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

Journal of the American Chemical Society
Ryohei UematsuTetsuya Taketsugu

Abstract

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 carbanio...Continue Reading

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Citations

Sep 24, 2015·Journal of the American Chemical Society·Xiang-Wei LiuRuben Martin
Jun 28, 2016·Journal of the American Chemical Society·Adelphe M MfuhOleg V Larionov
Dec 21, 2016·Journal of the American Chemical Society·Li Zhang, Lei Jiao
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Aug 5, 2018·Journal of the American Chemical Society·Xin WangWen-Bo Liu
Oct 8, 2020·Journal of the American Chemical Society·Ya-Ming TianTodd B Marder

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