Study On Nickel-catalyzed Carbofunctionalization Of Carbon-carbon Unsaturated Bond

Carbon-carbon bonds constitute the basic skeleton of organic compounds,so how to efficiently construct carbon-carbon bonds is one of the core scientific problems of synthetic chemistry.At present,transition-metal-catalyzed carbon-carbon coupling is a hot topic in organic chemistry.Transition-metal-catalyzed carbofunctionalization of carbon-carbon unsaturated bonds is one of effective means to construct carbon-carbon bonds in recent years.This reaction can efficiently construct one or multiple new carbon-carbon bonds from simple raw materials to form substituted alkyl or alkenyl compounds.Despite the important progress has been made in this field,this type of reaction still faces challenges in many aspects,such as how to control the reactivity and selectivity.Therefore,it is important significance to develop new catalytic systems to solve these problems.This thesis focuses on nickel-catalyzed intermolecular carbofunctionalization reactions of olefins or alkynes,which was mainly divided into the following three parts:Part Ⅰ:Based on the strategy of catalytic reductive cross-coupling,we first reported example of the three-component carboacylation of unactivated alkenes and acyl chlorides with perfluoroalkyl iodides by using Ni Cl₂·DME as nickel catalyst and dtbbpy as ligand.The reaction successfully regulates chemoselectivity and regioselectivity by utilizing a pendant weak chelating group.The reaction has good functional group tolerance and broad substrate scope.A series of unactivated olefins,aryl acyl chlorides,alkyl acyl chlorides,and polyfluoroalkyl iodides can formβ-fluoroalkyl ketones.Part Ⅱ:Based on the strategy of photoredox and nickel dual catalysis,we achieved intermolecular hydroaminocarbonylation of alkynes with amines and CO to afford a series ofα,β-unsaturated amides with moderate to high efficiency and excellent branched selectivity in the present of Ir[d F（CF₃）（ppy）₂（bpy）]（PF₆）as photoredox catalyst,Ni Cl₂·DME as nickel catalyst,4,4’-di（CF₃）-bpy as ligand,K₂CO₃ as base and Bn Bpin as Lewis acid additive.Interestingly,this synergistic strategy also enables an unprecedented sequential four-component hydroaminocarbonylation/radical alkylation process to form substituted aliphatic amides in the presence of tertiary and secondary alkyl boronate esters.A series of cyclic and acyclic tertiary alkyl boronate esters were subjected to this system.In addition,silylborates can also be compatible with system to formβ-silyl amide compounds.Part Ⅲ:Based on the strategy of photoredox and nickel dual catalysis,we achieved Markovnikov-selective hydrobenzylation of terminal alkynes with benzylic chlorides by using Ir[d F（CF₃）（ppy）₂（Phen）]（PF₆）as photoredox catalyst,Ni（acac）₂ as nickel catalyst,dtbbpy as ligand,1-ethylpiperidine as reductant and difluoroacetic acid as additive.A range of aryl and alkyl terminal alkynes are efficiently coupled with benzylic chlorides,resulting in branch-selectivity benzyl substituted olefin compounds with moderate to high yields.