Oxidation of Alcohols and Oxidative Cyclization of Diols using NaBr and Selectfluor

We present protocols for the oxidation of alcohols and aldehydes and for the oxidative cyclization of diols which use a combination of Selectfluor and NaBr. For most substrates, the optimal solvent system is a 1:1 mixture of CH3CN/H2O, but, in select cases, biphasic 1:1 mixtures of EtOAc/H2O or CH2Cl2/H2O are superior. This procedure is operationally simple, uses inexpensive and readily available reagents, and tolerates a variety of functional groups. Mechanistic studies suggest that the active oxidant is hypobromous acid, generated by the almost instantaneous oxidation of Br– by Selectfluor in an aqueous milieu.