Study On Cyclization Reaction Between 1,5(6)-enynes And Halogenated Acetonitrile

The 1,n-enyne cyclisation reaction is one of the most common and straightforward means of constructing this class of compounds,and bridge,spiro and heterocyclic framework structures are widely found in many natural products,drugs and functional materials.In this thesis,a variety of target products with different substituents have been designed and synthesised from the construction of spirocycles and nitrogen-containing heterocyclic compounds under different reaction conditions,using self-designed 1,5(6)-alkenyne structures,These compounds have been characterised in detail to investigate the physicochemical properties of the cyclised products.Detailed study are as follows.1.The C-Br bond on 2-bromo-p-methylenebenzoquinone was coupled to the C-H bond of the terminal alkyne by a Sonogashira palladium-catalyzed coupling reaction,which successfully introduced a phenylethynyl structure containing a substituent into the structure of p-methylenebenzoquinone to construct a 1,5-enynyl structure containing a quinone structure;A new nitrogen-containing 1,6-enynyl structure was successfully constructed after a two-step reaction process using a simple and readily available aniline structure to react with a phenylethynyl acid structure.2.Using Pt(+)/Pt(-)as the reaction chemical reaction electrode,while passing direct current through the reaction system,the halogenated acetonitrile was reacted with the quinone-containing structure of 1,5-arene,and 35 different structures of spirocyclization products were successfully constructed,and halogen functional groups and cyanomethyl functional groups were successfully introduced into the product structures;using copper(I)as the catalyst,under high temperature conditions The reaction of nitrogen-containing 1,6-enyne with halogenated acetonitrile was successfully carried out to construct 25 nitrogen-containing heterocyclic products containing succinate structures.After the substrate expansion was completed,different mechanistic control experiments were also designed in this thesis to provide preliminary speculations on the chemical reaction mechanism of the two reactions,respectively.3.The hydrogen and carbon spectra of sixty compounds were determined using isotope labelling methods,and the product structures of the compounds were initially determined by peak shape and chemical shift.The cis-trans conformations of the compounds were further determined by X-ray single crystal diffraction.Specific analytical data for the individual product structures are included in the thesis.