Origin of the regio- and stereoselectivity of allylic substitution of organocopper reagents

Naohiko Yoshikai, Song Lin Zhang, Eiichi Nakamura

研究成果: Article査読

74 被引用数 (Scopus)

抄録

(Chemical Equation Presented) The origin of the contrasting regioselectivities in allylic substitution found for a heterocuprate MeCu(CN)Li and a homocuprate Me2CuLi was studied using density functional calculations. The γ-selectivity of MeCu(CN)Li is determined at the oxidative addition stage of the reaction, where the different degree of trans effect of the Me and the CN groups dictates the relative orientation of the methyl group and the leaving acetate group. As the result, the transition state where the acetate group leaves trans to the Me group on the copper atom is favored, and the γ-selectivity results. The homocuprate Me2CuLi is symmetrical by nature and does not show such regioselectivity.

本文言語English
ページ(範囲)12862-12863
ページ数2
ジャーナルJournal of the American Chemical Society
130
39
DOI
出版ステータスPublished - 2008 10 1
外部発表はい

ASJC Scopus subject areas

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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