The reactions of arene- and methanesulfonyl chlorides with alkenes catalyzed by dichlorotris(triphenylphosphine)ruthenium (II) were found to give 1 : 1 adducts in high yield. Whereas, trichloromethanesulfonyl chloride added to alkenes with extrusion of sulfur dioxide under similar conditions. A reaction mechanism involving a radical intermediate which interacts to the ruthenium in the coordination sphere is proposed. The reactions of styrylsulfonyl chloride with alkenes under similar conditions afforded 1 : 1 adducts at the initial step, then followed dehydrochlorination and desulfonylation from the adducts successively to give divinyl sulfones and 1, 3-butadienes in high yield, respectively. The reaction is a novel and convenient methods for synthesis of substituted 1, 3-butadienes. The reactions of alkane- and arenesulfonyl chloride with alkenes in the presence of a catalytic amount of ruthenium (II) complex with chiral ligand, Ru₂Cl₄ [(+)-DION]₃ or Ru₂Cl₄- [(-)-DION]_3', were found to give optically active adducts with about 10-40 % e.e. These results suggest that radicals formed by the interaction with metal catalysts are coordinated with metals, and therefore such reactive species should be called “RADICALOID” since carbenes coordinated to metals are called carbenoid.