Regio‐Divergent C—H Alkynylation with Janus Directing Strategy via Ir(III) Catalysis

Directing strategy has been extensively exploited to maintain activity and selectivity for the rapid access to functionalized molecules and pharmaceutical targets. However, ‘one‐to‐one’ activation model was usually achieved through traditional directing strategy. Herein, we achieved ‘one‐to‐two’ activation model by slight modification of simple and practical ketoxime and amide functionality. With judicious choice of directing groups, Csp³—H and Csp²—H bond alkynylation reaction, and more significantly, dehydrogenative Csp³—H alkynylation, were realized, enabling the regio‐divergent late‐stage modifications of pharmaceuticals.