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

doi:10.1002/asia.201101011

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 journal › Article › peer-review

55 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 language	English
Pages (from-to)	1256-1260
Number of pages	5
Journal	Chemistry - An Asian Journal
Volume	7
Issue number	6
DOIs	https://doi.org/10.1002/asia.201101011
Publication status	Published - 2012 Jun
Externally published	Yes

Keywords

C-H activation
DFT calculations
catalysis
cross-coupling
palladium

ASJC Scopus subject areas

Biochemistry
Organic Chemistry

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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 journal › Article › peer-review

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AU - Grimme, Stefan

AU - Yamaguchi, Junichiro

AU - Kirchberg, Sylvia

AU - Itami, Kenichiro

AU - Studer, Armido

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AB - 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.

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

Abstract

Keywords

ASJC Scopus subject areas

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