Reductive Hydrocyanation And Hydrocyanation-michael Of Alkynes With Formamide As The Cyanogen Source

Nitriles widely exist in natural products and have important applications in the chemical and pharmaceutical fields.Among them,aliphatic nitriles play an irreplaceable role in daily production and life,such as nylon,synthetic rubber,engineering plastics,and spices.Therefore,it has attracted many organic chemists to develop new methods for synthesizing these nitriles.Currently,aliphatic nitriles compounds are mainly prepared by the(reduced)hydrocyanation of unsaturated hydrocarbons with HCN or the nucleophilic substitution of halogenated hydrocarbons or sulfonates with metal cyanides.These methods not only increase the cost but also produce a large amount of toxic wastes containing cyanide causing serious environmental problems.In order to solve these problems,an green synthetic methods of nitrile compounds were developed using formamide as a new cyano source,by the Lewis acid promoted dehydration of formamide,coordination to transition-metal and subsequent cyanation reactions in situ:In the first part,a nickel-catalyzed reductive hydrocyanation of arylalkynes and formamide we developed.This method uses formamide as a new cyano source,the raw materials are commercially available,and exhibits excellent functional group tolerance,high conversion rate,and high separated yield.This reaction provides a efficient green synthetic methods of propionitrile compounds.In the second part,a one-pot two-step strategy to realize the hydrocyanation-Michael addition of alkynes and formamide by microwaves we developed,introducing two cyano at the same time.This method uses microwave radiation heating different from the traditional external heat source heating method which greatly improves the reaction rate.This approach provides a new and efficient synthetic route for the succinonitriles.