Reaction Mechanism of the Anomalous Formal Nucleophilic Borylation of Organic Halides with Silylborane: Combined Theoretical and Experimental Studies.
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 re...
| Published in: | Journal of the American Chemical Society Vol. 137; no. 12; pp. 4090 - 4100 |
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| Main Authors: | , , , , |
| Format: | Article |
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American Chemical Society
4/1/2015
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=102925214&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 102925214 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 4/1/2015 vid: 137 iid: 12 pid: 997 pub: American Chemical Society artinfo: ui: 102925214 10.1021/ja507675f ppf: 4090 ppct: 10 formats: tig: atl: Reaction Mechanism of the Anomalous Formal Nucleophilic Borylation of Organic Halides with Silylborane: Combined Theoretical and Experimental Studies. aug: au: Ryohei Uematsu Eiji Yamamoto Satoshi Maeda Hajime Ito Tetsuya Taketsugu affil: Graduate School of Chemical Sciences and Engineering, Hokkaido University, Kita-13, Nishi-8, Kita-ku, Sapporo 060-8628, Japan Division of Chemical Process Engineering & Frontier Chemistry Center, Graduate School of Engineering, Hokkaido University, Kita-13, Nishi-8, Kita-ku, Sapporo 060-8628, Japan Department of Chemistry, Faculty of Science, Hokkaido University, Kita-10, Nishi-8, Kita-ku, Sapporo 060-0810, Japan su: Nucleophilic reactions Alkyl bromides Potassium Density functional theory Carbanions sug: subj: Nucleophilic reactions Alkyl bromides Potassium Density functional theory Carbanions 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. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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