1,4-Addition of Bis(iodozincio)methane to α,β-Unsaturated ketones: Chemical and theoretical/computational studies

Mutsumi Sada, Taniyuki Furayama, Shinsuke Komagawa, Masanobu Uchiyama, Seijiro Matsubara

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)

Abstract

1,4-Addition of bis(iodozincio)methane to simple α,β-unsaturated ketones does not proceed well; the reaction is slightly endothermic according to DFT calculations. In the presence of chlorotrimethylsilane, the reaction proceeded efficiently to afford a silyl enol ether of β-zinciomethyl ketone. The CZn bond of the silyl enol ether could be used in a cross-coupling reaction to form another C-C bond in a one-pot reaction. In contrast, 1,4-addition of the dizinc reagent to enones carrying an acyloxy group proceeded very efficiently without any additive. In this case, the product was a 1,3-diketone, which was generated in a novel tandem reaction. A theoretical/computational study indicates that the whole reaction pathway is exothermic, and that two zinc atoms of bis(iodozincio)methane accelerate each step cooperatively as effective Lewis acids.

Original languageEnglish
Pages (from-to)10474-10481
Number of pages8
JournalChemistry - A European Journal
Volume16
Issue number34
DOIs
Publication statusPublished - 2010 Sep 10

Keywords

  • Addition reactions
  • Density functional calculations domino reactions
  • Ketones
  • Tandem reactions
  • Zinc

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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