抄録
Theoretical and experimental studies have been conducted to elucidate the mechanism of the formal nucleophilic boryl substitution of aryl and alkyl bromides with silylborane in the presence of potassium methoxide. Density functional theory was used in conjunction with the artificial force induced reaction method in the current study to determine the mechanism of this reaction. The results of this analysis led to the identification of a unique carbanion-mediated mechanism involving the halogenophilic attack of a silyl nucleophile on the bromine atom of the substrate. These calculations have, therefore, provided a mechanistic rationale for this counterintuitive borylation reaction. Furthermore, the good functional group compatibility and high reactivity exhibited by this reaction toward sterically hindered substrates can be understood in terms of the low activation energy required for the reaction of the silyl nucleophile with the bromine atom of the substrate and the subsequent rapid and selective consumption of the carbanion species by the in situ generated boron electrophile. The results of an experimental study involving the capture of the anion intermediate provided further evidence in support of the generation of a carbanion species during the course of this reaction. The anomalous formal nucleophilic borylation mechanism reported in this study could be used to provide new insights into silicon and boron chemistry.
| 元の言語 | 英語 |
|---|---|
| ページ（範囲） | 4090-4099 |
| ページ数 | 10 |
| ジャーナル | Journal of the American Chemical Society |
| 巻 | 137 |
| 発行部数 | 12 |
| DOI | |
| 出版物ステータス | 出版済み - 4 1 2015 |
| 外部発表 | Yes |
Fingerprint
All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
これを引用
Reaction mechanism of the anomalous formal nucleophilic borylation of organic halides with silylborane : Combined theoretical and experimental studies. / Uematsu, Ryohei; Yamamoto, Eiji; Maeda, Satoshi; Ito, Hajime; Taketsugu, Tetsuya.
：: Journal of the American Chemical Society, 巻 137, 番号 12, 01.04.2015, p. 4090-4099.研究成果: ジャーナルへの寄稿 › 記事
}
TY - JOUR
T1 - Reaction mechanism of the anomalous formal nucleophilic borylation of organic halides with silylborane
T2 - Combined theoretical and experimental studies
AU - Uematsu, Ryohei
AU - Yamamoto, Eiji
AU - Maeda, Satoshi
AU - Ito, Hajime
AU - Taketsugu, Tetsuya
PY - 2015/4/1
Y1 - 2015/4/1
N2 - Theoretical and experimental studies have been conducted to elucidate the mechanism of the formal nucleophilic boryl substitution of aryl and alkyl bromides with silylborane in the presence of potassium methoxide. Density functional theory was used in conjunction with the artificial force induced reaction method in the current study to determine the mechanism of this reaction. The results of this analysis led to the identification of a unique carbanion-mediated mechanism involving the halogenophilic attack of a silyl nucleophile on the bromine atom of the substrate. These calculations have, therefore, provided a mechanistic rationale for this counterintuitive borylation reaction. Furthermore, the good functional group compatibility and high reactivity exhibited by this reaction toward sterically hindered substrates can be understood in terms of the low activation energy required for the reaction of the silyl nucleophile with the bromine atom of the substrate and the subsequent rapid and selective consumption of the carbanion species by the in situ generated boron electrophile. The results of an experimental study involving the capture of the anion intermediate provided further evidence in support of the generation of a carbanion species during the course of this reaction. The anomalous formal nucleophilic borylation mechanism reported in this study could be used to provide new insights into silicon and boron chemistry.
AB - Theoretical and experimental studies have been conducted to elucidate the mechanism of the formal nucleophilic boryl substitution of aryl and alkyl bromides with silylborane in the presence of potassium methoxide. Density functional theory was used in conjunction with the artificial force induced reaction method in the current study to determine the mechanism of this reaction. The results of this analysis led to the identification of a unique carbanion-mediated mechanism involving the halogenophilic attack of a silyl nucleophile on the bromine atom of the substrate. These calculations have, therefore, provided a mechanistic rationale for this counterintuitive borylation reaction. Furthermore, the good functional group compatibility and high reactivity exhibited by this reaction toward sterically hindered substrates can be understood in terms of the low activation energy required for the reaction of the silyl nucleophile with the bromine atom of the substrate and the subsequent rapid and selective consumption of the carbanion species by the in situ generated boron electrophile. The results of an experimental study involving the capture of the anion intermediate provided further evidence in support of the generation of a carbanion species during the course of this reaction. The anomalous formal nucleophilic borylation mechanism reported in this study could be used to provide new insights into silicon and boron chemistry.
UR - http://www.scopus.com/inward/record.url?scp=84926288376&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84926288376&partnerID=8YFLogxK
U2 - 10.1021/ja507675f
DO - 10.1021/ja507675f
M3 - Article
AN - SCOPUS:84926288376
VL - 137
SP - 4090
EP - 4099
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 12
ER -