Hydroesterification and Difunctionalization of Olefins with <i>N</i>-Hydroxyphthalimide Esters

Abstract

Irradiation of aryl esters of <i>N</i>-hydroxyphthalimides in the presence of unactivated olefins promotes a mild and regioselective hydroesterification. Optimal results are obtained with the aid of <i>fac</i>-Ir(dFppy)₃ in CH₂Cl₂. Terminal and 1,1-disubstituted olefins provide primary esters, and trisubstituted olefins provide secondary esters. The anti-Markovnikov selectivity is consistent with alkyl radical intermediates, which are also indicated by the formation of cyclized products from dienes. Mono-acylated diols are formed from tri- and tetrasubstituted olefins in the presence of water.