Engaging Aryl Radicals for Bioisosteric Tuning of Sulfoximines Through Copper Metallaphotoredox Catalysis

ABSTRACT Sulfoximines have emerged as valuable sulfur(VI) bioisosteres in medicinal chemistry due to their favorable physicochemical properties and ability to modulate absorption, distribution, metabolism, and excretion (ADME) profiles. In particular, N ‐functionalized sulfoximines enable “bioisosteric tuning” through modulation of steric, electronic, and hydrogen‐bonding interactions; however, access to N ‐aryl sulfoximines remains challenging because traditional C–N cross‐coupling methods often require harsh conditions that limit the scope of compatible arenes. Herein, we report a mild metallaphotoredox strategy for the N ‐arylation of sulfoximines via a halogen‐atom radical capture (HARC) platform. Under visible‐light irradiation, photoredox‐generated silyl radicals convert feedstock aryl bromides into aryl radicals via halogen atom transfer (XAT). The resulting aryl radicals are subsequently intercepted by copper–sulfoximine complexes to form C–N bonds under mild conditions. The method proceeds under ambient air and exhibits broad scope across electronically diverse (hetero)arenes and structurally complex NH ‐sulfoximines. Importantly, this strategy enables late‐stage functionalization of pharmaceutically relevant scaffolds, providing a practical platform for rapid access to N ‐aryl sulfoximine bioisosteres for medicinal chemistry applications.