Chemistry An Asian Journal 2012-06-01

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

Index: Chem. Asian J. 7(6) , 1256-60, (2012)

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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.Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.