Visible‐Light Photoredox‐Catalyzed Synthesis of β‐Aminosulfides and β‐Aminosulfoxides via Radical Addition to Imines

ABSTRACT A mild, efficient, and sustainable photoredox method has been developed for the synthesis of β‐aminosulfides and β‐aminosulfoxides. The transformation employs imines as readily available radical acceptors and organosilicon reagents as radical precursors, providing the desired products in good yields across a broad substrate scope. A one‐pot aerobic oxidation sequence was also established, enabling direct access to β‐aminosulfoxides under photocatalytic conditions with oxygen as the terminal oxidant. Mechanistic studies, including cyclic voltammetry, luminescence quenching, and radical inhibition experiments, revealed that α‐thiomethyl radicals are generated through a single‐electron transfer (SET) process, and that both SET and energy transfer (EnT) pathways contribute to the aerobic oxidation step.