High-yield synthesis of nitriles by oxidation of aldehyde N,N-dimethylhydrazones with dimethyldioxirane

Using dimethyldioxirane, the selective transformation of aldehyde N,N-dimethylhydrazones into the corresponding nitriles was achieved in high yield and under mild conditions. The determination of the substituent effect an rates, along with an estimate of the primary kinetic isotope effect using PhCH-NNMe2 and PhCD=NNMe2 provided useful hints concerning the reaction mechanism. It was also observed that the nitrile products do not undergo further oxidation, even with excess dioxirane.