Synthesis 2007(22): 3595-3598  
DOI: 10.1055/s-2007-983849
PSP
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Allenes by Palladium-Catalyzed SN2′ Reaction of Indium Organometallics with Propargylic Esters

Ricardo Riveiros, José Pérez Sestelo*, Luis A. Sarandeses*
Departamento de Química Fundamental, Universidade da Coruña, 15071 A Coruña, Spain
Fax: +34(981)167065; e-Mail: [email protected]; e-Mail: [email protected];
Further Information

Publication History

Received 4 April 2007
Publication Date:
08 August 2007 (online)

Abstract

Allenes have been efficiently prepared by the reaction of propargylic esters (benzoates, acetates, carbonates) with triorganoindium compounds (R3In) under palladium catalysis, via an SN2′ rearrangement. The reaction proceeds smoothly at room temperature with a variety of aryl-, alkenyl-, and alkynylindium reagents. The yields obtained are high and the regioselectivity is complete both in the case of terminal and nonterminal propargylic esters.

    References

  • 1 Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004. 
  • 2 Hoffmann-Röder A. Krause N. Angew. Chem. Int. Ed.  2004,  43:  1196 
  • For general references, see:
  • 3a Tsuji J. Mandai T. In Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.   de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004.  p.585 
  • 3b Alexakis A. Pure Appl. Chem.  1992,  64:  387 
  • 3c Hoffmann-Röder A. Krause N. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.51 
  • 4a Pasto DJ. Hennion GF. Shults RH. Waterhouse A. Chou S.-K. J. Org. Chem.  1976,  41:  3496 
  • 4b Jeffery-Luong T. Linstrumelle G. Tetrahedron Lett.  1980,  21:  5019 
  • 5 Negishi E. Liu F. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley; New York: 2002.  p.551 
  • 6 Pérez I. Pérez Sestelo J. Maestro MA. Mouriño A. Sarandeses LA. J. Org. Chem.  1998,  63:  10074 
  • 7a Pérez I. Pérez Sestelo J. Sarandeses LA. Org. Lett.  1999,  1:  1267 
  • 7b Pérez I. Pérez Sestelo J. Sarandeses LA. J. Am. Chem. Soc.  2001,  123:  4155 
  • 7c Pena MA. Pérez I. Pérez Sestelo J. Sarandeses LA. Chem. Commun.  2002,  2246 
  • 7d Pena MA. Pérez Sestelo J. Sarandeses LA. Synthesis  2003,  780 
  • 7e Pena MA. Pérez Sestelo J. Sarandeses LA. Synthesis  2005,  485 
  • 7f Pena MA. Pérez Sestelo J. Sarandeses LA. J. Org. Chem.  2007,  72:  1271 
  • 8a Rodríguez D. Pérez Sestelo J. Sarandeses LA. J. Org. Chem.  2003,  68:  2518 
  • 8b Baker L. Minehan T. J. Org. Chem.  2004,  69:  3957 
  • 8c Rodríguez D. Pérez Sestelo J. Sarandeses LA. J. Org. Chem.  2004,  69:  8136 
  • 9 Riveiros R. Rodríguez D. Pérez Sestelo J. Sarandeses LA. Org. Lett.  2006,  8:  1403 
  • 10a

    DPEphos = bis[o-(diphenylphosphino)phenyl] ether.

  • 10b Kranenburg M. van der Burgt YEM. Kamer PCJ. van Leeuwen PWNM. Goubitz K. Fraanje J. Organometallics  1995,  14:  3081 
  • 10c Huang Z. Qian M. Babinski DJ. Negishi E. Organometallics  2005,  24:  475 
  • 11a Rosini C. Giacomelli C. Salvadori P. J. Org. Chem.  1984,  49:  3394 
  • 11b Wang S. Zhang L. J. Am. Chem. Soc.  2006,  128:  8414 
  • 13 Höffe G. Steglich W. Vorbrüggen H. Angew. Chem., Int. Ed. Engl.  1978,  17:  569 
  • 14 Matsuda I. Komori K.-I. Itoh K. J. Am. Chem. Soc.  2002,  124:  9072 
  • 16 Ruitenberg K. Kleijn H. Elsevier CJ. Meijer J. Vermeer P. Tetrahedron Lett.  1981,  22:  1451 
  • 17 Caporusso AM. Zampieri A. Aronica LA. Banti D. J. Org. Chem.  2006,  71:  1902 
  • 18 Jansen A. Krause N. Inorg. Chim. Acta  2006,  359:  1761 
12

For general experimental methods, see ref. 8a.

15

Spectroscopic and analytical data for allenes 5-9 in Table [1] have been previously reported in ref. 9. Spectroscopic and analytical data for allenes 10-13 and 15-19 are reported herein.