Mild N‑Arylation of Sulfoximines With (Hetero)aryl Chlorides Enabled by α‐Methylnaphthyl‐ <i>t</i> BuBrettPhos Palladium Triflate

ABSTRACT N‐Arylated sulfoximines are privileged motifs in pharmaceuticals, natural products, and chiral ligands, yet their synthesis remains challenging. We report a readily accessible, air‐ and moisture‐stable precatalyst, [Pd(1‐MeNAP)( t BuBrettPhos)]OTf, that promotes the N‐arylation of NH‐sulfoximines with exceptional efficiency. The mild conditions (Cs 2 CO 3 , 25°C) enable a broad substrate scope, tolerating e.g. aryl chlorides with free NH, OH, and COOH groups and sensitive, drug‐like heterocycles, thereby allowing late‐stage functionalization beyond current systems. Mechanistic studies reveal that the methylnaphthyl substituent and non‐coordinating triflate counterion cooperatively accelerate precatalyst activation via transmetalation/reductive elimination, generating the active monoligated Pd(0) species even in the presence of weakly nucleophilic sulfoximines.