Transition Metal-catalyzed Hydrogen Transfer Reduction Of Nitriles

One of the most common methods for the preparation of amines in organic synthesis is the hydrogenation of nitriles to the synthesis of amines.The hydrogen transfer reduction reaction of transition metal catalyzed nitriles has been studied by many scientists.However,the hydrogen transfer reduction reaction of copper-catalyzed nitrile compounds has been widely concerned due to its very mild reaction conditions,inexpensive and readily available catalysts,and the general applicability of substrates.Catalytic transfer hydrogenation uses a hydrogen donor as a hydrogen source,eliminating the need for hydrogen and requiring less operating equipment.This paper is an exploration of the reaction conditions for hydrogen transfer reduction of nitrile compounds.In this paper,the effects of transition metals,especially copper salt compounds(mainly monovalent and divalent copper),as reaction catalysts or additives on the hydrogen transfer reduction of nitrile compounds were studied.These metal salt compounds are not only highly efficient but also cheap and easy to obtain.In addition,with oxazaborolidine as hydrogen donor,this kind of hydrogen donor has better hydrogen supply capacity,and can react with nitrile compound under mild conditions,and can be selectively reduced under different conditions to obtain the hydrogenation product of an amine borane complex or a secondary amine.The product has a higher yield and better selectivity,and the substrate has a wide range of applications.It can be applied to more than twenty kinds of substrates.The yield of primary amine borane complex can reach 86.6%,the yield of secondary amine can reach 96.5%,and the selectivity of both products can be as high as 99%.Through the investigation of the hydrogenation reduction reaction of nitriles,a high-yield reaction method for hydrogen transfer reduction of nitriles was found,which is of great significance for the hydrogen transfer reduction study of aromatic nitriles.In the first chapter of this thesis,recent advances in the catalytic hydrogenation and hydrogen transfer reactions of nitrile compounds are reviewed.The preliminary study on the hydrogen transfer reduction of quinoline compounds in nitrogen-containing heterocyclic compounds is briefly described.The latter study laid a solid foundation.The second chapter mainly introduces the research content of hydrogen transfer and reduction of nitrile compounds into primary amine borane complexes in research work.Including the purpose and theoretical basis,the conditions for the reduction to the primary amine borane complex,the substrate expansion,the preliminary mechanism of the reaction mechanism.The third chapter mainly introduces the research content of hydrogen transfer and reduction of nitrile compounds into secondary amines in research work.Including research background,optimization of reaction conditions for reduction to secondary amines,substrate expansion,and further optimization of substrates during expansion.The fourth chapter summarizes the synthesis methods of the primary amine borane complex and the secondary amine in the whole hydrogen transfer reduction system,the experimental procedures in the experimental process,and the characterization map of some synthetic products.