Synthesis 2009(22): 3897-3904  
DOI: 10.1055/s-0029-1217067
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Enol Phosphinates and Phosphonates: Practical Electrophiles for Cross-Coupling Strategies

Patrick G. Steel*a, Tom M. Woodsa,b
a Department of Chemistry, University of Durham, Science Laboratories, South Road Durham, DH1 3LE, UK
Fax: +44(191)3844737; e-Mail: [email protected];
b Chemical Synthesis Laboratory, Swiss Federal Institute of Technology (EPFL), 1015 Lausanne, Switzerland
e-Mail: [email protected];
Further Information

Publication History

Received 18 June 2009
Publication Date:
22 October 2009 (online)

Abstract

Enol phosphinates and phosphonates can be readily prepared from simple lactams in high yields and are both stable and storable. Both these substrates can be employed successfully in homogeneous Suzuki-Miyaura and Stille cross-couplings protocols. Additionally, the phosphonate group can be immobilised on a phenol-on-polystyrene resin and utilised in a simple diversity linker strategy in which the coupled product is cleaved from the resin under Suzuki-Miyaura cross-coupling conditions.

    References

  • 1 For a review, see: Metal-Catalysed Cross-Coupling Reactions, 2nd ed.   Diederich F. de Meijere A. Wiley-VCH; Weinheim: 2004. 
  • 2a Ritter K. Synthesis  1993,  735 
  • 2b Luker T. Hiemstra H. Speckamp WN. J. Org. Chem.  1997,  62:  8131 
  • 2c Occhiato EG. Trabocchi A. Guarna A. J. Org. Chem.  2001,  66:  2459 
  • 2d Stang PJ. Summerville RJ. J. Am. Chem. Soc.  1969,  91:  4600 
  • 3 Roth GP. Fuller CE. J. Org. Chem.  1991,  56:  3493 
  • 4a Perec V. Bae J.-Y. Hill DH. J. Org. Chem.  1995,  60:  1060 
  • 4b Cho C.-H. Kim I.-S. Park K. Tetrahedron  2004,  60:  4589 
  • 5 Wu J. Sun X. Zhang L. Chem. Lett.  2005,  34:  796 
  • 6 Rottlander M. Knochel P. J. Org. Chem.  1998,  63:  203 
  • 7 Blaszczak L. Winkler J. Kuhn SO. Tetrahedron Lett.  1976,  49:  4405 
  • 8 Takai K. Oshima K. Nozaki H. Tetrahedron Lett.  1980,  21:  2531 
  • 9a Nicolaou KC. Shi G.-Q. Gunzer JL. Gartner P. Yang Z. J. Am. Chem. Soc.  1997,  119:  5467 
  • 9b Nicolaou KC. Shi G.-Q. Namoto K. Bernal F. Chem. Commun.  1998,  1757 
  • 10a Lepifre F. Buon C. Rabot R. Bouyssou P. Coudert G. Tetrahedron. Lett.  1999,  40:  6373 
  • 10b Chacun-Lefevre R. Buon C. Rabot R. Bouyssou P. Coudert G. Tetrahedron  2000,  56:  605 
  • 10c Lepifre F. Clavier S. Bouyssou P. Coudert G. Tetrahedron  2001,  57:  6969 
  • 11a Galbo FL. Occhiato EG. Guarna A. Faggi C. J. Org. Chem.  2003,  68:  6360 
  • 11b Galbo FL. Occhiato EG. Guarna A. J. Org. Chem.  2005,  70:  7324 
  • 12a Hansen AL. Ebran J.-P. Gogsig TM. Skrydstrup T. Chem. Commun.  2006,  4137 
  • 12b Hansen AL. Skrydstrup T. J. Org. Chem.  2007,  72:  3392 
  • 13 Guo J. Harling JD. Steel PG. Woods TM. Org. Biomol. Chem.  2008,  6:  4053 ; Article highlighted in Synfacts 2009, 89
  • 14 Campbell IB. Guo J. Jones E. Steel PG. Org. Biomol. Chem.  2004,  2:  2725 
  • 15 Harling JD. Steel PG. Woods TM. Yufit DM. Org. Biomol. Chem.  2007,  5:  3472 
  • 17 Still WC. Kahn M. Mitra AJ. J. Org. Chem.  1978,  43:  2923 
16

In all cases, the 2-arylenamide products 6 are isolated as rotameric mixtures interconvertable at 60 ˚C as ascertained by simple VT NMR studies.