TY - JOUR
T1 - 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
AU - Torigoe, Takeru
AU - Ohmura, Toshimichi
AU - Suginome, Michinori
N1 - Funding Information:
This work is supported by Grants-in-Aid for Scientific Research (B) No. 26288048 (T.O.) and for JSPS Fellow No. 26.5249 (T.T.) from JSPS, Grant-in-Aid for Scientific Research on Innovative Area No. 25105728 from MEXT (T.O.), and ACT-C FS from JST (T.O.).
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/17
Y1 - 2017/3/17
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85015685971&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85015685971&partnerID=8YFLogxK
U2 - 10.1021/acs.joc.6b02917
DO - 10.1021/acs.joc.6b02917
M3 - Article
C2 - 28185456
AN - SCOPUS:85015685971
VL - 82
SP - 2943
EP - 2956
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 6
ER -