Mechanistic insights into radical formation and functionalization in copper/<i>N</i>-fluorobenzenesulfonimide radical-relay reactions
Mukunda Mandal, Joshua A. Buss, Si-Jie Chen, Christopher J. Cramer, Shannon S. Stahl
Abstract
organometallic complex, and radical addition to a Cu-bound ligand. The preferred mechanism is shown to depend on the ligands bound to copper. (4) Finally, the energetics of three different pathways that convert benzylic C-H bonds into benzylic cations are compared, including HAT/ET (ET = electron transfer), relevant to the RPC mechanism with Cu/NFSI; hydride transfer, involved in reactions with high-potential quinones; and sequential ET/PT/ET (PT = proton transfer), involved in catalytic photoredox reactions. Collectively, the results provide mechanistic insights that establish a foundation for further advances in radical-relay C-H functionalization reactions.