Studies On The Palladium-Catalyzed Synthesis Of Aryl Acrylonitriles

Transition-metal-catalyzed C-H functionalization has been rapidly developed due to its remarkable atomic and step economics.It is widely used by organic chemists in the synthesis of natural products and drug molecules.Aryl acrylonitrile is a very important structural unit in the field of organic chemistry.It exists in many drug molecules and is also an important organic synthesis intermediate.Because of its significance in organic synthetic chemistry,aryl acrylonitriles have been synthesized in many literatures.However,the synthetic methods a harsh reaction conditions,poor reactivity,and unsatisfactory yield.Therefore,it is necessary to develop a simple and rapid method of synthesizing aryl acrylonitrile compounds.Based on this,a novel synthesis method for synthesizing aryl acrylonitrile compounds was developed in this thesis.The aryl acetonitriles were used as the reactants,the transition metal palladium(Pd(OAc)2)was used as the catalyst,NIXANTPHOS was the ligand,and the sodium tert-butoxide(NaOtBu)was used as a base.aryl acrylonitriles were obtained alkenylation/isomerization reaction with vinyl halides/trifluoromethanesulfonic anhydrides.This thesis is divided into two chapters.The first chapter review the application of aryl/alkyl acrylonitrile compounds and the synthesis methods of aryl/alkyl acrylonitrile compounds in recent years.The second chapter introduced the reaction conditions of phenylacetonitrile and 2-bromopropene,screening the catalysts,bases,solvents,time,temperature,substrate equivalent ratio and catalysts ratio.Then,the optimal reaction condition was determined.In order to investigate the applicability of the optimal reaction condition to the substrate,the substrate scope was extended in this thesis,and finally 20 aryl acrylonitrile compounds were obtained up to 95%yields.A gram-level reaction and the aryl acrylonitrile subjected to derivatization studies to obtain four aryl acrylonitrile derivatives.In summary,aryl acrylonitriles were prepared by alkenylation/isomerization of aryl acetonitrile with vinyl halide/trifluoromethanesulfonic anhydride using transition-metal-palladium catalyzed reaction of aryl acrylonitriles was developed.