Fryszkowska Anna, Fisher Karl, Gardiner John M, Stephens Gill M
Manchester Interdisciplinary Biocentre, University of Manchester, 131 Princess Street, Manchester, United Kingdom.
J Org Chem. 2008 Jun 6;73(11):4295-8. doi: 10.1021/jo800124v. Epub 2008 May 2.
This is the first report of the use of Clostridium sporogenes extracts for enantioselective reduction of CC double bonds of beta,beta-disubstituted (1) and alpha,beta-disubstituted nitroalkenes (3). Crude enzyme preparations reduced aryl derivatives 1a-e and 1h, in 35-86% yield with > or =97% ee. Reduction of (E)- and (Z)-isomers of 1c gave the same enantiomer of 2c (> or =99% ee). In contrast, alpha,beta-disubstituted nitroalkene 3a was a poor substrate, yielding (S)- 4a in low yield (10-20%), and the ee (30-70% ee) depended on NADH concentration. An efficient synthesis of a library of nitroalkenes 1 is described.
这是关于利用生孢梭菌提取物对β,β-二取代（1）和α,β-二取代硝基烯烃（3）的碳-碳双键进行对映选择性还原的首次报道。粗酶制剂将芳基衍生物1a - e和1h还原，产率为35 - 86%，对映体过量值（ee）≥97%。1c的（E）-和（Z）-异构体还原得到相同对映体的2c（ee≥99%）。相比之下，α,β-二取代硝基烯烃3a是一种较差的底物，以低产率（10 - 20%）生成（S）- 4a，且对映体过量值（30 - 70% ee）取决于烟酰胺腺嘌呤二核苷酸（NADH）浓度。本文描述了一种高效合成硝基烯烃1文库的方法。
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