Mechanistic studies on the Pd-catalyzed direct C-H arylation of 2-substituted thiophene derivatives with arylpalladium bipyridyl complexes

Marc Steinmetz, Kirika Ueda, Stefan Grimme, Junichiro Yamaguchi, Sylvia Kirchberg, Kenichiro Itami, Armido Studer

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

Direct C-H phenylation of 2-ethylthiophene and 2-chlorothiophene with PhPdI(bipy) complex to form either the corresponding 4-phenyl or 5-phenylthiophene derivative is studied under stoichiometric conditions using various Lewis acids as additives. It is shown that reactions occur via the corresponding cationic Pd complex (PhPdbipy +) and that the counteranion determines the regioselectivity. High-level DFT calculations reveal that C-C bond formation occurs via a carbopalladation pathway and not via electrophilic palladation. These calculations give some indications regarding the regioselectivity of the thiophene arylation.

Original languageEnglish
Pages (from-to)1256-1260
Number of pages5
JournalChemistry - An Asian Journal
Volume7
Issue number6
DOIs
Publication statusPublished - 2012 Jun
Externally publishedYes

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Thiophenes
Lewis Acids
Regioselectivity
2,2'-Dipyridyl
Derivatives
Discrete Fourier transforms

Keywords

  • C-H activation
  • catalysis
  • cross-coupling
  • DFT calculations
  • palladium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Mechanistic studies on the Pd-catalyzed direct C-H arylation of 2-substituted thiophene derivatives with arylpalladium bipyridyl complexes. / Steinmetz, Marc; Ueda, Kirika; Grimme, Stefan; Yamaguchi, Junichiro; Kirchberg, Sylvia; Itami, Kenichiro; Studer, Armido.

In: Chemistry - An Asian Journal, Vol. 7, No. 6, 06.2012, p. 1256-1260.

Research output: Contribution to journalArticle

Steinmetz, Marc ; Ueda, Kirika ; Grimme, Stefan ; Yamaguchi, Junichiro ; Kirchberg, Sylvia ; Itami, Kenichiro ; Studer, Armido. / Mechanistic studies on the Pd-catalyzed direct C-H arylation of 2-substituted thiophene derivatives with arylpalladium bipyridyl complexes. In: Chemistry - An Asian Journal. 2012 ; Vol. 7, No. 6. pp. 1256-1260.
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