Synthesis Of Homopropargyl Amides By Ir-catalytic ?-alkynylation

?,?--unsaturated carbonyl compounds and nucleophilic reagents—alkynyl anion can react with each other by 1,4-conjugated nucleophilic addition and form conjugated alkynylation addition products of ?,?-unsaturated carbonyl compounds,that is,homopropargyl acyl compounds.This reaction can also be catalyzed by the transition metal.However,it is rarely reported for the synthesis of homopropargyl amides.Our group has explored the process of promoting the asymmetric alkynylation reaction using an iridium catalyst to activate the carbonyl group.Therefore,this study plans to explore the alkynylation of unsaturated amides using the similar method.The main contents of this study are as follows.(1)The reaction process of the conjugated addition reaction of triisopropylsilyl-acetylene to phenylacetyl pentene is proposed,and the suitable transition metal catalytic precursors and ligands for the reaction are explored.The iridium-catalyzed precursors with cyclooctadiene coordination and achiral bisphosphine ligands complexes were ultimately identified as catalysts.At the same time,the catalytic ability of some chiral ligand catalysts to the reaction was studied,but the research of this part still needs further study.(2)The reaction solvent,reaction temperature,reactant concentration and catalytic material ratio of the conjugated addition reaction of triisopropylsilylacetylene and phenylacetyl pentene were optimized.Detailly,this part includes synthesis and characterizations of phenylacetyl pentene and the corresponding addition products at first.Then the GC detection method and GC quantitative equation of phenylpentyl pentene and its corresponding addition products were identified.Finally,the optimum reaction temperature,by optimizing the reaction yield The optimum reaction solvent,reaction temperature,reactant concentration and feeding ratio of catalytic material were determined,and the reason or trend of these factors' influence on addition reactions'yields the was analyzed.(3)Some of the alkynylation addition products were synthesized using the optimized conditions of the addition reaction of triisopropylsilylacetylene and phenylacetyl pentene.Detailly,this part includes synthesis and characterizations of ?,?-unsaturated amide compounds at first.Then some of homopropargyl amides were synthesized and isolated using the above-mentioned optimum conditions through the alkynylation conjugation addition reaction.Finally,the synthesis effect was evaluated,and the synthesized homopropargyl amides were characterized.In this study,an efficient alkynylation conjugation addition scheme for ?,?-unsaturated amide compounds was found.Some of homopropargyl amides were synthesized with good isolated yields using this scheme including catalytic action of iridium catalyst.Thus the expected results were obtained.