Mechanistic Investigation of Aromatic C(sp2)-H and Alkyl C(sp3)-H Bond Insertion by Gold Carbenes

Yuan Liu, Zhunzhun Yu, Zhoujie Luo, John Zhang, Lu Liu, Fei Xia

Research output: Contribution to journalArticle

Abstract

It was recently reported that the gold-carbenes have an unprecedented catalysis toward the functionalization of C(sp2)-H bonds of aromatic compounds. However, the associated mechanisms of C(sp2)-H bonds inserted by gold-carbenes have not been comprehensively understood. We carried out a detailed mechanistic investigation of gold-carbene insertion into the C(sp2)-H bond of anisole by means of theoretical calculations and control experiments. It significantly reveals that the aromatic C(sp2)-H bond activation starts with the electrophilic addition of aromatic carbon toward the carbene carbon and subsequently followed the [1,3]-proton shift to form an enol intermediate. The rearrangement of enol proceeds through the mechanisms of proton transfer assisted by water molecules or enol intermediates, which are supported by our control experiments. It was also found that the C(sp3)-H insertions of alkanes by gold-carbenes proceed through a concerted process via a three-centered transition state. The further comparison of different mechanisms provides a clear theoretical scheme to account for the difference in aromatic C(sp2)-H and alkyl C(sp3)-H bond activation, which is instructive for the further experimental functionalization of C-H bonds by gold-carbenes.

Original languageEnglish (US)
Pages (from-to)1925-1932
Number of pages8
JournalJournal of Physical Chemistry A
Volume120
Issue number11
DOIs
StatePublished - Mar 31 2016

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carbenes
Gold
insertion
gold
Carbon
Chemical activation
activation
anisole
Alkanes
Proton transfer
protons
aromatic compounds
Aromatic compounds
carbon
alkanes
Catalysis
catalysis
carbene
Protons
Experiments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Mechanistic Investigation of Aromatic C(sp2)-H and Alkyl C(sp3)-H Bond Insertion by Gold Carbenes. / Liu, Yuan; Yu, Zhunzhun; Luo, Zhoujie; Zhang, John; Liu, Lu; Xia, Fei.

In: Journal of Physical Chemistry A, Vol. 120, No. 11, 31.03.2016, p. 1925-1932.

Research output: Contribution to journalArticle

Liu, Yuan ; Yu, Zhunzhun ; Luo, Zhoujie ; Zhang, John ; Liu, Lu ; Xia, Fei. / Mechanistic Investigation of Aromatic C(sp2)-H and Alkyl C(sp3)-H Bond Insertion by Gold Carbenes. In: Journal of Physical Chemistry A. 2016 ; Vol. 120, No. 11. pp. 1925-1932.
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