The enantioselective Birch-Cope sequence for the synthesis of carbocyclic quaternary stereocenters. Application to the synthesis of (+)-mesembrine
The enantioselective Birch-Cope sequence for the synthesis of carbocyclic quaternary stereocenters. Application to the synthesis of (+)-mesembrine
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DOI：
10.1021/ol0615228
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发表时间：
2006-08-31
期刊：
影响因子：
5.2
通讯作者：
Lee, Jisun
中科院分区：
文献类型：
--
作者：
Paul, Tapas;Malachowski, William P.;Lee, Jisun
描述了一种合成具有高水平对映选择性的碳环四元立体中心的技术。通过对映选择性Birch还原-烯丙基化反应、烯醇醚水解反应和Cope重排反应，立体选择性地在2-环己烯-1- 1环上生成手性季中心。该序列的产物为4,4-二取代-2-羧基酰胺-2-环己烯-1- 1结构，是复杂天然产物合成中用途广泛的中间体。该序列在(+)-间膜合成中的应用说明了这些中间体的用途。
A synthetic technique for generating carbocyclic quaternary stereocenters with exceptionally high levels of enantioselectivity is described. A sequence of three reactions, enantioselective Birch reduction - allylation, enol ether hydrolysis, and Cope rearrangement, is used to stereoselectively generate chiral quaternary centers on a 2-cyclohexen-1-one ring. The products of the sequence are 4,4-disubstituted-2-carboxamide- 2-cyclohexen-1-one structures which are versatile intermediates in complex natural product synthesis. An application of the sequence to the synthesis of (+)-mesembrine illustrates the utility of these intermediates.