Hydrosilylation of acetylene and monosubstituted acetylenes in the presence of rhodium complexes

Dehydrogenative Coupling of Terminal Alkynes with O/N-Based Monohydrosilanes Catalyzed by Rare-Earth Metal Complexes

“…The catalytic cross-dehydrogenative coupling of terminal alkynes with hydrosilanes presents the most attractive and atom-economic synthetic route, because the only byproduct is H 2 . Thus, several catalytic systems including transition-metal, alkaline-metal, alkaline-earth metal, main-group element, and a divalent ytterbium-imine complex have been successfully developed for this reaction system in the previous work (Scheme ). Despite these impressive advances, such reaction systems suffer more or less from some side reactions associated with this cross-coupling, for example, competitive hydrosilylation of alkynes, isomerization, and dimerization of terminal alkynes. ,, Moreover, most reaction systems have relied on hydrocarbon silanes as a reaction partner, while the heteroatom-substituted hydrosilanes, such as alkoxysilanes and aminosilanes, have been rarely used, probably due to the presence of more polarized Si–O and Si–N bonds, as observed in the stoichiometric reactions of a scandium phosphinoalkylidene complex with triethoxysilane or the reactions of yttrium hydride with methoxysilane, involving the cleavage of the Si–O bond to form scandium or yttrium alkoxides, while alkoxysilylalkynes are an important building block, utilized in a range of transformations, such as the Hiyama alkynylation/cyclization reaction, , [4 + 2] cycloaddition, and alkynylation of ketones. , Recently, RCCSi­(OMe) 3 was used in trifluoromethylalkynylation of alkenes via a copper-catalyzed radical relay process .…”