65118-95-8Relevant academic research and scientific papers
Utilization of a Trimethylsilyl Group as a Synthetic Equivalent of a Hydroxyl Group via Chemoselective C(sp3)-H Borylation at the Methyl Group on Silicon
Torigoe, Takeru,Ohmura, Toshimichi,Suginome, Michinori
, p. 2943 - 2956 (2017)
A conversion of trimethylsilylalkanes into the corresponding alcohols is established based on an iridium-catalyzed, chemoselective C(sp3)-H borylation of the methyl group on silicon. The (borylmethyl)silyl group formed by C(sp3)-H borylation is treated with H2O2/NaOH, and the resulting (hydroxymethyl)silyl group is converted into a hydroxyl group by Brook rearrangement, followed by oxidation of the resulting methoxysilyl group under Tamao conditions. An alternative route proceeding through the formylsilyl group formed from a (hydroxymethyl)silyl group by Swern oxidation is also established. The method is applicable to substituted trimethylsilylcycloalkanes and 1,1-dimethyl-1-silacyclopentane for conversion into the corresponding stereodefined cycloalkyl alcohols and 1,4-butanediol.
Effects of Proximate Polar Groups on the Rates of Hydrosilylation
Eddy, Victoria J.,Hallgren, John E.
, p. 1903 - 1906 (2007/10/02)
Endo-, exo-, and trans-2,3-disubstituted bicyclohept-5-enes were found to react with dimethylchlorosilane in the presence of a platinum catalyst to yield the corresponding 5-silyl derivatives.The reaction of the endo anhydride proceeded in high yield, although quite slowly.The exo anhydride was found to react faster than the analogous endo epimer.Furthermore, the endo N-phenylimide did not react under these conditions, while the exo N-phenylimide epimer reacted rapidly and in high yield.A similar ordering of reactivity was observed with the endo-, trans-, and exo-2,3-dicarbomethoxybicyclohept-5-enes.Silicon was found exclusively on the exo face of the bicycloheptyl skeleton, remote from substituents at the 2,3-positions.Purely steric arguments are insufficient to explain the anomalous reactivity of the endo anhydride and endo N-phenylimide.However, the reactivity differences can be rationalized in terms of field effects exerted by the electron-deficient anhydride and imide rings.
