Insertion reactions of silacyclopropanes: Evidence for a radical-based mechanism

Christina Z. Rotsides, K. A. Woerpel

Research output: Contribution to journalArticlepeer-review

Abstract

Silacyclopropanes reacted rapidly and selectively with p-benzoquinones to provide oxasilacyclopentanes. Ring-expansion products were observed in the absence of a catalyst, elevated temperatures, or irradiation. As substitution was increased on the silacyclopropane ring, improved stereoselectivity was observed. In some cases, the regiochemistry was controlled depending on the extent of stabilization of the reactive intermediates involved. A radical clock experiment, along with stereochemical studies, confirmed that radical intermediates were involved in the ring-expansion reaction. The scope of this radical reaction was expanded to include dienones, aryl aldehydes, and electron-deficient enones in addition to benzoquinones. In the case of aryl aldehydes and electron-deficient enones, the radical reaction can be used to generate silylenes from silacyclopropanes.

Original languageEnglish (US)
Pages (from-to)3132-3138
Number of pages7
JournalOrganometallics
Volume35
Issue number18
DOIs
StatePublished - Sep 26 2016

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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