A Mn-catalyzed remote C(sp3)-H bond peroxidation triggered by radical trifluoromethylation of unactivated alkenes.

A manganese-catalyzed radical relay strategy for the remote trifluoromethylation-peroxidation of unactivated alkenes is disclosed. The electrophilic CF3 group was added to the C[double bond, length as m-dash]C double bonds to afford remote C-centered radicals upon 1,5-HAT, which could be efficiently trapped by Mnn+1OOBu-t species to deliver 1,6-difunctionalized products selectively under mild conditions. t-BuOOH serves as both the oxidant and the peroxy precursor in this transformation.