Hydrosilylation of olefins in the presence of metal carbonyls

Cobalt Complex-Catalyzed Hydrosilylation of Alkenes and Alkynes

“…In contrast to the hydrosilylation of the linear diene, the hydrosilylation of 1,3-cyclohexadiene, and 1,3-cyclooctadiene with HSi­(OEt) 3 could selectively afford the 1,4-addition products in good yields (Scheme ). This result is consistent with Kalinin’s study on Co 2 (CO) 8 -catalyzed hydrosilylation of cyclopentadiene with HSi­(OEt) 3 …”

“…In addition to the hydrosilylation of the alkyl substituted alkenes, Kalinin et al investigated Co 2 (CO) 8 -catalyzed hydrosilylation of styrene, vinyltrimethylsilane, 1-vinyl- o -carborane, and allyl di­(triethoxysilyl)­amine with HSi­(OEt) 3 (Scheme ). These reactions can operate with an equimolar ratio of the substrates and selectively furnish the anti -Markovnikov addition products. The reaction yields were found to be dependent on the alkenes.…”

“…A comparative study on the reactions of vinyltrimethylsilane with HSi­(OEt) 3 using Co 2 (CO) 8 (0.023 M) and Rh 4 (CO) 12 (0.0011 M) as catalysts revealed that both reactions can furnish the anti -Markovnikov addition product in comparable yields. However, the rate of the cobalt-catalyzed reaction is slower …”

Advances in Base-Metal-Catalyzed Alkene Hydrosilylation

“…The side reactions, dehydrogenative silylation and hydrogenation that often occurred in the catalysis using Fe­(CO) 5 , were not observed in the Co-catalyzed process. , However, Co 2 (CO) 8 could effect the isomerization of 1-alkenes to form inactive internal alkenes, and thus, an excess of alkenes (3 equiv relative to silane) was required. Later, Kalinin and co-workers broadened the substrate scope of the Co 2 (CO) 8 -catalyzed hydrosilylation . Styrene and several functionalized alkenes, including allyl di­(triethoxysilyl)­amine and 1-vinyl- o -carborane, could be hydrosilylated with (EtO) 3 SiH to give the corresponding anti -Markovnikov products in moderate to high yields.…”

“…Later, Kalinin and co-workers broadened the substrate scope of the Co 2 (CO) 8 -catalyzed hydrosilylation. 58 Styrene and several functionalized alkenes, including allyl di(triethoxysilyl)amine and 1-vinyl-o-carborane, could be hydrosilylated with (EtO) 3 SiH to give the corresponding anti-Markovnikov products in moderate to high yields. In addition, Darling and co-workers applied this Co catalyst to the synthesis of chlorosilyl-functionalized polystyrene via the hydrosilylation of the residual vinyl groups in (vinyl)polystyrene.…”