Biocatalytic oxidative kinetic resolution of sec-alcohols:: stereocontrol through substrate-modification

被引：25

作者：

Stampfer, W ^{[1
]}

Kosjek, B ^{[1
]}

Faber, K ^{[1
]}

Kroutil, W ^{[1
]}

机构：

[1] Graz Univ, Dept Chem Organ & Bioorgan Chem, A-8010 Graz, Austria

来源：

TETRAHEDRON-ASYMMETRY | 2003年 / 14卷 / 02期

基金：

奥地利科学基金会;

关键词：

D O I：

10.1016/S0957-4166(02)00795-4

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Whole lyophilised cells of Rhodococcus ruber DSM 44541 were employed for the oxidative kinetic resolution of sec-alcohols using acetone as hydrogen acceptor. The enantioselectivity of this process could be controlled effectively by introducing C-C multiple bonds into substrates, which were inefficiently recognised, in particular short-chain (omega-1)-alcohols and (omega-2)-analogs. Thus, the enantioselectivities of rac-2-pentanol (E= 16.8) and rac-3-octanol (E= 13.3) were significantly improved by introducing a C=C bond adjacent to the alcohol moiety to give racemic (E)-pent-3-en-2-ol and 4-(E)-octen-3-ol, which were resolved with excellent selectivities (E >100 and 50, respectively). In addition, it was found that high stereodifferentiation between the E- and Z-configured double bonds occurred, as the corresponding (Z)-isomers were not converted. Similar selectivity-enhancing effects were observed with acetylenic analogs. (C) 2003 Elsevier Science Ltd. All rights reserved.

引用

页码：275 / 280

页数：6

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