Alkenes can undergo a variety of chemical reactions to form more complex molecules with a range of functional groups. This makes them useful starting materials for synthesizing a wide range of organic compounds. Chapter I provided an overview of the development history of alkenyl C8́2H bond activation. The early reactions of C8́2H compounds with metal complexes, as well as stoichiometric activation of the transition metal-activated C-H bond, were discussed. Then the first successful and efficient organometallic-catalyzed transformations of a C8́2H bond, the first transition metal-catalyzed vinylic C-H functionalization, and the first transition metal-catalyzed olefinic C-H functionalization under mild conditions were demonstrated. Finally, enantioselective vinylic C-H functionalization was discussed. In Chapter II, a method for enantioselective vinylic C(sp2)8́2H bond activation using a Ru(II) catalyst and a chiral transient directing group was developed. Chiral amine was also utilized to control the Z/E stereoselectivity. The method demonstrated a broad substrate scope with good yield, high Z/E ratio stereoselectivity, and excellent enantioselectivity. Its synthetic utility was demonstrated by the synthesis of key structural motifs of particularly useful natural products and pharmaceutical compounds. Additionally, a rare vinylic C8́2H bond activated ruthenic complex was isolated and determined by single-crystal X-ray diffraction. The methodology suggested in this work is expected to facilitate the further development of asymmetric vinylic C8́2H functionalization reactions. In Chapter III, a practical and efficient methodology for Ru(II)-catalyzed enantioselective alkenyl C-H bond functionalization of indole-substituted acrylaldehyde derivatives via the chiral transient directing group (CTDG) strategy to obtain optically active pyrrolo[1,2-a]indole derivatives was suggested. The methodology resulted in a series of optically active products with good yields (up to 80%), good stereoselectivity (up to 25.0:1 Z/E), and excellent enantioselectivity (up to 95% ee). Furthermore, synthetic transformations were explored. Chapter IV presented the first demonstration of a sequentially composed catalytic substitution reaction of alkenes for building multi-amido methylated derivatives while reserving the Ï0- components. The process involved a simple Fe (III)-catalyst and bisamidomethane reagent, which directly and selectively transformed Îł-substituted styrenes into several biologically and pharmaceutically relevant N-heterocycles through tandem processes.