Transition-metal-catalyzed C-H Bond Functionalization Reactions Using F~+ As Oxidant

C–H bond activation such a strategy would eliminate the prefunctionalization which make synthetic schemes shorter, more efficient and get the expected products easier than using traditional ways. There are some important applications on natural products and drugs syntheses. The catalytic cycle needs catalyzed amount catalyst and a or more than stoichiometry oxidant during the C–H bond activation/functionalization progress. Because C–F bond is very difficult to formate in high-value metal central using F~+ as oxidant, so this is a good chance to get our expected C–C bond and other bonds.C–C bond coupling is the basic reaction to constrcation complex compounds. Undoubtedly, developing a novel and directly cross-dehydrogenative coupling avoiding prefunctionalization of C–H bond which have a positive economic and green chemistry that is the one of best ways to constrction C–C bond. More than 90% drugs containing at least one N atom and C–N bond formation of one sixth reactions in drug synthesis which has been a long-term objective for chemists to develop a new method to formation C–N bond.The thesis developed a new way to constrction C–C bonds and C–N bonds using palladium and copper as catalysts via F~+ as oxidants. The thesis includes the following four aspects.1. Developed a novel approach to circumvent the common ortho aromatic C–H selectivity in directed palladium catalyzed C–H amination. An unprecedented remote amide-directed palladium-catalyzed intermolecular highly selective benzylic C–H amination with N-fluorobenzenesulfonimide is developed, which represents the first direct benzylic C–H amination with a non-nitrene nitrogen source.2. The first highly regioselective oxidative allylic amination of alkenes with NFSI was developed. At room temperature, Selectfluor mediated palladium catalyzed aminations of allylbenzene derivatives with N-tosylcarbamates in water was also realized. Other advantages such as suitable for various alkenes with a wide range of functionalities and mild reaction conditions made this method attractive. This methodology might open a new way to direct C~–H functionalization in water.3. We developed a novel Cu(OTf)2 catalyzed Selectfluor and water mediated annulation reaction of readily available N-p-toylamides via the first intermolecular successive C–H activation cross-dehydrogenative-coupling (CDC) reaction of benzylic methyl sp~3 C–H and aromatic sp~2 C–H bond, followed by intramolecular C–O bond formation. During the transformation, water played an important role for in situ generation of key F–Cu(III)–OH moiety catalyst with potential dichotomous behaviour for highly regioselective activation of two kinds of C–H bonds in a successive manner. Variously substituted 4H-3,1-benzoxazines were efficiently constructed in good to excellent yields.4. We development a novel method for the construction of quinazoline derivatives via Cu(II) catalyzed intermolecular [5+1] annulation of amidines and widely available DMSO (as a one carbon synthon) is realized, during which methyl C–H bond of DMSO was efficiently activated. Development a successive C–H bond activation、C–N bond formation、C–S bond cleavage and C–C bond formation to costruction quinazoline derivatives.