Nitrogenation and Oxygenation of an Unstrained C–C Bond Enabled by the Merger of Visible-Light and Cu-Catalysis

Unstrained carbon–carbon bonds are among the most prevalent and inert chemical bonds. Thus, developing synthetic transformations directly from unstrained carbon–carbon bonds under mild conditions is ideal yet challenging due to the inertness and steric hindrance. Here, a visible-light and copper-catalyzed azidation and etherification of a remote and unstrained C–C bond of amines via 1,4-aryl migration have been reported. This redox-neutral protocol shows exquisite site-selectivity, broad scope, and good functional group tolerance, directly transforming unstrained C–C bonds to C–N and C–O bonds at room temperature. Facile derivatizations of benzyl azide products into free amines, triazoles, and phosphamides highlight the potential utility of this method for target molecule synthesis and medicinal chemistry.