The catalytic oxidative cleavage reactions of aryl-alkenes by tert-butyl hydroperoxide were investigated to understand the mechanistic pathway for cleavage of the carbon-carbon double bond. The intermediates formed in the cleavage reactions have been identified and clarify the pathway for cleavage. Addition to the double bond by the tert-butylperoxy radical initiates the reaction forming the resulting benzylic radical 1. Subsequently, 1 is trapped either by the tert-butylperoxy radical to give vicinal bisperoxide 2, or by dioxygen to form the analogous hydroperoxide-peroxide 3 to account for the initial oxidative addition. With a slower rate, the bisperoxide 2 is converted to the carboxylic product 4 mainly through the Kornblum–DeLaMare process. On the other hand, with a faster rate peroxide 3 is reduced to the final product 4 mediated by the catalyst. The focus of prior investigations has been mainly on the formation of specific products, and competing reactions have generally been neglected. Herein, we now report the outcome of catalytic free radical addition reactions of TBHP and the probable pathways to cleavage products.

Catalytic oxidative reactions of arylalkenes by tert-Butyl hydroperoxide: Mechanistic assessment

2019 Fall National Meeting

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