Selective Aerobic Oxidation of Primary Alcohols to Aldehydes

The 2-azaadamantane-N-oxyl (AZADO)- and 9-azanoradamantane-N-oxyl (nor-AZADO)-catalyzed selective oxidation of primary alcohols to the corresponding aldehydes is described. The use of tert-butyl nitrite as the co-catalyst enables efficient aerobic oxidation in MeCN instead of previously reported AcOH; this is important for the selectivity of the reaction. The addition of a solution of saturated aqueous NaHCO3 after the completion of the reaction was effective to suppress the overoxidation of the product to the corresponding carboxylic acid during the workup.