Preparation of Monosilyl Acetals from Esters via ÍBu2AIH Reduction and Trapping with iV-(Trimethylsilyl)imidazole. Addition of Allyltrimethylsilane to Yield Homoallylic Alcohols or Ethers

Dalibor Sames, Yunqi Liu, Lynn DeYoung, Robin Polt, Lynn DeYoung

Research output: Contribution to journalArticle

27 Scopus citations

Abstract

Alkyl esters were reduced with 1BU2AIH or a 1:1 mixture of 1BU2AIH and 1Bu3AI (iBu2AlH-iBu3Al or 1BU5AI2H), followed by trapping of the resulting tetrahedral intermediate with TMS-imidazole to produce monosilyl acetals. Reaction of the mixed acetals with allyltrimethylsilane in the presence of Lewis acids (Hosomi-Sakurai reaction) generated homoallylic alcohols or ethers selectively, depending on the substitution of the monosilyl acetal. TMS methoxy acetals (MeO—CH—OTMS) and TMS ethoxy acetals bearing additional complexing groups such as MeO- or Ph2C=N- provided alcohols with 1.5:1-9:1 threoselectivity, while simple TMS ethoxy acetals provided only ethyl ethers as products. The monosilyl acetal configuration was easily epimerized or racemized, and the configuration of the Hosomi-Sakurai product was apparently independent of the initial monosilyl acetal reactant configuration.

Original languageEnglish (US)
Pages (from-to)2153-2159
Number of pages7
JournalJournal of Organic Chemistry
Volume60
Issue number7
DOIs
StatePublished - Jan 1 1995

ASJC Scopus subject areas

  • Organic Chemistry

Fingerprint Dive into the research topics of 'Preparation of Monosilyl Acetals from Esters via ÍBu2AIH Reduction and Trapping with iV-(Trimethylsilyl)imidazole. Addition of Allyltrimethylsilane to Yield Homoallylic Alcohols or Ethers'. Together they form a unique fingerprint.

  • Cite this