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

Complex molecules and simple alkanes present fundamentally different challenges for catalytic C–H functionalization—precise, catalyst-controlled selectivity versus high intrinsic activation barriers—precluding a generalizable solution. Herein, we report a unified strategy that address both challenges by repurposing a classic chiral auxiliary framework from carbonyl chemistry into a stereocontrolled C–H amination platform via silver-catalyzed sulfur(VI) nitrene transfer. This system enables stereodivergent, late-stage amination of activated C–H bonds in complex molecules with broad functional-group tolerance and aqueous compatibility, while also mediating mild, selective amination of unactivated chemical feedstocks. The modular, stereodefined S(VI) motif functions as a multi-vector pharmacophore, providing a versatile linchpin for rapid library diversification and enabling both target- and diversity-oriented synthesis.