Copper(I)-Catalyzed Aerobic Alcohol Oxidation with Bicyclic Nitroxyl Cocatalysts.

摘要

Aerobic alcohol oxidation reactions are attractive and have broad potential utility, but they are seldom used in bench-scale and industrial chemistry due to limited reaction scope and/or safety concerns. TEMPO is widely used as a catalyst for alcohol oxidation, and significant recent advances have identified Cu/TEMPO-catalyzed alcohol oxidation methods that use O2 as the stoichiometric oxidant for the oxidation of primary alcohols. Described herein are the advantages of a copper-based catalyst system with a bicyclic nitroxyl derivative, ABNO. When paired with a copper catalyst, ABNO and other bicyclic nitroxyls promote rapid oxidation of both primary and secondary activated and aliphatic alcohols. Cu/ABNO catalyzed aerobic alcohol oxidation methods amenable to bench and production scale as well as the development of an enantioselective Cu/nitroxyl-based aerobic alcohol oxidation catalyst will be discussed.