Selectivity in Lewis acid-mediated fragmentations of peroxides and ozonides: Application to the synthesis of alkenes, homoallyl ethers, and 1,2-dioxolanes

Patrick H. Dussault, Hyung Jae Lee, Xuejun Liu

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Abstract

Fragmentation of dialkyl peroxides and ozonides is strongly influenced by the choice of Lewis acid. TiCl4 promotes C-O ionization (SN1 reaction) of tertiary peroxides while SnCl4 and BF3·OEt2 promote O-O heterolysis (Hock reaction). The cationic intermediates are trapped with allyltrimethylsilane to afford allylated alkanes and homoallyl ethers. In the absence of a nucleophile, ozonides (1,2,4-trioxolanes) invariably undergo O-O heterolysis. However, the combination of allyltrimethylsilane and SnCl4 results in formation of 1,2-dioxolanes via trapping of intermediates derived from SN1 ionization.

Original languageEnglish (US)
Pages (from-to)3006-3013
Number of pages8
JournalJournal of the Chemical Society, Perkin Transactions 1
Issue number17
DOIs
StatePublished - Jan 1 2000

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ASJC Scopus subject areas

  • Chemistry(all)

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