高对映体富集全碳季碳中心的合成：手性有机锂亲核试剂对α,α-二腈β,β-二取代烯烃的共轭加成反应。

Synthesis of highly enantioenriched all-carbon quaternary centers: conjugate additions of chiral organolithium nucleophiles to alpha,alpha-dinitrile beta,beta-disubstituted olefins.

作者信息

Jang Doo Ok, Kim Dwight D, Pyun Do Kyu, Beak Peter

机构信息

Department of Chemistry, Yonsei University, Wonju 220-710, Korea.

出版信息

Org Lett. 2003 Oct 30;5(22):4155-7. doi: 10.1021/ol035601k.

DOI:10.1021/ol035601k

PMID:14572273

Abstract

[reaction: see text]. Highly enantioenriched quaternary centers are obtained by the reaction of chiral lithiated intermediates complexed to (-)-sparteine with tetrasubstituted, alpha,alpha-dinitrile activated olefins. Lithiated N-Boc-N-Aryl benzylamine furnishes products with drs from 78:22 to 95:5, with ers exceeding 94:6. Lithiated N-Boc-N-Aryl allylamine reactants provide enecarbamate products with drs from 55:45 to 99:1, with ers ranging from 87:13 to 97:3.

摘要

[反应：见正文]。通过将与（-）-鹰爪豆碱络合的手性锂化中间体与四取代的α，α-二腈活化烯烃反应，可得到高度对映体富集的季碳中心。锂化的N-叔丁氧羰基-N-芳基苄胺提供的产物的非对映体比例为78:22至95:5，对映体比例超过94:6。锂化的N-叔丁氧羰基-N-芳基烯丙胺反应物提供的烯氨基甲酸酯产物的非对映体比例为55:45至99:1，对映体比例为87:13至97:3。