Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents: Development of the method and mechanistic investigations

Jason R. Harris, M. Taylor Haynes, Andrew M. Thomas, K. A. Woerpel

Research output: Contribution to journalArticle

Abstract

(Figure presented) A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with 17O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

Original languageEnglish (US)
Pages (from-to)5083-5091
Number of pages9
JournalJournal of Organic Chemistry
Volume75
Issue number15
DOIs
StatePublished - Aug 6 2010

ASJC Scopus subject areas

  • Organic Chemistry

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