Development of Highly Selective Alcohol Oxidation Using Precisely Designed Catalysts.

Nitroxyl radicals have long been recognized as powerful catalysts for alcohol oxidation. However, challenges remain regarding their efficiency, selectivity, and substrate scope. This review summarizes the author's efforts to advance alcohol oxidation catalysis through two complementary approaches: the discovery of new nitroxyl radical-based catalysts and the development of cooperative catalytic systems to address chemoselectivity challenges. Studies on 2-azaadamantane N-oxyl derivatives have led to the unexpected identification of alkoxyamine catalysts, whose unique structures and mechanistic features provide new insights into catalyst design. Further studies have established cooperative systems combining nitroxyl radicals with copper salts that exhibit distinctive chemoselectivity and enable transformations previously inaccessible to purely organocatalytic methods. Collectively, these studies demonstrate how mechanistic understanding and catalyst development can expand the utility of alcohol oxidation in synthetic chemistry, thereby offering new tools for the selective oxidation of complex molecules.