Substrate-Controlled Regioselective Iodooxygenation of Olefins

An unexpected regioselective I 2 /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.