Study On ?-trifluoromethylation And ?-decarboxyl Trifluoromethylation Of Dithioketene

Trifluoromethyl-containing compounds have significant physical,chemical and biological properties and play an important role in modern drug innovation and discovery of new drugs.The introduction of trifluoromethyl groups into organic molecules is a hot research topic in the field of organic synthesis.The development and use of trifluoromethylation reagents has proven to be the key to the development of efficient trifluoromethylation methods.The development of ArICF₃X as an electrophilic trifluoromethylation reagent has been an urgent research topic in the field of organic fluorine chemistry.However,due to the limitations of ArICF₃X in the preparation process and the instability of the reagent itself,the research work is extremely challenging.Currently,Togni reagents with only two cyclic structures in the field are widely used.Our research team has carried out continuous research work in the field of trifluoromethylation methodology.Based on the detection of the presence of[PhICF₃]⁺species by HRMS,the first preparation by simple,direct ligand exchange reaction was carried out.The stable acyclic structure of PhICF₃Cl provides a basis for the synthesis and application of ArICF₃X.Since PhICF₃Cl is partially ionic,it has a more efficient CF₃ transfer ability than the covalently structured Togni reagent.It has been shown that PhICF₃Cl can directly carry out various types of trifluoromethylation reactions without catalyst or activator.The systematic development of the application of PhICF₃Cl in synthesis will provide a new opportunity for the study of trifluoromethylation methodology.In this thesis,PhICF₃Cl was used as a trifluoromethylation reagent.The?-trifluoromethylation reaction of?-oxodithioketal and the?-decarboxyl trifluoromethylation reaction were systematically investigated to establish a highly efficient method.The research content of the thesis consists of the following four parts:1:Introduce some electrophilic trifluoromethylation reagents and their applications.The electrophilic trifluoromethylation reagent mainly includes Umemoto reagent and Togni reagent,they are trifluoromethyl source commonly used in the trifluoromethylation reaction.2:introduce the significance of the topic of this paper.Based on the open-chain trifluoromethyl iodine reagent developed by our group and disulfide ketone as a nucleophile,trifluoromethylation of?-dithioketal and?-decarboxyl were efficiently realized.A series of trifluoromethyl-containing compounds were synthesized.3:The use of PhICF₃Cl as a trifluoromethylating reagent to achieve?-trifluoromethylation of?-oxodithioketal,which is highly efficient without the addition of any catalyst or activator.19 trifluoromethyl compounds were prepared and characterized by ¹H NMR,¹⁹F NMR,¹³C NMR and MS.4:The use of PhICF₃Cl as a trifluoromethylating reagent to achieve the?-decarboxyl trifluoromethylation of?-carboxydithioketal,and the efficient preparation of 9 trifluoromethyl compounds.¹H NMR,¹⁹F NMR,¹³C NMR,MS characterization provides a new way to synthesize substituted olefins containing trifluoromethyl group.