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

Naohiko Yoshikai, Song Lin Zhang, Eiichi Nakamura

Research output: Contribution to journalArticlepeer-review

74 Citations (Scopus)

Abstract

(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.

Original languageEnglish
Pages (from-to)12862-12863
Number of pages2
JournalJournal of the American Chemical Society
Volume130
Issue number39
DOIs
Publication statusPublished - 2008 Oct 1
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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