Catalytic amount of vanadium reagent with tert-butylhydroperoxide as the oxidant was found to be an excellent oxidizing agent in aqueous medium. Vanadium pentoxide with aq tert- butylhydroperoxide readily oxidizes primary benzylic azides to the corresponding acids and secondary benzylic azides to the corresponding ketones in excellent yields. Further, vanadium pentoxide and aq tert-butylhydroperoxide combination turned out to be an ...