Download PDF
Synlett 2009(15): 2492-2496  
DOI: 10.1055/s-0029-1217744
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

N-(β,β-Difluorovinyl)oxazolidin-2-ones: First Synthesis and Application in [3+2]- and [4+2]-Cycloaddition-Type Reactions

Thanh Binh Nguyen, Arnaud Martel, Robert Dhal, Gilles Dujardin*
UCO2M UMR 6011 CNRS, Université du Maine, 72085 Le Mans, France
Fax: +33(243)833344; e-Mail: gilles.dujardin@univ-lemans.fr;
Further Information

Publication History

Received 8 June 2009
Publication Date:
27 August 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

N-(β,β-Difluorovinyl)oxazolidin-2-ones were conveniently prepared in good yields in two steps from the parent oxazolidin-2-ones. The [3+2]- and [4+2]-cycloaddition-type reactions with electron-deficient partners were investigated as first application of these new enamides. TMSOTf was efficient in promoting these two reactions, and the corresponding heterocyclic difluoro adducts were obtained in high yields.

Key words

N-(β,β-difluorovinyl)oxazolidin-2-ones - trimethylsilyl trifluoromethanesulfonate - 1,3-dipolar cycloaddition - Diels-Alder reaction - dipolarophile - nitrone - heterodiene

    References and Notes

  • 1a Thayer AM. Chem. Eng. News  2006,  84 (23):  15 
    Google Scholar
  • 1b Thayer AM. Chem. Eng. News  2006,  84 (23):  27 
    Google Scholar
  • 2a Purser S. Moore PR. Swallow S. Gouverneur V. Chem. Soc. Rev.  2008,  37:  320 
    Google Scholar
  • 2b Kirk KL. Org. Process Res. Dev.  2008,  12:  305 
    Google Scholar
  • 2c O’Hagan D. Chem. Soc. Rev.  2008,  37:  308 
    Google Scholar
  • 2d Müller K. Faeh C. Diederich F. Science  2007,  317:  1881 
    Google Scholar
  • 2e Sun S. Adejare A. Curr. Top. Med. Chem.  2006,  6:  1457 
    Google Scholar
  • 2f Iseki K. Tetrahedron  1998,  54:  13887 
    Google Scholar
  • 2g Welch JT. Eswarakrishnan S. Fluorine in Bioorganic Chemistry   Wiley; New York: 1991. 
    Google Scholar
  • 2h Tozer MJ. Herpin TF. Tetrahedron  1996,  52:  8219 
    Google Scholar
  • 2i Welch JT. Tetrahedron  1987,  43:  3123 
    Google Scholar
  • 3 Singh RP. Schreeve JM. Synthesis  2002,  2561 
    Article in Thieme ConnectGoogle Scholar
  • 4 Percy JM. Top. Curr. Chem.  1997,  193:  131 
    Google Scholar
  • 5a Arany A. Crowley PJ. Fawcett J. Hursthouse MB. Kariuki BM. Light ME. Moralee AC. Percy JM. Salafia V. Org. Biomol. Chem.  2004,  2:  455 
    Google Scholar
  • 5b Okano T. Nakajima A. Eguchi S. Synlett  2001,  1449 
    Google Scholar
  • 5c Purrington SZ. Thomas HN. J. Fluorine Chem.  1998,  90:  47 
    Google Scholar
  • 5d Howarth JA. Owton WM. Percy JM. Tetrahedron  1995,  51:  10289 
    Google Scholar
  • 5e Bennette AJ. Percy JM. Synlett  1992,  483 
    Google Scholar
  • 5f Percy JM. Rock MH. Tetrahedron Lett.  1992,  33:  6177 
    Google Scholar
  • 6a Gogsig TM. Sobjerg LS. Lindhardt AT. Jensen KL. Skrydstrup T. J. Org. Chem.  2008,  73:  3404 
    Google Scholar
  • 6b Fang X. Wu YM. Deng J. Wang SW. Tetrahedron  2004,  60:  5487 
    Google Scholar
  • 6c Ichikawa J. Wada Y. Fujiwara M. Sakoda K. Synthesis  2002,  1917 
    Google Scholar
  • 6d Ichikawa J.
    J. Fluorine Chem.  2000,  105:  257 
    Google Scholar
  • 6e Ichikawa J. Fujiwara M. Nawata H. Okauchi T. Manami T. Tetrahedron Lett.  1996,  37:  8799 
    Google Scholar
  • 6f Ichikawa J. Ikeura C. Minami T. Synlett  1992,  739 
    Google Scholar
  • 6g Ichikawa J. Hamada S. Sonoda T. Kobayashi H. Tetrahedron Lett.  1992,  33:  337 
    Google Scholar
  • 6h Ichikawa J. Moriya T. Sonoda T. Kobayashi H. Chem. Lett.  1991,  20:  961 
    Google Scholar
  • 6i Ichikawa J. Sonoda T. Kobayashi H. Tetrahedron Lett.  1989,  30:  1641 
    Google Scholar
  • 6j Ichikawa J. Sonoda T. Kobayashi H. Tetrahedron Lett.  1989,  30:  5437 
    Google Scholar
  • 6k Ichikawa J. Sonoda T. Kobayashi H. Tetrahedron Lett.  1989,  30:  6379 
    Google Scholar
  • 6l Tanaka K. Nakai T. Ishikawa N. Tetrahedron Lett.  1978,  4809 
    Google Scholar
  • 6m Percy JM. Tetrahedron Lett.  1990,  31:  3931 
    Google Scholar
  • 7a Fustero S. Sanz-Cervera JF. Aceña JL. Sánchez-Roselló M. Synlett  2009,  525 
    Google Scholar
  • 7b Zhi L, Van Oeveren CA, Chen J.-H, and Higuchi RI. inventors; PCT Int. Appl., WO 2002066475,  A220020829. 
  • 7c Kudo Y, Katsumata A, Maeda K, Akiyama S, Yaosaka M, Morimoto K, Nakahira K, Ohki T, Hamada N,
    Yano     T, Noguchi J, and Watanabe S. inventors; PCT Int. Appl., WO 2001068613,  A120010920. 
  • 7d Okamoto H, and Kato S. inventors; Jpn. Kokai Tokkyo Koho, JP 02178259,  A19900711. 
  • 7e Haszeldine RN. Tipping AE.
    J. Chem. Soc. C  1968,  4:  398 
    Google Scholar
  • 8a Nguyen TB. Vuong TMH. Martel A. Dhal R. Dujardin G. Tetrahedron: Asymmetry  2008,  19:  2084 
    Google Scholar
  • 8b Nguyen TB. Martel A. Dhal R. Dujardin G. Synlett  2008,  2041 
    Google Scholar
  • 8c Nguyen TB. Martel A. Dhal R. Dujardin G. J. Org. Chem.  2008,  73:  2621 
    Google Scholar
  • 8d Nguyen TB. Gaulon C. Chapin T. Tardy S. Tatibouet A. Rollin P. Dhal R. Martel A. Dujardin G. Synlett  2006,  3255 
    Google Scholar
  • 9a Gohier F. Bouhadjera K. Faye D. Gaulon C. Maisonneuve V. Dujardin G. Dhal R. Org. Lett.  2007,  9:  211 
    Google Scholar
  • 9b Gaulon C. Dhal R. Chapin T. Maisonneuve V. Dujardin G. J. Org. Chem.  2004,  69:  4192 
    Google Scholar
  • 9c Gaulon C. Gizecki P. Dhal R. Dujardin G. Synthesis  2003,  2269 
    Google Scholar
  • 9d Gaulon C. Gizecki P. Dhal R. Dujardin G. Synlett  2002,  952 
    Google Scholar
  • 10a Feiring AE. Wonchoba ER. J. Org. Chem.  1992,  57:  7014 
    Google Scholar
  • 10b Dlouba I. Kvicala J. Paleta O. J. Fluorine Chem.  2002,  117:  149 
    Google Scholar
  • 12 Dhavale DD. Trombini C. J. Chem. Soc., Chem. Commun.  1992,  1268 
    CrossrefGoogle Scholar
  • 14 Amiii H. Kobayashi T. Terasawa H. Uneyama K. Org. Lett.  2001,  3:  3103 
    CrossrefGoogle Scholar
11

Procedures and compounds are described in the Supplementary Information.

13

Only minor adduct 9b, of cis configuration, could be separated from the adduct mixture by column chroma-tography.

15

From the NMR study on adduct 11b, the cis/trans distribution (cis I/cis II/trans I/trans II = 52:22:18:8) was deduced.