Efficient and Highly Selective Oxidation of Primary Alcohols to Aldehydes by N-Chlorosuccinimide Mediated by Oxoammonium Salts

2,2,6,6-Tetramethyl-1-piperidinyloxy catalyzes efficient oxidation of primary alcohols to aldehydes by N-chlorosuccinimide, in a biphasic dichloromethane-aqueous pH 8.6 buffer system in the presence of tetrabutylammonium chloride. Aliphatic, benzylic, and allylic alcohols are readily oxidized with no overoxidation to carboxylic acids. Secondary alcohols are oxidized to ketones with a much lower efficiency. Very high chemoselectivities are observed when primary alcohols are oxidized in the presence of secondary ones. Primary-secondary diols are selectively transformed into hydroxy aldehydes, with, in some cases, no detectable formation of the isomeric keto alcohols.