Zirconium-catalyzed highly regioselective hydrosilation reaction of alkenes and x-ray structures of silyl(hydrido)zirconocene derivatives

Rapid, Regioconvergent, Solvent-Free Alkene Hydrosilylation with a Cobalt Catalyst

“…This has been seen previously with certain Zr catalysts, 28 Pt catalysts, 29 and Fe catalysts. 11 We propose that this transformation is a tandem isomerization−hydrosilylation consisting of two steps: (1) rapid isomerization of the alkene and (2) selective hydrosilylation of the terminal alkene.…”

Hydrozirconation

“…Recently, Cp 2 Zr(H)OTf, soluble in THF up to a concentration of 0.1 M, was prepared by Luinstra and coworkers from the borohydride complex Cp 2 ZrBH 4 (OTf) and 1 equiv. [64]. The larger triflate anion gave a well-defined and very reactive dimeric hydrozirconating reagent, which was successfully applied for the hydrozirconation of alkenes, alkynes, and imines [49,50].…”

Zirconocene-Catalyzed Silylation of Alkenes with Chlorosilanes

“…We also conducted several control experiments in order to elucidate the reaction pathway leading to dialkylzirconocene intermediates such as 8 or 11. Since a small amount of the corresponding silane R 3 SiH is formed as a by-product (`5 %) in the present silylation reaction and since it is known that zirconocene complexes catalyze the addition of R 3 SiH to alkenes, [13] we first examined whether hydrosilylation is involved. When a reaction similar to that in entry 5 of Table 2 was carried out in the presence of Et 3 SiH, only 4 b was obtained as the silylated product in 86 % yield, and unchanged Et 3 SiH was recovered.…”