Substrate-Controlled Regioselective Iodooxygenation of Olefins

An unexpected regioselective I2/TBHP-mediated 1,2-iodooxygenation of alkenes with N-hydroxylamines is described. The reaction proceeds through a radical coupling mechanism or a iodonium mechanism, which is controlled by the structures of both N-hydroxylamines and alkenes, to form vicinal iodo-substituted N-alkoxyamines regioselectively. Both the iodo and alkoxyamine group of the resulting products offer rich possibilities of synthetic manipulations.