Studies On The Radical Aminative-Carbon Migration Of Alkene/Alkyne

N-containing compounds are ubiquitous in biologically active natural products and man-made compounds,especially in pharmaceutical molecule.Therefore,the development of efficient synthetic methods for the construction of C-N bond has attracted much attention.Alkene/alkyne is a common petrochemical feedstocks and usually served as an important organic synthetic block,which can undergo flexible and diverse chemical conversion to synthesize various important compounds.1,2-Difunctionalization of alkene/alkyne,introducing two different functional groups to the C-C multi-bond in one step,has emerged as a powerful synthetic strategy for preparing multi-functional and complex compounds.In recent years,intramolecular functional-group migration triggered by radical addition to alkene/alkyne has been increasingly explored,providing an alternative strategy for difunctionalization of unsaturated ? bond.With this strategy,numerious of versatile coumponds has been synthesized in atomic and step economy fashion.In this thesis,we realized aminative difunctionalization of alkene/alkyne via functional-group migration(aryl,vinyl,alkynyl,alkyl etc.)initiated by nitrogen-centered radical addition to alkene/alkyne,providing new methodology for the synthesis of diversified N-containing compounds.The thesis divided into six chapters:The first chapter reviews the radical aminative functionalization of alkene/alkyne and migration reaction triggered by radical addition;In chapter two,the proposal of the thesis is presented;In chapter 3,we explored the amination/1,4-arylation migration of alkynes,and realized the radical cascade aminoarylation between propargylic alcohols and N-fluoroarylsulfonimides(NFSI).With this methodology,various ?,?-unsaturated carbonyl compounds were efficiently constructed.In this transformation,NFSI was served as oxidant,nitrogen source and aryl source.Additionally,using 1-aryl-3-alkyl propargylic alcohol as starting material,the reaction underwent regio-specific nitrogen-centred radical adding to C-C triple bond and followed by intramolecular aryl trap,providing indenone derivatives.The hydroxyl group of propargylic alcohols played a role of directing group,which could realize high regio-selectivity in radical addition step.This may open a new entry for the development of regio-selective radical addition.Moreover,we tried to use N-chloroarylsulfonimides(NCSI)as an animation reagent to extand difunctionalization of alkynes.A series of oxychlorination products were obtained;In chapter 4,we used 1-en-4-yn-3-ol as substrate,NFSI as radical nitrogen source,through nitrogen radical addition to alkynes incured intramolecular vinyl migration access to various(E)-2-imido-2,4-dienals.These transformations proceeded under mild conditions and show good functional group compatibility with exellent chemo-,regio-and stereo-selectivity.This transformation also represents the first 1,3-carbon migration of propargylic alcohols and their derivatives.The strategy for alkynes imidovinylation might provide a new way toward vinylative functionalization of unsaturated system;In chapter 5,we disclosed the imidoalkynylation of 1,4-diyn-3-ol and NFSI with copper catalyst via 1,3-alkynyl migration to access various ynenones.These transformations proceed with exellent chemo-,regio-and stereo-selective.This strategy provided a new synthetic method toward ynenones.Furtheremore,derivatizations of the prepeared ynenones have been performed and afforded free amine and alcohol;In chapter 6,we developed copper-catalyzed tandem radical amination/1,2-carbon migration of allylic alcohols,using N-F reagent as an efficient amination source,directly access to ?-quaternary-?-amino ketones in single step.This transformation privileged mild raection conditions,good substrate scope,and good functional group compatibility.The reaction leads to the formation of ?-quaternary-?-amino ketones with various cyclic and open-chain structures,including spiro ketones.NHFSO2Ar-type N-F reagent was firstly used as radical amination source in this transformation.