Palladium-catalyzed Aerobic Reactions Of Alcohols And Amines And Their Applications In The Synthesis Of Amine Derivatives

Organonitrogen compounds are a class of important chemicals in many fields sincenitrogen functionalities such as the amines occur in numerous biologically active molecules,natural products, pharmaceuticals, and are also important synthetic intermediates in organicchemistry. Therefore, preparation of these organonitrogen compounds by constructing C-Nsingle or C=N double bonds starting from a wide range of simple, readily available, andcheap substrates is of particular importance in current researches, which have been one of thehottest topics in organic synthesis. This thesis mainly focuses on transition metal-catalyzedmethods for the synthesis of amine derivatives and imines by directly using alcohols andamines as the substrates, and will be divided to two parts:1) Pd-catalyzed air-promotedaerobic N-alkylation reactions of amides and amines with alcohols;2) Pd-catalyzed aerobicoxidative synthesis of imines from alcohols and amines under ambient conditions.In the first part, we firstly reviewed the recent literatures on the construction of C-Nsingle bond for the synthesis of amine derivatives. Then we present the details of our studieson the Pd-catalyzed air-promoted aerobic N-alkylation reactions of amides and amines withalcohols. During the research, we found the reaction is more likely to proceed via the relayrace mechanism our group recently proposed, but not the well-documented borrowinghydrogen mechanism in the literature.In the second part, we firstly reviewed various methods on the synthesis of imines,during which we found a greener method for the imines directly from alcohols and amines ishighly desirable in the field. Thus, based on our Pd-catalyzed N-alkylation studies, and bycontrolling the reaction conditions and a careful condition screening, we developed a mildPd-catalyzed aerobic oxidative imine preparation method that uses alcohols and amines as the substrates, can be readily carried out at room temperature in open air, and generates water asthe only byproduct.