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

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

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)13360-13361
Number of pages2
JournalJournal of the American Chemical Society
Volume129
Issue number44
DOIs
Publication statusPublished - 2007 Nov 7

ASJC Scopus subject areas

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

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    Uchiyama, M., Nakamura, S., Furuyama, T., Nakamura, E., & Morokuma, K. (2007). Reaction pathway of conjugate addition of lithium organozincates to s-trans-enones. Journal of the American Chemical Society, 129(44), 13360-13361. https://doi.org/10.1021/ja070123k