Asymmetric reduction of ethynyl ketones and ethynylketoesters by secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus

被引:62
作者
Heiss, C
Phillips, RS [1 ]
机构
[1] Univ Georgia, Dept Chem, Athens, GA 30602 USA
[2] Univ Georgia, Dept Biochem & Mol Biol, Athens, GA 30602 USA
[3] Univ Georgia, Ctr Metalloenzyme Studies, Athens, GA 30602 USA
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 2000年 / 16期
关键词
D O I
10.1039/b001329n
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Secondary alcohol dehydrogenase (SADH) from Thermoanaerobacter ethanolicus, an NADP-dependent, thermostable oxidoreductase, reduces ethynyl ketones and ethynylketoesters enantioselectively to the corresponding propargyl (propargyl=prop-2-ynyl) alcohols. Ethynyl ketones, in general, are reduced with moderate enantioselectivity (with the exception of 4-methylpent-1-yn-3-one, which gives the (S)-alcohol with > 98% ee). Although ethynyl ketones bearing a small (up to n-propyl) alkyl substituent are reduced to (S)-alcohols, larger ethynyl ketones give (R)-alcohols. In contrast, ethynylketoesters are converted to (R)-ethynylhydroxyesters of excellent optical purity. Unexpectedly, isopropyl ethynylketoesters give higher chemical yields and higher enantioselectivities of ethynylhydroxyesters than methyl or ethyl ethynylketoesters. The optically pure ethynylhydroxyesters may serve as useful chiral building blocks for asymmetric synthesis.
引用
收藏
页码:2821 / 2825
页数:5
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