Recent advances in the synthetic and mechanistic aspects of the ruthenium-catalyzed carbon–heteroatom bond forming reactions of alkenes and alkynes

The group’s recent advances in catalytic carbon-to-heteroatom bond forming reactions of alkenes and alkynes are described. For the C–O bond formation reaction, a well-defined bifunctional ruthenium-amido catalyst has been successfully employed for the conjugate addition of alcohols to acrylic compounds. The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the regioselective alkyne-to-carboxylic acid coupling reaction in yielding synthetically useful enol ester products. Cationic ruthenium-hydride catalyst generated in-situ from (PCy3)2(CO)RuHCl/HBF4·OEt2 was successfully utilized for both the hydroamination and related C–N bond forming reactions of alkenes. For the C–Si bond formation reaction, regio- and stereoselective dehydrosilylation of alkenes and hydrosilylation of alkynes have been developed by using a well-defined ruthenium-hydride catalyst. Scope and mechanistic aspects of these carbon-to-heteroatom bond forming reactions are discussed.