Abstract
New synthetic methods of transition metal-catalyzed annulation and coupling reaction with alkynes using ruthenium, iron and nickel as catalysts are described in this thesis. In first chapter, ruthenium-catalyzed C－H bond activation and [3+2] annulation from N-tosylarylimines and alkynes to synthesize substituted N-tosylindenamine is described. The proposed mechanism involves an intramolecular insertion of the C=NTs group into the C-Ru bond instead of forming [4+2] annulation product via reductive elimination. The second chapter reveals iron-promoted oxidative [4+2] annulation of arylglyoxals with alkynes for the synthesis of substituted 1,2-naphthoquinones at room temperature in short time. Interestingly, the products show an unusual pseudo-migration of the substituent on the arene ring of arylglyoxals. In the proposed mechanism, Fe(III)-promoted electrophilic addition of the vinyl cation to the ipso carbon of the aryl group to give a spiral intermediate and then migration of the keto carbon to the ortho carbon is proposed as key steps. In the final chapter, an economically efficient synthetic method of multi-substituted acrylic acid via nickel-catalyzed carbomagnesiation with alkynes and Grignard reagents and then fixation of carbon dioxide is developed. The catalytic reaction proceeds well with board substrate scopes and high regioselectivity. An alternative method for fixation of CO2 into organic compounds is feasible with this synthetic method and it proceed in gram scale without loss of efficiency in the same time.