Catalytic Conversion of N‑Heteroaromatics to Functionalized Arylamines by Merging Hydrogen Transfer and Selective Coupling

To date, although tremendous advances have been made in N-heteroaryl C–H functionalization, there remain significant unmet challenges in the deconstruction of extensively applied but poorly reactive N-heteroaromatics to useful frameworks. Here, by a strategy merging hydrogen transfer and selective coupling, we present a ruthenium-catalyzed deconstruction of N-heteroaromatics to functionalized arylamines with 2-aminoaryl methanols. The reaction is achieved via sequential functionalization of the β and α sites of the initially formed N-heteroarenium salts followed by a C–N cleavage, which proceeds with the striking features of broad substrate scope, excellent functional group tolerance, high chemoselectivity and atom efficiency, and suitability for a streamlined synthesis of some biomedical molecules. The strategy utilized will pave the way for further development of catalytic transformations of inert organo systems to functional frameworks.