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Synthesis 2008(16): 2645-2649  
DOI: 10.1055/s-2008-1067182
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Ortho-Selective Cross-Coupling of Fluorobenzenes with Grignard Reagents: Acceleration by Electron-Donating Ortho-Directing Groups

Kei Manabe*, Shunpei Ishikawa
RIKEN, 2-1 Hirosawa, Wako 351-0198, Japan
Fax: +81(48)4624662; e-Mail: keimanabe@riken.jp;
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Publikationsverlauf

Received 31 March 2008
Publikationsdatum:
17. Juli 2008 (online)

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Abstract

Fluorobenzenes with directing groups such as hydroxy, hydroxymethyl, and amino underwent ortho-selective cross-coupling with Grignard reagents in the presence of palladium-based catalysts, with dichlorobis(tricyclohexylphosphine)palladium [PdCl2(PCy3)2] found to be the optimum catalyst. Fluoro and chloro groups at positions other than ortho to the directing groups survived under the reaction conditions.

Key words

fluorine - cross-coupling - palladium - site selective - Grignard reagents

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13

Saeki and Tamao et al. assumed a chelating effect of
o-difluorobenzene in their cross-coupling with a Grignard reagent.7g The ortho selectivity in our system may be attributable to a similar chelating effect.