The Research On Palladium-Catalyzed Difunctionalization Reactions Of Alkenes And Trifluoromethylation Of Indoles Reactions

Functionalizations of olefins are very important in chemical transformation. It made great contributions to the synthesis of diversity of organic molecules. In this thesis our group synthesized the six membered ring nitric products by palladium-catalyzed oxidation of unactivated alkenes at the first time. It provided more choices to synthesize the six membered ring nitrogen heterocyclic compounds. At the same time, our group has developed a novel palladium-catalyzed oxidative trifluoromethylation of indoles. It was an innovation in the field of trifluoromethylation reaction and it has great theoretical significance and practical value.This thesis was made up of three chapters. In the first chapter, two species of catalytic mechanistic of palladium were introducted and the reaction of alkene difunctionalization was reviewedIn the second chapter, A Palladium catalyzed intramolecular oxidative aminonitroxylation of unactivated alkenes was reported. In the reaction, the silver nitrate was used as the source of nitrate anion, in situ generation of iodine(III) nitrate reagent PhI(NO3)₂ as the oxidant, DCE(1,2-dichloroethane) was used as the solvent, at room temperature, the six membered ring nitric products were formed effectively and selectively. Mechanistic studies was also carried out, it considered the reaction was started through aminopalladation, then it has gone through a process of Pd(IV) intermediate which followed by reductive elimination to form product with C-O bond formation. It provided theoretical basis for constructing six membered ring nitrogen heterocyclic compounds. At last, all the experiment process about the compounds which we studied in this chapter was described.In the third chapter, our group preliminary researched palladium catalyzed oxidative trifluoromethylation of indoles at room temperaturte. In the reaction, the Pd(OAc)₂ was used as the catalysts, the TMSCF3 was used as CF3 source, the PhI(OAc)₂ was used as the oxidant. Our group successfully realized trifluoromethylation of indoles. At last, all the experiment process about the compounds which we studied in this chapter was described. All the new compounds were determined by 1H NMR, 13C NMR, 19F NMR and MS. And all the structural Characterizations were analyzed.