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 carbon-hydrogen (C-H) functionalizations. Whereas densely functionalized scaffolds require precise targeting among multiple reactive sites while tolerating sensitive functionalities, unactivated substrates that lack directing groups require selective activation of exceptionally inert, nearly identical C-H bonds. In this work, we addressed 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 sulfur(VI) motif functions as a modular, stereodefined, and medicinally relevant synthetic linchpin for rapid library diversification, enabling both target- and diversity-oriented synthesis.