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

Abstract

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 coppercatalyzed 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.