Copper Involved In The Trifluoromethylthiolation And Perfluoroalkylation Reaction And Nickel-Catalyzed Acylation Reaction

The trifluoromethylthio-substituted or perfluoroalkyl-substituted compounds are very important fluorine-containing compounds and widely used in medicine and pesticide.Meanwhile,the carbonyl compounds are vital building blocks in organic synthesis as well as an important functionality found in several natural products and in various pharmaceutical compounds.Therefore,we reported here a method for introducing trifluoromethylthio group into organic molecules using copper to participate in constructing the C-S bond,a class of effective decarboxylative perfluoroalkylating reagents were invented for the decarboxylative perfluoroalkylation of aryl and heteroaryl halides,and a nickel-catalyzed the acylation of aryl iodides with various readily available alkyl carboxylic acids.This dissertation includes five chapters.Chapter 1:IntrodutionFor trifluoromethylthiolation reaction,we mainly reviewed recent the development of radical-type,electrophilic-type and nucleophilic-type trifluoromethylthiolation's method strategy.For perfluoroalkylation reaction,we mainly introduced the method for directly introduction of longer-chain perfluoroalkyl moieties into aryl compound.And for acylation reaction,we reviewed the progress of direct transition metal catalyzed the acyl and carbonylaton reaction.Chapter 2:Copper involved in the Trifluoromethylthiolation of?-bromoketonesThe ?-trifluoromethylthio-substituted ketones have great potential application value;however,the development of preparation of ?-trifluoromethylthio-substituted carbonyl compounds is much less explored.Therefore,we reported the two methods for the trifluoromethylthiolation of ?-bromoketones.First,a new protocol to the direct construction of a-trifluoromethylthio-substituted ketones from readily available starting materials has been achieved using copper catalysis.This method is simple and easy to operate and use raw materials of tap cheaply.Second,we described a procedure for the preparation of ?-trifluoromethylthio-substituted ketones by using[(bpy)Cu(SCF3)]as the nucleophilic trifluoromethylthiolation reagent.The reaction provides an efficient and practical approach to ?-trifluoromethylthiosubstituted ketones with a wide range of functional groups and good chemoselectivity.The above two methods work together to provide an efficient and practical way for the trifluoromethylthiolation of a-bromoketones.Chapter 3:Copper-Mediated Trifluoromethylthiolation of Vinyl BromidesDouble bond group is the functional group in olefin and has strong reactivity can occur hydrogenation,halogenation,polymerization and some other variety of chemical conversion.The vinyl trifluoromethyl thioether can serve as an important intermediate for synthesis of trifluoromethylthio-substituted functional molecules.Therefore,we developed a copper-mediated trifluoromethylthiolation of vinyl bromides using[(bpy)Cu(SCF3)]as the trifluoromethylthiolation reagent.The reaction describes a broad substrate scope and a variety of functional groups as well as the complete retention of the olefin geometry.Chapter 4:Copper-Mediated Perfluoroalkylation of Aryl and Heteroaryl HalidesIt's fail to use Swarts-type reaction to direct introduction of longer-chain perfluoroalkyl moieties into organic compound,most of longer-chain perfluoroalkyl compound were synthesized by carbon-carbon bonds formation using expensive raw materials as fluorine source.Here,we describes the invention of a class of copper(I)perfluorocarboxylato complexes using inexpensive and readily available perfluorinated carboxylic acid as fluorine source.Further,the decarboxylative perfluoroalkylation of these reagents with aryl and heteroaryl halides have been investigated.These complexes can serve as efficient reagents for the decarboxylative perfluoroalkylation of aryl and heteroaryl halides with good functional group compatibility.Finally,the reaction progress was calculated by DFT theory as well as the mechanism was predicted.Chapter 5:Nickel-Catalyzed Acylation of Aryl IodidesAlkyl aryl ketones are vital building blocks in organic synthesis as well as an important functionality found in many natural products.We reported a practical and highly effective one-pot synthesis of versatile alkyl aryl ketones from economical carboxylic acids and aryl halides via nickel catalyzed under mild conditions.A wide range of primary,secondary,tertiary acids are competent.And a broad substrate scope and a variety of functional groups are tolerated.