Initiated, tert-butyl hydroperoxide-loaded, low-temperature autoxidation of alkenes: a chemoselective synthesis of allylic hydroperoxides, allowing analysis of the regioselectivity of hydrogen atom abstraction from some unsymmetrically substituted substrates
- 1 January 1992
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 1
- No. 12,p. 1531-1538
- https://doi.org/10.1039/p19920001531
Abstract
A method for the preparation of allylic hydroperoxides is introduced: the method involves the rapid, low-temperature, initiated autoxidation of an alkene (in these instances 1-methylcyclohexene and the isomeric 4-methyloct-4-enes) in the presence of tert-butyl hydroperoxide. The success of the method relies upon the selectivity of hydrogen atom abstraction from the substrate by the chain-carrying tert-butylperoxyl radicals, according to the preference for formation of the most stable intermediate allylic radicals, and the reduced rates of chain termination via these same radicals. The method gives a regioselectivity for attack broadly in agreement with predictions from Bolland's rules, and a sufficiently high chemoselectivity for allylic hydroperoxide formation that ready isolation of these products in good yield is achieved.Keywords
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