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由光学活性钴配合物催化的对映选择性硼氢化物还原反应。

Enantioselective borohydride reduction catalyzed by optically active cobalt complexes.

作者信息

Yamada Tohru, Nagata Takushi, Sugi Kiyoaki D, Yorozu Kiyotaka, Ikeno Taketo, Ohtsuka Yuhki, Miyazaki Daichi, Mukaiyama Teruaki

机构信息

Basic Research Laboratories for Organic Synthesis, Mitsui Petrochemical Industries Ltd., Nagaura, Sodegaura-shi, Chiba 299-0265, Japan.

出版信息

Chemistry. 2003 Sep 22;9(18):4485-509. doi: 10.1002/chem.200304794.

Abstract

The highly enantioselective borohydride reduction of aromatic ketones or imines to the corresponding alcohols was developed in the presence of a catalytic amount of an optically active cobalt(II) complex catalyst. This enantioselective reduction is carried out using a precisely premodified borohydride with alcohols such as tetrahydrofurfuryl alcohol, ethanol and methanol. High optical yields are obtained by choosing the appropriate alcohol as modifiers and a suitable beta-ketoiminato ligand of the catalyst. The enantioselective borohydride reduction has been successfully applied to the preparation of optically active 1,3-diols, the stereoselective reduction of diacylferrocenes, and dynamic and/or kinetic resolution of 1,3-dicarbonyl compounds.

摘要

在催化量的手性钴(II)配合物催化剂存在下,开发了将芳香族酮或亚胺高度对映选择性硼氢化还原为相应醇的方法。这种对映选择性还原是使用精确预改性的硼氢化物与醇(如四氢糠醇、乙醇和甲醇)进行的。通过选择合适的醇作为改性剂和催化剂的合适β-酮亚胺基配体,可以获得高光学产率。对映选择性硼氢化还原已成功应用于制备光学活性1,3-二醇、二酰基二茂铁的立体选择性还原以及1,3-二羰基化合物的动态和/或动力学拆分。

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