Construction Of CF₃-containing Heterocycle And Amine Compounds Starting From 2,2,2-trifluorodiazoethane

Trifluoromethyl-containing chemicals are extremely useful in chemistry,pharmaceuticals and materials science.Thus,the efficient construction of CF₃-containing compounds has become one of the most important research fields in organicsyntheticchemistry.2,2,2-trifluorodiazoethane,asavaluable trifluoromethylated building block in the construction of trifluoromethyl-containing compounds,has attracted great attentions of organic chemists.Based on our previous research works,this dissertation focuses on 2,2,2-trifluorodiazoethane involved electrophilic addition reactions,nucleophilic addition reactions and annulation reactions.We successfully synthesized a series of CF₃-cotaining N-heterocyclic compounds and CF₃-cotaining amines.The thesis includes three parts as followed:Firstly,we have successfully developed a facile and efficient procedure for the N-electrophilic reaction of CF₃CHN₂ with the in situ generated aminocarbenes.Under the base condition,a range of trifluoromethylated N-aminoguanidines can be accessed in 61–95%yields.Furthermore,two of the molecular's structures were confirmed by means of X-ray crystallographic analysis.The reaction showed many advantages,such as the condition is mild,the reaction time is short and the substrate scope is wide.The realization of the reaction enriches the reaction type of 2,2,2-trifluorodiazoethane,and expands the application range of the reaction.At the same time,we turned our attention to the application of the current protocol to the synthesis of the imidacloprid analogues,and got the analogues smoothly.Secondly,respecting to the active?-H of 2,2,2-trifluorodiazoethane,we have developed the novel dimethylzinc-mediated nucleophilic addition reaction of trifluorodiazoethane with a wide variety of N-?diphenylphosphinoyl?imines.This protocol represents a direct and efficient way to construct?-diazoamines under mild reaction conditions,and a range of trifluoromethylated?-diazoamines can be accessed in 53–94%yields.The synthetic potential has been demonstrated by further transformedtheproductsintotrifluoroethyl-containingaminesand anti-?-amino-?-hydroxy trifluoro-ethyl-ols in good yields,and the products are of high value for multiple synthetic applications.We also applied the current protocols to the synthesis of the Idelalisib analogues,and successfully got the CF₃-containing Idelalisib analogues.Finally,we have developed the[3+2]cycloaddtion reaction of trifluorodiazoethane with various 1,3-diaryl ynones,and a series of3-trifluoromethyl-4,5-disubstituted pyrazoles can be accessed in 64–97%yields and moderate regioselectivity under mild conditions.The reaction can process well without any metals and additives.Moreover,the reaction can also be applied to the alkyne esters and the alkyne nitriles with high regioselectivity.