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  High Site Selectivity in Electrophilic Aromatic Substitutions: Mechanism of C–H Thianthrenation

Juliá, F., Shao, Q., Duan, M., Plutschack, M. B., Berger, F., Mateos, J., et al. (2021). High Site Selectivity in Electrophilic Aromatic Substitutions: Mechanism of C–H Thianthrenation. Journal of the American Chemical Society, 143(39), 16041-16054. doi:10.1021/jacs.1c06281.

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 Creators:
Juliá, Fabio1, Author              
Shao, Qianzhen2, Author
Duan, Meng2, Author
Plutschack, Matthew B.1, Author              
Berger, Florian1, Author              
Mateos, Javier1, Author              
Lu, Chenxi2, Author
Xue, Xiao-Song2, Author
Houk, K. N.2, Author
Ritter, Tobias1, Author              
Affiliations:
1Research Department Ritter, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2040308              
2Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569 United States, ou_persistent22              

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 Abstract: The introduction of thianthrene as a linchpin has proven to be a versatile strategy for the C–H functionalization of aromatic compounds, featuring a broad scope and fast diversification. The synthesis of aryl thianthrenium salts has displayed an unusually high para regioselectivity, notably superior to those observed in halogenation or borylation reactions for various substrates. We report an experimental and computational study on the mechanism of aromatic C–H thianthrenation reactions, with an emphasis on the elucidation of the reactive species and the nature of the exquisite site selectivity. Mechanisms involving a direct attack of arene to the isolated O-trifluoracetylthianthrene S-oxide (TT+-TFA) or to the thianthrene dication (TT2+) via electron transfer under acidic conditions are identified. A reversible interconversion of the different Wheland-type intermediates before a subsequent, irreversible deprotonation is proposed to be responsible for the exceptional para selectivity of the reaction.

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Language(s): eng - English
 Dates: 2021-06-172021-09-212021-10-06
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.1c06281
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 143 (39) Sequence Number: - Start / End Page: 16041 - 16054 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870