Reaction mechanism of the anomalous formal nucleophilic borylation of organic halides with silylborane: Combined theoretical and experimental studies

Ryohei Uematsu, Eiji Yamamoto, Satoshi Maeda, Hajime Ito, Tetsuya Taketsugu

研究成果: ジャーナルへの寄稿記事

50 引用 (Scopus)

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
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

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Bromine
Boron
Nucleophiles
Theoretical Models
Silicon
Substrates
Bromides
Anions
Atoms
Potassium
Functional groups
Density functional theory
Substitution reactions
Negative ions
Activation energy

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

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AU - Taketsugu, Tetsuya

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