ABSTRACT This thesis discusses development of a few new methodogies involving transition metal catalysis. For sake of convenience and better understanding, the thesis is divided into five chapters. In the first chapter a novel ruthenium catalyzed cyclization of epoxide with a tethered alkynehas been described. We found that Treatment of (o-ethynyl)phenyl epoxides with TpRuPPh3(CH3CN)2PF6(10 mol%) in hot toluene gave naphthanol or 1-alkylidene-2-indanone very selectively with isolated yields exceeding 80%, depending on the nature of epoxide substituents. Surprisingly, the reaction intermediate was proved to be ruthenium-π-ketene species that can be trapped efficiently by alcohol to give ester compound. This phenomenon indicates a novel oxygen transfer from epoxide to its terminal alkyne catalyzed by ruthenium complex. A plausible mechanism is proposed on the basis of deuterium-labeling experiment. The second chapter deals with a oxidation of platinum-carbene intermediates derived from 2-Ethenyl-1-(prop-2’-yn-1’-ol)benzenes. 2-Ethenyl-1-(prop-2’-yn-1’-ol)benzenes were cyclized through catalytic oxidation with PtCl2/CO/H2O and the metal–naphthylidene intermediates were oxygenated by water. The metal-carbene species has also been intercepted by cyclopropanation. The third chapter describes a platinum catalyzed tandem 6-exo-dig cyclization/Nazarov cyclization sequence to give 1H-cyclopenta[a]naphthalenes efficiently and regioselectively from 2-alkenyl-(1’-hydroxyl-4-en-2-ynyl)benzenes. The fourth chapter presents a unique cycloisomerization of 4,6-dien-1-yn-3-ols to bicyclo[4.1.0]heptenones which involves a 6-endo-dig cyclization resulting from a metal catalyzed carbophilic activation of carbon-carbon triple bond. The last chapter discusses a mild and catalytic protocol for isomerization of trisubstituted epoxides to corresponding allylic alcohols.