Studies On Transition Metal And Br(?)nsted Acid Catalyzed C-H Bond Functionalizations

The catalytic C-H bond functionalization as an efficient, enviromentally-friendly and atom-economic organic systhesis strategy has been well developed in the past years, different reaction types and catalytic systems were established. This thesis focus on the development of three new reactions of transition-metal-catalyzed C-H bond functionalization and one example of bronsted acid catalyzed Friedel-Crafts reaction to construct dibenzo[a,d]cycloheptene cores.According to the contents, this thesis is composed of six parts:1. On the basis of my PhD study, the research progress of the following three aspects were summarized:(1) transition-metal-catalyzed allylic C-H bond functionalizations, (2) transition-metal-catalyzed C-H bond addition to the unsaturated carbond-heteroatom bond, (3) transition-metal-catalyzed sp3C-H bonds oxdation reactions.2. We introduced a palladium-catalyzed allylic C-H bond arylation reaction with binol as the key ligand. The reaction used polyfluorobenzene as the arylation reagent and carefully investigated the effect of the ligands in reaction, and applied the catalytic system in different kinds of allylic C-H functionalization reactions.3. We described an example of palladium-catalyzed C-H bond activation of azole derivatives/CH3CN and subsequently addition to the carbonyl of isatin to contruct 3-substituted-3-hydroxy-2-oxindoles, and made a preliminary exploration of the reaction mechanism.4. We summarized the classical and new approaches to systhesis the isoxazoline derivatives, and introduced a copper-catalyzed,sp3C-H bonds oxidation of 2-methylazaarenes and substituted acetophenones to acess isoxazoline derivatives. On the basis of the this results, we extended the reaction system:we used 2-ethylquinoline as the substrate to achieve the cascade sp3C-H bonds oxidation to contruct isoxazoline derivatives. Through the control experments, we proposed a tentative pathway for the transformation.5. We presented a Bronsted acid trifluoromethanesulfonic acid (produced by hydrolization of trifluoromethanesulfonic anhydride) catalyzed olefin Friedel-Crafts alkylation reaction to construct dibenzo[a,d]cycloheptene cores, and applied catalytic system in the totally systhesis of Paucifloral F, Ampelopsin B and the precurser of Diptoindonesin D.