The Experimental Designs And Theoretical Studies On Some Nickel And Copper Catalyzed Organic Reactions

The experimental design and the detailed theoretical studies on the reaction mechanisms for the Nickel catalyzed tandem reactions and the Copper catalyzed dipolar reaction between azides and metal acetylides (R-C?C-M, M = Au, Ag, Cu) were studied in the thesis.The first part of this thesis presented a synthetic route design for the nickel catalyzed benzofuran and substitute benzofuran synthesis through a tandem reaction. Then, the theoretical calculations were done to evaluate the synthetic route we designed. The reaction is proceeding through oxidative addition of benzene halide to the Ni complexes and then a migratory insertion of coordinated alkyne to the Ni-C bond, and the substituent group of benzofuran was introduced through Suzuki reactions. The calculated energy barrier of this designed tandem reaction is only 100.3 kJ/mol. Some other possibilities were also considered, such as the Suzuki coupling reaction could occur directly after the oxidative addition of Nickel instead of migratory insertion reaction; whether a six-membered ring can be generated; and in the Suzuki coupling reaction whether coupling for different directions could occur. Our calculations show that these possibilities are energetically unfavorable. Our calculations have provided a simple tandem reaction route for the synthesis of benzofuran and introduced substituent on it, which can react in mild conditions.The second part of the thesis presented a theoretical studies on the reaction mechanism and regioselectivity of Copper catalyzed dipolar reaction between azides and metal acetylides (R-C C-M, M = Au, Ag, Cu). Our calculation results suggest that the dipolar reaction undergo a stepwise process in existence of metal acetylides and Copper catalyst. Our investigation indicates that the catalysts and metal substituent can active the triple bond of alkynes. FMO and NBO charge analysis were also carried out in order to find out how the catalysts and metal substituent affect the 1,4-selectivity of the dipolar reaction. We consider that the substituents of alkynes can affect the selectivity of the dipolar reaction because of their electronic effects. ?...