Ammonolytic transfer dehydrogenation of amines and amides: a versatile method to valorize nitrogen compounds to nitriles

Abstract

The dehydrogenation of amines has been identified as an efficient method for nitrile synthesis. At present, this approach is restricted to (oxidative) dehydrogenations of primary amines, most often with specialized homogeneous catalysts. In this work, amines were transfer dehydrogenated to nitriles using simple and cheap alkenes (e.g. ethylene or propene) as hydrogen scavengers. The scope was expanded to secondary amines, tertiary amines and even aldehydes. Additional nitrogen is built in from NH₃. The versatility of the process was proven by coupling it to the ammonolysis of secondary amides. This enabled us to recycle long-chain polyamides (LCPA) into monomeric compounds, i.e. α,ω-amidonitriles and dinitriles. Reactions were performed with a recyclable heterogeneous Pt catalyst, at 200 °C and with limited addition of NH₃ and ethylene. High yields of up to 94% were obtained for the corresponding nitriles.