Synthesis Of(Z,Z)-1,4-Bis-Chalcogenbuta-1,3-dienes,Vinyl Sulfides And N-Vinylindole Derivatives

Diarylalkyne is a conjugated diyne with a unique structure,which has the wide application in the fields of organic synthesis,functional materials and heterocyclic chemistry.Most commonly,vinyl chalcogenides can be synthesized from diarylalkyne by the addition reaction of sulfur nucleophiles.However,the currently reported methods have some disadvantages,such as low reaction selectivity,limited functional group tolerance,or the use of expensive diaryldiynes as the raw materials.Therefore,it is of great significance to find a new method for the synthesis of vinyl chalcogenides.The main contents of this paper are as follows:In the first chapter,we describe the applications of diaryldiynes in organic synthesis in recent years,including the cycloaddition and non-cycloaddition reactions.Based on the previous research by our group,the main research perspectives of this thesis are proposed.Inchaptertwo,varioussyntheticmethodsfor?Z,Z?-1,4-bis-chalcogenbuta-1,3-dienes are briefly introduced.The experiment in this section is a one-pot two-step process.Firstly,diaryldiynes was synthesized by the reaction of aryl halides and 1,4-bis?trimethylsilyl?butadiyne with a low loading combination of Cu?Xantphos?I and Pd?OAc?₂.Then,thiol or thiophenol is added to the reaction system for the second step.When the aryl halides is an iodide,the reaction was carried out at room temperature.A series of?Z,Z?-1,4-bis-chalcogenbuta-1,3-dienes were synthesized under the optimal conditions.It was found that the reactions exhibited a good functional group tolerance.The synthesized compounds in this chapter were confirmed by ¹H NMR,¹³C NMR,IR and HRMS.The structure of compound II-4b was further verified by X-ray single crystal diffraction.In chapter 3,On the basis of nitrogen,oxygen and sulfur as classification criteria,the applications and synthesis methods of vinyl compounds are reviewed.Then,the synthesis of vinyl sulfide compounds using trimethylsilylacetylene as an alkyne source was introduced.And the optimal reaction condition was obtained as follows:DMF as solvent at 100 ^oC,potassium carbonate as base under the argon protection.In accordance with the previous research of our group,the newly synthesized isothiourea salt as a substitute for thiol was used in the reaction,leading to the same product.These compounds were characterized by ¹H NMR and ¹³C NMR,and some compounds were also confirmed by IR and MS.In chapter 4,the synthesis of vinylindole derivatives from trimethylsilylacetylene was reported.The optimal reaction condition was as follows:DMSO as solvent at 100^oC,potassium hydroxide as base in sealed tube.The reaction scope using a variety of indoles was examined.Substrates bearing an electron-deficient?-NO₂?substitutents on the indole ring resulted in a lower yield.It was also found that nitrogen-containing compound carbazole was also suitable for this reaction.These known synthesized compounds were characterized by ¹H NMR and ¹³C NMR.