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.

Abstract

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.

DOI: 10.1021/acs.joc.6b02917

Cite this paper

@article{Torigoe2017UtilizationOA, title={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.}, author={Takeru Torigoe and Toshimichi Ohmura and Michinori Suginome}, journal={The Journal of organic chemistry}, year={2017}, volume={82 6}, pages={2943-2956} }