Yoshio Seki

The synthesis of (E)-1,2-disilylethenes from a triorganosilylethene with the aid of Ru3(CO)12 and a hydrosilane

Abstract The Ru 3 (CO) 12 -catalyzed reaction of trimethylsilylethene with triethylsilane gives a mixture of ( E )-1,2-bis(trimethylsilyl)ethene and ( E )-1-triethylsilyl-2-trimethylsilylethene. The yield of ( E -1,2-bis(trimethylsilyl)ethene increases with an increase in the molar ratio of trimethylsilylethene to triethylsilane. The Ru 3 (CO) 12 -catalyzed reaction of trimethylsilylethene in the presence of a catalytic amount of triphenylsilane also gives ( E )-1,2-bis(trimethylsilyl)ethene in good yields. Triorganosilylethenes such as dimethyl(ethoxy)silylethene and triethoxysilylethene also give the corresponding ( E )-1,2-disilylethenes. The similar, catalyzed reaction of styrene with trimethylsilylethene gives 1-trimethylsilyl-2-phenylethene in good yields.

Reaction of terminal olefins with a hydrosilane and with carbon monoxide catalyzed by complexes of cobalt, ruthenium, and rhodium

Abstract The Co2(CO)8-catalyzed reaction of 1-hexene with diethylmethylsilane and carbon monoxide gave high total yields of four isomers of enol silyl ethers (regio- and stereoisomers) as the results of CO incorporation. The effects of changes in reaction conditions (CO pressure, molar ratio of the reactants, and temperature) on the isomer composition were studied. The catalytic activity of various transition metal complexes was examined and Co2(CO)8, Ru3(CO)12, and RhCl(PPh)3)3 shown to be effective. The catalyzed reaction of methyl acrylate also gave the corresponding enol silyl ethers. The Co2(CO)8-catalyzed reaction of 1,5-hexadiene with a hydrosilane and carbon monoxide afforded a cyclic compound in addition to straight-chain enol silyl ethers.