Reaction pathway of conjugate addition of lithium organozincates to s-trans-enones

Masanobu Uchiyama, Shinji Nakamura, Taniyuki Furuyama, Eiichi Nakamura, Keiji Morokuma

研究成果: Article査読

18 被引用数 (Scopus)

抄録

Density functional theory (DFT) calculations were performed to understand the reaction mechanism of organozincates in 1,4-addition to methyl vinyl ketone (MVK). Examination of the addition of Me3ZnLi to MVK as compared with that of (MeLi)2 showed that the precise transition state structures critically determine the reaction selectivity for α,β-unsaturated carbonyl compounds. In the case of organozincates, the 1,4-addition proceeds smoothly through an open form TS, whereas alkyllithiums favor 1,2-addition through a closed TS. This 1,4-addition mechanism of Zn-ates does not involve an electron transfer process and is different from the reaction of organocuprates, in which oxidation/reduction of the copper atom occurs.

本文言語English
ページ(範囲)13360-13361
ページ数2
ジャーナルJournal of the American Chemical Society
129
44
DOI
出版ステータスPublished - 2007 11月 7

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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