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C–H alkynylations of electron-rich anilines were accomplished by means of user-friendly nickel catalysis. The C–H functionalization occurred with high positional selectivity and ample scope by kinetically relevant C–H activation. The robust nickel catalyst tolerated synthetically useful functional groups, which set the stage for the facile synthesis of substituted indoles. The chemoselectivity of the cost-effective nickel catalyst was reflected by enabling transformative nickel-catalyzed C–H functionalization with purine nucleobases through monodentate chelation assistance.