Transition Metal-catalyzed Decarboxylative A~3 Coupling Of Propiolic Acid

Decarboxylative coupling reaction has been recognized as an important tool for functional transformation,including the construction of carbon-carbon bonds,for the generation of important organic intermediates.Transition metal catalyzed decarboxylative coupling has attracted the attention of the organic chemists,and also made the development of organic chemistry.In this paper,a variety of 1,4-diheterocyclo-2-butynes and 1,4-diamino-2-butynes were obtained by decarbonylative coupling reactions using transition metal copper as a catalyst.Compared with the traditional methods,this method provided a mild reaction condition,simple operation,high yield,environmental friendliness,widely applicability of the substrate etc.The research work of this thesis includes the following three parts:Part ?:Transition metal CuI/CuBr₂ catalyzed decarboxylation coupling reaction for the synthesis of 1,4-diheterocyclo-2-butyne.Here,The 1,4-diheterocyclo-2-butynes were synthesized by one-pot method using transition metal copper as a catalyst.This method has good substrates suitability,mild reaction condition,simple operation,high yield,environmentally friendly and fitting for the concept of green chemistry.Part ?:The transition metal CuCl₂/CuCl catalyzed decarbonylative coupling to asymmetric 1,4-diamino-2-butyne.Investigation of the CuCl₂/CuCl catalyzed chemoselective reaction of two aldehydes with one amine,the asymmetric 1,4-diamino-2-butynes were producted by decarbonylative coupling reaction.The reaction used water as the solvent,and the byproducts were only low toxic carbon dioxide gas and water,which was environmentally friendly.Part ?:The transition metal CuCl₂/CuCl catalyzed one-pot,two-step decarbonylative coupling to asymmetric 1,4-diamino-2-butyne.On the basis of the second part,another amine was added to synthesize asymmetric1,4-diamino-2-butyne in one-pot,two-step in the presence of a combination catalyst.The substrates had wide applicability,and atomic economy,was environment-friendly with high chemical selectivity.