Palladium Or Nickel Promoted Oxidative C(sp~3)-H/P-H Cross-coupling Reactions

Organophosphorus compounds have been wildly applied in the fields of pesticides,medicine,material chemistry and organic catalysis duo to their excellent photoelectric properties and special chemical and biological reactivity.Traditional methods to construct C-P bonds mainly rely on the Michaelis-Arbuzov and the Hirao reactions.Regrettably,these reactions usually exhibit toxicity,narrow substrate scope,and harsh reaction condition.At the same time,C(sp~3)-P bonds,which are ubiquitous in organic compounds are also difficult to achieve by the above mentioned reactions.Therefore it is extremely important and challenging to develop new methods to construct C(sp~3)-P bonds.In recent years,transition-metal-catalyzed inert C(sp~3)-H bonds activations have developed as a powerful method to construct different carbon-carbon or carbon-heteroatom bonds.These reactions atomic economy,and avoid the pre-activations of substrates.Therefore,it is undoubtably an ideal strategy to synthesize organophosphine compounds containing C(sp~3)-P bonds via transition-metal-catalyzed oxidative C(sp~3)-H/P-H cross-coupling reactions.This paper demonstrated two types of transion-metal-catalyzed oxidative C(sp~3)-H/P-H cross-coupling reactions.The first part focused on palladium-catalyzed oxidative cross-coupling reaction between 8-methylquinoline derivatives and H-phosphonates.The reaction system exhibited high functional tolerance and wide substrate scope.In addition,we investigated the reaction mechanism detailedly according to isotopic labling and X-ray single crystal diffraction.In the second part of this thesis,we investigated the nickel-promoted oxidative phosphorylation of unactivated C(sp~3)-H bonds with the assistance of 8-aminoquinoline moiety.According to our preliminary studies about the optimizations of reaction conditions,we found that the current reaction system may undergo a different pathway to the previous examples on nickel-catalyzed C(sp~3)-H activation reactions.However,the optimal reaction condition and the detailed reaction mechanism are not available yet,and more efforts are still on the way.