Selectivity in Lewis acid-mediated fragmentations of peroxides and ozonides: application to the synthesis of alkenes, homoallyl ethers, and 1,2-dioxolanes †
- 15 August 2000
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 1
- No. 17,p. 3006-3013
- https://doi.org/10.1039/b001391i
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.Keywords
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