Study On Alkylation Of Unsaturated Carbon-Carbon Bonds Catalyzed By Transition Metals

Carbon-carbon bond is the basic structural unit of living organisms.Its important nature is self-evident.How to construct carbon-carbon bonds efficiently has always been one of the most important topics in the field of organic synthetic chemistry.In recent years,cross-coupling reactions using transition metal catalysis have evolved into an effective method for synthesizing carbon-carbon bonds.The discovery and development of such reactions is a major breakthrough in the field of organic synthesis.Their basic strategy is to use the unique properties of transition metals and corresponding ligands to promote the corresponding cross-coupling reaction between organic electrophiles and organic nucleophiles.Thereby a new carbon-carbon bond is obtained.This method has many advantages not found in conventional synthetic strategies,such as the ability to obtain selectively distinct products by modulating the reaction system,or the use of chiral ligands to obtain products of high chiral purity,which are for the preparation of complex drug molecules or for high polymerization.Functional materials provide more synthetic pathways that greatly complement the synthesis of complex natural products.The cross-coupling reaction of transition metal catalyzed synthesis of carbon-carbon bonds has been widely used in the industrial synthesis of medicines,natural products and conductive materials,and has made outstanding contributions to the development of the corresponding fields and the whole society.Transition metal catalyzed alkynylation of unsaturated carbon-carbon bonds is one of the common methods for constructing functional organic compounds containing carbon-carbon triple bonds.Such reactions have the advantages of simple operation,mild reaction,high atomic economy,etc.The attention of research scholars.In this paper,the alkynylation of the terminal non-activated alkyne and the alkynylation of the terminal non-activated olefin have been studied in depth.The content is mainly divided into the following two parts.First,the high-regioselectivity and high-stereoselective alkynylation boronization reaction of terminal non-activated alkyne by copper catalyst and nitrogen heterocyclic carbene ligand had been studied.The reaction uses an ether solvent to efficiently react at room temperature,and a higher yield can be obtained after reducing the catalyst loading from 10%to 2%.In terms of substrate compatibility,functional groups such as the alkyl,the aryl group,the heterocyclic,the silicon,the benzyloxy and the like can obtain good yield and selectivity.Second,the high-selective alkynylation hydrogenation of terminal non-activated olefins by nickel catalysts and diazo ligands was investigated.This is the first nickel-catalyzed terminal alkyne hydrogenation alkynylation reaction.Previously,the products of such terminal olefin hydrogenation functionalization reactions were mostly migration addition product or anti-Martensitic addition product.