The Trifuoromethylation Of Arylpropiolic Acids And Styrenes

The synthetic methods for trifluoromethylated acetylenes through decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3 and ?-CF3 ketones from oxidative trifluoromethylation of alkenes have been developed in this thesis, which contains two sections as following.Section one focuses on decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3. Trifluoromethylated acetylene (RC?CCF3) is a very important structural unit in the field of organic chemistry. Usually, terminal alkynes have been employed as alkyne sources for the synthesis of Csp-CF3 bonds. However, there is a limitation that terminal alkynes are cumbersomely handled because of the relatively low boiling point. Compared to terminal alkynes, the arylpropiolic acids as alkyne sources have many advantages. They are usually solid-state without strong smells and easy to store and handle. And this method has potential application in some degree.In this paper, we choose the phenylpropiolic acid with Me3SiCF3 as the initial substrates, and explore the optimal conditions of this reaction. The optimal conditions are:arylpropiolic acid:0.1 mmol, Me3SiCF3:5.0 equiv, KF:3.0 equiv, Ag2CO3:2.0 equiv, CuI/phen:1.0 equiv, DMF as the solvent, under nitrogen at room temperature for 6.5 h. With the optimal reaction conditions in hand, we next investigated the substrate scope of decarboxylative trifluoromethylation of arylpropiolic acids and get 18 corresponding products in modest to good yields. Moreover, a plausible mechanism for the decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3 was proposed.Section two focuses on a copper-catalyzed oxidative trifluoromethylation of styrenes to synthesize ?-CF3 ketones. ?-CF3 ketones are important organic intermediate, which are widely applied in chemistry. After a series of condition experiments, we make sure the optimal conditions for this reaction:alkenes 0.1 mmol, Togni's reagents(?) 1.2 equiv, (CF3COO)2Cu 10 mol%, TBHP 3 equiv, DMSO as the solvent, under nitrogen at 65? for 48 h. With the optimal reaction conditions in hand, we next investigated the substrate scope. This method is easy to handle, and only requires cheap subjects.