Investigating Competing Inner‐ and Outer‐Sphere Electron‐Transfer Pathways in Copper Photoredox‐Catalyzed Atom‐Transfer Radical Additions: Closing the Cycle

This integrated computational and experimental study comprehensively examines the viability of competing inner‐sphere electron transfer (ISET) and outer‐sphere electron transfer (OSET) processes in [Cu(dap)2]+‐mediated atom‐transfer radical additions (ATRA) of olefins and CF3SO2Cl that can deliver both R–SO2Cl and R–Cl products. Five sterically‐ and electronically‐varied representative alkenes were selected from which to explore and reconcile the range of experimentally observed outcomes. Findings are consistent with photoexcited [Cu(dap)2]+ initiating photoelectron transfer via ISET and the subsequent regeneration of the oxidized catalyst via single‐electron transfer in the ground state via ISET to close the catalytic cycle and liberate products. R–SO2Cl/R–Cl product ratios appear to be primarily governed by the relative rates of direct catalyst regeneration {i.e., [Cu(dap)2SO2Cl]•+ + R•} and ligand exchange {i.e., [Cu(dap)2SO2Cl]•+ + Cl– }. Through this work, a more consistent and more complete conceptual framework has been developed to better understand this chemistry and how catalyst regeneration occurs. It is this important ground state process, which closes the catalytic cycle, and ultimately controls the enantioselectivity of ATRA reactions employing chiral copper photocatalysts