TEMPO-copper(II) diimine-catalysed oxidation of benzylic alcohols in aqueous media

Abstract

In situ generated copper(II)-diimine complexes combined with TEMPO (2,2,6,6-tetramethyl-piperidinyl-1-oxyl radical) were studied in the oxidation of benzylic alcohols, the focus being on enviromentally benign reaction conditions. In this respect, reactions were studied in aqueous alkaline solutions and dioxygen was used as an end oxidant. This simple catalytic system turned out to be highly efficient and selective in the oxidation of primary and secondary benzylic alcohols to their corresponding carbonyl compounds. Under optimised reaction conditions [5 mol% of TEMPO, 3 mol% of copper(II) diimine, pH 12.6-13.5, 80°C, 10 bar O2] benzyl alcohol was quantitatively and selectively oxidised to benzaldehyde. According to ESI-MS studies, coordination of TEMPO, as well as deprotonated benzyl alcohol to the parent copper-diimine complex in aqueous solutions is feasible. Supported by these observations a plausible reaction mechanism is proposed for the oxidation reaction. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.