Synthesis 2008(19): 3180-3182  
DOI: 10.1055/s-2008-1067270
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Substituted Monohalobenzenes via Ortho-Selective Cross-Coupling of Dihalobenzenes with Electron-Donating Ortho-Directing Groups

Shunpei Ishikawa, Kei Manabe*
Manabe Initiative Research Unit, RIKEN, 2-1 Hirosawa, Wako 351-0198, Japan
Fax: +81(48)4624662; e-Mail: [email protected];
Further Information

Publication History

Received 16 July 2008
Publication Date:
05 September 2008 (online)

Abstract

Dihalobenzenes that possess directing groups such as OH, CH2OH, NH2, NHAc, or NHBoc were subjected to ortho-selective cross-coupling with Grignard reagents in the presence of palladium-based catalysts to give the corresponding substituted monohalobenzenes. For the dibromo- and dichlorophenols and anilines, hydroxylated terphenylphosphines 1 and 2 were found to be effective ligands for palladium, whereas tricyclohexylphosphine was preferable for the dichlorobenzyl alcohols, dichloroanilides, and difluorobenzenes.

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8

Phosphine 1 was purified and stored as the HBF4 salt.