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.