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 | |
| Publication status | Published - 2012 Jun |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
T1 - Mechanistic studies on the Pd-catalyzed direct C-H arylation of 2-substituted thiophene derivatives with arylpalladium bipyridyl complexes
AU - Steinmetz, Marc
AU - Ueda, Kirika
AU - Grimme, Stefan
AU - Yamaguchi, Junichiro
AU - Kirchberg, Sylvia
AU - Itami, Kenichiro
AU - Studer, Armido
PY - 2012/6
Y1 - 2012/6
N2 - 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.
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.
KW - C-H activation
KW - catalysis
KW - cross-coupling
KW - DFT calculations
KW - palladium
UR - http://www.scopus.com/inward/record.url?scp=84861536355&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84861536355&partnerID=8YFLogxK
U2 - 10.1002/asia.201101011
DO - 10.1002/asia.201101011
M3 - Article
C2 - 22334438
AN - SCOPUS:84861536355
VL - 7
SP - 1256
EP - 1260
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
SN - 1861-4728
IS - 6
ER -