Intramolecular Hydrogen Atom Transfer Induced 1,2-Migration of Boronate Complexes

[Image: see text] Radical α-C-H functionalization of alk-5-enyl boronic esters with concomitant functionalization of the alkene moiety is reported. These cascades comprise perfluoroalkyl radical addition to the alkene moiety of a boronate complex, intramolecular hydrogen atom transfer (HAT), single electron oxidation, and 1,2-alkyl/aryl migration. The boronate complexes are readily generated in situ by reaction of the alkenyl boronic esters with alkyl or aryl lithium reagents. Products are formed in a divergent approach by varying carbon radical precursors as well as alkyl/aryl lithium donors, and reactions proceed under mild conditions upon UV irradiation.