Utilization of a Trimethylsilyl Group as a Synthetic Equivalent of a Hydroxyl Group via Chemoselective C(sp(3))-H Borylation at the Methyl Group on Silicon

作者：Torigoe Takeru; Ohmura Toshimichi^*; Suginome Michinori^*

来源：Journal of Organic Chemistry, 2017, 82(6): 2943-2956.

DOI：10.1021/acs.joc.6b02917

A conversion of trimethylsilylalkanes into the corresponding alcohols is established based on an iridium-catalyzed, chemoselective C(sp(3))-H borylation of the methyl group on silicon. The (borylmethyl)silyl group formed by C(sp(3))-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-l-silacyclopentane for conversion into the corresponding stereodefined cycloalkyl alcohols and 1,4-butanediol.

• 出版日期2017-3-17