A new procedure for the selective and direct oxidation of aliphatic primary alcohols having substitution at - and -positions to corresponding carboxylic acids was developed using a catalytic amount of ligand and additive-free CuCl with anhydrous tBuOOH in acetonitrile solvent under very mild reaction conditions. This procedure is very simple and mild and works efficiently without any additives at room temperature. © 2010 Taylor & Francis Group, LLC.