Ruthenium-Catalyzed 1,3-Aryl Redox Isomerization of Allylic Alcohols.

The isomerization of allylic alcohols to the corresponding carbonyl compounds is a well-established reaction in organic synthesis. However, 1,3-carbon migration is a quite challenging field, and thus transformation has remained elusive until now. Herein, we present the ruthenium-catalyzed intramolecular 1,3-aryl migrative isomerization, which provides a mild and environmentally friendly method to synthesize various ketones with high step- and atom-economy and broad substrate scope. Meanwhile, the Ru(III)-catalyzed C(sp3)-C(aryl) bond cleavage of unactivated allylic alcohols may serve as a heuristic paradigm for transition-metal-catalyzed C-C activation.