Organocatalytic peroxidation of malonates, β-ketoesters, and cyanoacetic esters using n-Bu4NI/t-BuOOH-mediated intermolecular oxidative C(sp3)–O coupling

Abstract

A new organocatalytic approach for the synthesis of peroxides based on СН activation of a sp3-hybridized carbon atom is reported. Peroxides were prepared in 31–89% yield by the reaction of malonates, β-ketoesters, and cyanoacetic esters with a Bu4NI/tert-butyl hydroperoxide system. The formation of the expected hydroxylation products was not observed. In the discovered reaction, tert-butyl hydroperoxide plays a dual role by acting as the oxidant and the O-reagent for the C–O coupling. The synthesis can be scaled up to generate gram quantities of the target products.