Download PDF
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: keimanabe@riken.jp;
Further Information

Publication History

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

    Permissions and Reprints All articles of this category

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.

Key words

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

    References

  • 1a Naumann K. J. Prakt. Chem.  1999,  341:  417 
    Google Scholar
  • 1b Müller K. Faeh C. Diederich F. Science  2007,  317:  1881 
    Google Scholar
  • 2 Urch CJ. In Comprehensive Organic Functional Group Transformations   Vol. 2:  Katritzky AR. Taylor RJK. Pergamon; Cambridge: 1995.  p.605 
    Google Scholar
  • 3a Reddy GS. Tam W. Organometallics  1984,  3:  630 
    Google Scholar
  • 3b Singh R. Just G. J. Org. Chem.  1989,  54:  4453 
    Google Scholar
  • 3c Dirk SM. Price DW. Chanteau S. Kosynkin DV. Tour JM. Tetrahedron  2001,  57:  5109 
    Google Scholar
  • 3d Ackermann L. Althammer A. Angew. Chem. Int. Ed.  2007,  46:  1627 
    Google Scholar
  • 3e Houpis IN. Hoeck J.-PV. Tilstam U. Synlett  2007,  2179 
    Google Scholar
  • 3f Ishii Y. Chatani N. Yorimitsu S. Murai S. Chem. Lett.  1998,  27:  157 
    Google Scholar
  • 3g Wang T. Alfonso BJ. Love JA. Org. Lett.  2007,  9:  5629 
    Google Scholar
  • For site-selective cross-coupling of polyhalogenated heteroarenes, see:
  • 3h Schröter S. Stock C. Bach T. Tetrahedron   2005,  61:  2245 
    Google Scholar
  • 3i Fairlamb IJS. Chem. Soc. Rev.  2007,  36:  1036 
    Google Scholar
  • 4a Ishikawa S. Manabe K. Chem. Lett.  2007,  36:  1304 
    Google Scholar
  • 4b Ishikawa S. Manabe K. Org. Lett.  2007,  9:  5593 
    Google Scholar
  • 4c Manabe K. Ishikawa S. Synthesis  2008,  2645 
    Google Scholar
  • For reviews on cross-coupling with Grignard reagents, see:
  • 5a Tsuji J. Palladium Reagents and Catalysts   Wiley; West Sussex: 2004.  p.335 
    Google Scholar
  • 5b Cepanec I. Synthesis of Biaryls   Elsevier; Oxford: 2004.  p.83 
    Google Scholar
  • 6 Ishikawa S. Manabe K. Chem. Lett.  2007,  36:  1302 
    CrossrefGoogle Scholar
  • 7 The design of these terphenylphosphines is based on biphenylphosphines developed by Buchwald et al., see: Wolfe JP. Buchwald SL. Angew. Chem. Int. Ed.  1999,  38:  2413 
    CrossrefPubMedGoogle Scholar
8

Phosphine 1 was purified and stored as the HBF4 salt.