Selective Synthesis of Unsymmetrical Peroxides: Transition-Metal-Catalyzed Oxidation of Malononitrile and Cyanoacetic Ester Derivatives by tert-Butyl Hydroperoxide at the α-Position

Abstract

A novel method was developed for the selective oxida- tion of a-monosubstituted malononitrile and cyanoacetic ester de- rivatives at the a-position based on transition-metal-catalyzed reaction (Cu, Fe, Mn, Co) with tert-butyl hydroperoxide giving un- symmetrical peroxides in 63-94% yields. The method is facile, does not require large excesses of reagents, and is amenable to gram- scale synthesis.