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.
| Original language | English |
|---|---|
| Pages (from-to) | 2943-2956 |
| Number of pages | 14 |
| Journal | Journal of Organic Chemistry |
| Volume | 82 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Mar 17 2017 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Organic Chemistry
Cite this
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.
In: Journal of Organic Chemistry, Vol. 82, No. 6, 17.03.2017, p. 2943-2956.Research output: Contribution to journal › Article
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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
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.
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U2 - 10.1021/acs.joc.6b02917
DO - 10.1021/acs.joc.6b02917
M3 - Article
VL - 82
SP - 2943
EP - 2956
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 6
ER -