Donor/Acceptor-Stabilized 1-Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction

Morelia Lopez Reyes, Thibault Troadec, Ricardo Rodriguez, Antoine Baceiredo, Nathalie Saffon-Merceron, Vicenç Branchadell, Tsuyoshi Kato

Research output: Contribution to journalArticleResearchpeer-review

14 Citations (Scopus)

Abstract

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1-silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1-silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila-β-lactam 3. Of particular interest, in the presence of 4-dimethylaminopyridine (DMAP), 1-silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1-silaketene complex 8 and cis-stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four-membered-ring intermediate, similar to that proposed by Chauvin and co-workers for the transition-metal-based olefin metathesis.
Original languageEnglish
Pages (from-to)10247-10253
JournalChemistry - A European Journal
Volume22
Issue number29
DOIs
Publication statusPublished - 1 Jan 2016

Keywords

  • 1-silaketene
  • atomic silicon insertion
  • olefin metathesis
  • silanone
  • transition-metal-like behavior

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