Rh(Ⅲ)-Catalyzed Oxidative Coupling Of Benzamidines And Olefination Of Isonicotinamides

The metal-catalyzed C-H bond activation is an effective way to formation the C-C, C-O,C-N bond. This method has the advantages of simplicity, atom economy. Since2007, rhodiumcomplexes as a new type of metal catalysts widely used in activation of C-H bonds for thereplacement of palladium complexes. In order to form of C-C, C-N and C-O bonds, rhodiumcan catalyze the oxidative coupling of the C-H bond with unsaturated molecules such asalkenes, alkynes and aldehydes. This has been concerned widespreadly and has been advievedrapid developments in the field of basic research and organic synthesis because of lowamount of catalyst, high stability, mild conditions and high selectivity.Chapter1: Rhodium-Catalyzed Oxidative C–H ActivationThis chapter focuses on the progress in the Rh-catalyzed C-H activation to generate theC-E (E=C, O, N) bond. Direct and chelated Rh catalyzed C-H bond activation reactions wereintroduced. The applications about these compounds in organic synthesis were also described.Chapter2: Rh(III)-Catalyzed Oxidative Coupling of Benzamidines and Alkynes[RhCp*Cl2]2can catalyze the oxidative coupling of N-aryl and N-alkyl benzamidineswith alkynes to give N-substituted1-aminoisoquinolines in high selectivity and yield up to99%. Steric bulk of the C-aryl ring of benzamidines has significant effect on the selectivityand reactivity of the coupling.Chapter3: Rh(III)-Catalyzed Oxidative Mono-and Di-olefination of Isonicotinamides[RhCp*Cl2]2can catalyze the oxidative olefination of secondary isonicotinamides withactivated olefins using Cu(OAc)2as an oxidant. The selectivity is largely controlled by thesolvent. In MeCN, mono-olefination, two-fold oxidation reaction is the major pathway. Theselectivity is switched toward diolefination when the reaction is conducted in THF. In bothcases, the coupled products contain an exo-cyclic C=C bond.