient biocatalyst for the reduction of α-hydroxy acetophenones at high substrate concentrations. The products were isolated with high yield and excellent optical purity, offering a practical biocatalytic method for the preparation of vicinal diols.
Catalytic Diastereo- and Enantioconvergent Synthesis of Vicinal Diamines from Diols through Borrowing Hydrogen
Feng, Wei,Gao, Taotao,Lau, Kai Kiat,Lin, Yamei,Pan, Hui-Jie,Yang, Binmiao,Zhao, Yu
supporting information, p. 18599 - 18604 (2021/08/09)
We present herein an unprecedented diastereoconvergent synthesis of vicinal diamines from diols through an economical, redox-neutral process. Under cooperative ruthenium and Lewis acid catalysis, readily available anilines and 1,2-diols (as a mixture of diastereomers) couple to forge two C?N bonds in an efficient and diastereoselective fashion. By identifying an effective chiral iridium/phosphoric acid co-catalyzed procedure, the first enantioconvergent double amination of racemic 1,2-diols has also been achieved, resulting in a practical access to highly valuable enantioenriched vicinal diamines.
Selective monochlorination of unsymmetrical vicinal diols with chlorinated iminium chlorides
Li, Chengyang,Li, Xiaotong,Wang, Yu,Wu, Xiaoyu,Xie, Xiaomin,Yang, Liqun,Zhang, Zhaoguo
supporting information, (2020/03/23)
Chlorinated iminium chlorides have been identified to promote the highly efficient and selective mono-chlorination of unsymmetrical vicinal diols. Vilsmeier reagent, namely, (chloromethylene)dimethyliminium chloride, enables highly reactive and regioselective chlorination of 1,2- and 1,3-diols featured one secondary benzylic hydroxy group and one primary aliphatic hydroxy group to give the corresponding 1,2- and 1,3-chlorohydrins. Viehe's salts (α,α-dichloro iminium salts) exhibit excellent reactivity and good selectivity for vicinal diols to give the corresponding chlorohydrin carbamates via a cyclic intermediate in situ. The chlorination protocols tolerate diverse functional groups, including halogens, naphthalene rings, nitro, and cyano. Moreover, the optical purity of chiral diols could be retained during this chlorination reaction.
One-step method for preparing racemic aryl vicinal diol in pure water
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Paragraph 0027-0029, (2019/03/08)
The invention provides a one-step method for preparing racemic aryl vicinal diol in pure water. The method is characterized by comprising the following steps: dissolving metachloroperbenzoic acid intodeionized water, adding styrene compounds, heating in a water bath at 30 DEG C, stirring at a rotation speed of 200-300 revolutions per minute for reacting for 2-3 hours, extracting the reaction solution with ethyl acetate, drying, and removing the ethyl acetate, thereby obtaining the racemic aryl vicinal diol. According to the one-step method for preparing racemic aryl vicinal diol in pure waterdisclosed by the invention, the metachloroperbenzoic acid serves as an oxidizing agent in the deionized water, dihydroxylation of the styrene compounds is realized within 2-3 hours at high chemoselectivity and high yield, and the racemic aryl vicinal diol is prepared. The method avoids use of any organic solvent or heavy metal catalyst, is short in reaction time, mild in reaction condition, greenand environmental-friendly, simple in operation and readily available in catalyst, has potential application prospects, and solves the problems that the target product is low in yield, the catalyst is difficult to obtain, and the organic solvent is needed.
Transition-Metal-Free Stereospecific Cross-Coupling with Alkenylboronic Acids as Nucleophiles
Li, Chengxi,Zhang, Yuanyuan,Sun, Qi,Gu, Tongnian,Peng, Henian,Tang, Wenjun
supporting information, p. 10774 - 10777 (2016/09/09)
We herein report a transition-metal-free cross-coupling between secondary alkyl halides/mesylates and aryl/alkenylboronic acid, providing expedited access to a series of nonchiral/chiral coupling products in moderate to good yields. Stereospecific SN2-type coupling is developed for the first time with alkenylboronic acids as pure nucleophiles, offering an attractive alternative to the stereospecific transition-metal-catalyzed C(sp2)-C(sp3) cross-coupling.
Ru-MACHO-Catalyzed Highly Chemoselective Hydrogenation of α-Keto Esters to 1,2-Diols or α-Hydroxy Esters
Gao, Shaochan,Tang, Weijun,Zhang, Minghui,Wang, Chao,Xiao, Jianliang
supporting information, p. 1748 - 1752 (2016/07/06)
A ruthenium pincer catalyst has been shown to be highly effective for the hydrogenation of a wide range of α-keto esters, affording either diols or hydroxy esters depending on the choice of reaction conditions. Strong base, high temperature, and pressure favor the formation of diols whilst the opposite is true for the hydroxy esters.
Enantioselective hydrolysis of racemic and meso -epoxides with recombinant escherichia coli expressing epoxide hydrolase from Sphingomonas sp. HXN-200: Preparation of epoxides and vicinal diols in high ee and high concentration
Wu, Shuke,Li, Aitao,Chin, Yit Siang,Li, Zhi
, p. 752 - 759 (2013/06/05)
A unique epoxide hydrolase (SpEH) from Sphingomonas sp. HXN-200 was identified and cloned based on genome sequencing and expressed in Escherichia coli. The engineered E. coli (SpEH) showed the same selectivity and substrate specificity as the wild type strain and 172 times higher activity than Sphingomonas sp. HXN-200 for the hydrolysis of styrene oxide 1. Hydrolysis of racemic styrene oxide 1, substituted styrene oxides 3, 5-7, and N-phenoxycarbonyl-3,4-epoxypiperidine 8 (200-100 mM) with resting cells of E. coli (SpEH) gave (S)-epoxides 1, 3, 5-7 and (-)-8 in 98.0-99.5% enantiomeric excess (ee) and 37.6-46.5% yield. Hydrolysis of cyclopentene oxide 9, cyclohexene oxide 10, and N-benzyloxycarbonyl-3,4-epoxypyrrolidine 11 (100 mM) afforded the corresponding (R, R)-vicinal trans-diols 12-14 in 86-93% ee and 90-99% yield. The ee of (1R, 2R)-cyclohexane-1,2-diol 13 was improved to 99% by simple crystallization. These biotransformations showed high specific activity (0.28-4.3 U/mg cdw), product concentration, product/cells ratio, and cell-based productivity. Hydrolysis at even higher substrate concentration was also achieved: (S)-1 was obtained in 430 mM (51 g/Lorg) and 43% yield; (1R, 2R)-13 was obtained in 500 mM (58 g/L) and >99% yield. Gram-scale preparation of epoxides (S)-1, (S)-3, (S)-6 and diols (1R, 2R)-12, (1R, 2R)-13, (3R, 4R)-14 were also demonstrated. E. coli (SpEH) cells showed the highest enantioselectivity to produce (S)-1 (E of 39) among all known EHs in the form of whole cells or free enzymes and the highest enantioselectivities to produce (S)-3, 5, 6, 7, (-)-8, and (R, R)-14 (E of 36, 35, 28, 57, 22, and 28) among all known EHs. The easily available and highly active E. coli (SpEH) cells are the best biocatalysts known thus far for the practical preparation of these useful and valuable enantiopure epoxides and vicinal diols via hydrolysis.
Metal-free dihydroxylation of alkenes using cyclobutane malonoyl peroxide
Jones, Kevin M.,Tomkinson, Nicholas C. O.
experimental part, p. 921 - 928 (2012/02/16)
Cyclobutane malonoyl peroxide (7), prepared in a single step from the commercially available diacid 6, is an effective reagent for the dihydroxylation of alkenes. Reaction of a chloroform solution of 7 with an alkene in the presence of 1 equiv of water at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (30-84%). With 1,2-disubstituted alkenes, the reaction proceeds with syn-selectivity (3:1 → 50:1). A mechanism consistent with experimental findings is proposed, which is supported by deuterium and oxygen labeling studies and explains the stereoselectivity observed. Alternative reaction pathways that are dependent on the structure of the starting alkene are also described leading to the synthesis of allylic alcohols and γ-lactones.
Selective reduction of aldehydes and ketones to alcohols with ammonia borane in neat water
Shi, Lei,Liu, Yingying,Liu, Qingfeng,Wei, Bin,Zhang, Guisheng
scheme or table, p. 1372 - 1375 (2012/06/04)
Chemoselective reduction of various carbonyl compounds to alcohols with ammonia borane (AB), a nontoxic, environmentally benign, and easily handled reagent, in neat water was achieved in quantitative conversions and high isolated yields. Interestingly, α- and β-keto esters were selectively reduced to corresponding hydroxyl esters by AB, while diols were obtained when sodium borohydride was used as a reducing agent. The procedure is also compatible with the presence of a variety of base-labile protecting groups, such as tosyl, acetyl, benzoyl, ester groups, and acid-labile protecting groups such as trityl and TBDMS groups, and others, such as the unsaturated double bond, nitro and cyano groups. Finally, a kilo scale reaction of methyl benzoylformate with AB was conducted in water and gave methyl mandelate in 94% yield.
One-pot synthesis of enantiomerically pure 1, 2-diols: Asymmetric reduction of aromatic α-oxoaldehydes catalysed by Candida parapsilosis ATCC 7330
Mahajabeen, Pula,Chadha, Anju
experimental part, p. 2156 - 2160 (2012/05/04)
A facile and simple one-pot method was developed to produce a series of optically active (S)-1-phenyl-1,2-ethanediols with good yields (up to 70%) and high enantiomeric excess (>99%) via asymmetric reduction of various substituted aromatic α-oxoaldehydes using Candida parapsilosis ATCC 7330.
