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

PH Dussault, HJ Lee, X Liu

Index: Dussault, Patrick H.; Lee, Hyung-Jae; Liu, Xuejun Journal of the Chemical Society, Perkin Transactions 1, 2000 , # 17 p. 3006 - 3013

Full Text: HTML

Citation Number: 26

Abstract

Fragmentation of dialkyl peroxides and ozonides is strongly influenced by the choice of Lewis acid. TiCl 4 promotes C–O ionization (S N 1 reaction) of tertiary peroxides while SnCl 4 and BF 3 ·OEt 2 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, ...