Anaerobic Nitroxide-Catalyzed Oxidation of Alcohols Using the NO+/NO• Redox Pair

A new method for alcohol oxidation using TEMPO or AZADO in conjunction with BF3 center dot OEt2 or LiBF4 as precatalysts and tert-butyl nitrite as a stoichiometric oxidant has been developed. The system is based on a NO+/NO center dot pair for nitroxide reoxidation under anaerobic conditions. This allows the simple, high-yielding conversion of various achiral and chiral alcohols to carbonyl compounds without epimerization and no formation of nonvolatile byproducts.