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Stereochemical evidence for aryl participation in the ring opening of oxiranes ring opening reactions of 1 benzyl 1 2 epoxy cyclo hexane under acidic conditions



Stereochemical evidence for aryl participation in the ring opening of oxiranes ring opening reactions of 1 benzyl 1 2 epoxy cyclo hexane under acidic conditions



Journal of Organic Chemistry 47(15): 2917-2923



The reactions of the carcinogen 1-benzyl-1,2-epoxycyclohexane (1) were investigated and compared with those of the corresponding methyl-substituted oxirane (3) to evaluate the possibility that an aryl group not directly linked to the oxirane ring can participate in the ring-opening processes. The acid-catalyzed ring-opening reactions of 1 are not completely anti stereoselective and give mixtures of syn and anti addition products accompanied by rearrangement compounds. The stereoselectivity and the amounts of rearrangement products vary noticeably with the reaction conditions. The results obtained and, in particular, the presence of substantial amounts of syn products observed in the ring-opening reactions of 1, markedly higher than those from epoxide 3, strongly suggest the incursion of aryl participation and have been rationalized through a mechanism implying the intermediacy of a phenonium-type ion.

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Accession: 006476736

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