Studies On The Intermolecule Aminative Functionalization Of Alkynes

N-containing compounds widely exist in biologically active natural products and synthetic medicines molecules.Accordingly,the selective assembly of N-containing compounds from readily available starting materials is a prominent objective in organic synthesis.Aminative functionalization of alkynes,which are abundant and accessible starting materials,represents a highly attractive alternative for the atom and step economic synthesis of diverse N-containing compounds.The thesis involved six chapters.The first chapter reviews the aminative functionalization of alkynes.The proposal of the thesis is presented in chapter two.In chapter 3,based on regio-selective C–N bond construction from alkynes to generate vinyl radicals and followed by 1,4-aryl migration,a general multi-component cascade reaction of alkynes,N-Fluorobenzenesulfonmide and alcohols/TMSN3 was realized.In this work,commercial available N-Fluorobenzenesulfonmide was served as oxidant,nitrogen source and aryl source.This novel transformation may open a new entry for designing radical aminative functionalization reaction.In chapter 4,we explores three-component coupling reactions of NFSI,alkynes and TMSNCS,realizing copper catalyzed aminative thiocyanation of alkynes.Mechanism studies indicated the reaction proceeds via regioselective N-centered radical addition to alkynes and subsequent C–SCN bond formation.Although the reaction need to be further optimized,this transformation represents the first example of radical aminative di-functionalization of simple alkynes,establishing a foundation for designing radical di-functionalization of alkynes.In chapter 5,we disclosed a highly regio-and stereoselective intermolecular chalcogenative amination of alkynes with N-fluorosufonamide(NFSI)and diphenyl dichalconide,wherein NFSI was used as both oxidant and nucleophilic amination source.The reactions feature ambient conditions,high yielding and selectivities,broad substrate scope and excellent functional group tolerance.To our knowledge,it is the first example of intermolecular aminative chalcogenation of alkynes.This new chalcogenative amination provides straightforward way for the synthesis of multi-substituted chalcogenated enamide derivatives from readily available starting materials.In chapter 6,we developed an efficient protocol for the synthesis of iodinated enamines via highly chemo-,regio-and stereo-selective intermolecular aminoiodination of alkynes with N-iodosaccharin(NISac).As known,NISac is a classic electrophilic iodinative reagent.While in this transformation,NISac was used not only as electrophilic iodination but also nucleophilic amination source.This novel reaction highly atom economic realized aminoiodination of alkynes under mild conditions.