Simple metal-free oxidative cleavage of 1,2-diols

Abstract

Cleavage of 1,2-diols is easily carried out under mild conditions with the Oxone/KBr (or Oxone/NaCl) method in either acetonitrile/water or tert-butanol/water medium at room temperature. This procedure is highly efficient for the cleavage of dihydroxyfatty esters and acids. The reaction takes place through a double oxidation of the 1,2-diol, leading to the 1,2-diketone that undergoes a Baeyer-Villiger oxidation, with a final hydrolysis of the generated anhydride. The application to other diols, including simple internal and terminal diols, is also possible, but the nature of the diol substrate conditions the optimal halide/solvent system, given that important differences in reactivity are observed. These differences are ascribed to the change in the rate limiting step depending on the substrate/halide/solvent combination.