Chiral S(VI) Platform Unifies Selective C–H Amination of Complex Molecules and Alkane Feedstocks

Complex molecules and simple alkanes pose distinct challenges for catalyst-controlled C–H functionalizations. While densely functionalized scaffolds require precise targeting amongst multiple reactive sites while tolerating sensitive functionalities, unactivated substrates lacking directing groups require selective activation of exceptionally inert, nearly identical C–H bonds. Herein, we address both challenges by repurposing a classic chiral auxiliary into a unified, selective, and predictable C–H amination platform mediated by silver catalysis and chiral sulfur(VI) nitrene precursors. This system enables stereodivergent, late-stage aminations of activated C–H bonds with broad functional group tolerance and compatibility with aqueous conditions, while also mediating mild, selective aminations of chemical feedstocks. The S(VI) motif functions as a modular, stereodefined, and medicinally relevant synthetic linchpin for rapid library diversification, enabling both target- and diversity-oriented synthesis.