| As the widely application of fluorine-containing compounds in the fields of medicine and pesticides,the efficiently synthesize of fluorine-containing compounds with different structures has aroused wide interest among fluorologists.Recently,compounds containing fluoroketone structural fragments have been found to have some special biological activities,and drawn much attention in the field of drug discovery and synthesis.This article focuses on the synthesis of the target product of the fluorine-containing ketone structural fragment,and try to use the two types of fluorine-containing reagentsα-monofluorohaloketone blocks andα,α-difluorohaloketone blocks designed by our team to synthesis this fragment with different types of substrates.This highly efficient reaction system provides a variety of options for the synthesis of fluorine-containing ketone structural fragments with various structures.Based on the design,this article is divided into two parts:The first part reported the nucleophilic reaction betweenα-monofluorobromoketone blocks and arylthiophenol compounds or phenolic compounds to synthesizeα-fluoro-βketone（thio）ether compounds.The types of the base and solvent in the template reaction system were screened to obtain the optimal reaction conditions of two types of nucleophilic reactions.1)α-Bromo-α-fluoroketone and p-methoxythiophenol are reacted in THF solvent with K2CO3as base at room temperature for 1-2h.Under the optimal conditions,the structure expansion of the two reaction substrates was carried out,and it was found that thiol compounds are also suitable for this reaction.A total of 21α-fluoro-β-ketosulfides were synthesized.2)α-Bromo-α-fluoroketone and phenol are reacted in Me CN solvent with K3PO3 as base at room temperature for 1-2h.Under the optimal conditions,the structure expansion of the two reaction substrates was carried out,and a total of 24α-fluoro-βketone ethers were synthesized.The second part showed the tandem free radical addition/elimination reaction ofα,α-difluoroketone blocks and olefins under photocatalytic conditions to obtain the allyl difluoroketone compounds.The types of the solvent,light source intensity and base in the template reaction system were screened to obtain the optimized reaction conditions.Specifically,α,α-difluoroketone and p-methoxystyrene were reacted in DME solvent,Et3N were used as a base under 35W blue LED irradiation and Ru（bpy）Cl2·6H2O was used as a catalyst at room temperature for 12-18 h.Under the optimal conditions,the structure expansion of the two reaction substrates was carried out,and it was found that perfluoroiodine reagents are also suitable for this reaction.A total of 24 allyl difluoroketone compounds and 2perfluorovinyl compounds were obtained. |
