PDF herunterladen
Synlett 2009(9): 1471-1473  
DOI: 10.1055/s-0029-1217161
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Synthesis of Oxazolidinones from N,N-Dibenzylamino Epoxides

Gabriel E. Vargas, María M. Afonso, J. Antonio Palenzuela*
Instituto Universitario de Bio-Orgánica ‘Antonio González’, Departamento de Química Orgánica, Universidad de La Laguna, 38206 La Laguna, Tenerife, Spain
Fax: +34(922)318442; e-Mail: jpalenz@ull.es;
Weitere Informationen

Publikationsverlauf

Received 3 February 2009
Publikationsdatum:
13. Mai 2009 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Enantiomerically pure oxazolidinones are easily prepared from N,N-dibenzylamino epoxides through a one-pot procedure involving monodeprotection of the amino group and treatment with NaHCO3.

Key words

amino epoxides - cyclization - oxazolidinones - heterocycles

    References and Notes

  • 1 Zappia G. Menendez P. Delle Monache G. Misiti D. Nevola L. Botta B. Mini Rev. Med. Chem.  2007,  7:  389 
    CrossrefGoogle Scholar
  • 2a Ager DJ. Prakash I. Schaad DR. Chem. Rev.  1996,  96:  835 
    Google Scholar
  • 2b Evans DA. Aldrichimica Acta  1982,  2:  23 
    Google Scholar
  • 3 Bergmeier SC. Tetrahedron  2000,  56:  2561 ; and references therein
    CrossrefGoogle Scholar
  • 4 Zappia G. Gacs-Baitz E. Delle Monache G. Misiti D. Nevola L. Botta B. Curr. Org. Synth.  2007,  4:  81 
    CrossrefGoogle Scholar
  • 5 Ayad T. Faugeroux V. Génisson Y. André C. Baltas M. Gorrichon L. J. Org. Chem.  2004,  69:  8775 
    CrossrefGoogle Scholar
  • 6 Yoshida M. Ohshima M. Toda T. Heterocycles  1993,  35:  623 
    CrossrefGoogle Scholar
  • 7 Osa Y. Hikima Y. Sato Y. Takino K. Ida Y. Hirono S. Nagase H. J. Org. Chem.  2005,  70:  5737 
    CrossrefGoogle Scholar
  • 8 Barluenga J. Baragaña B. Concellón JM. J. Org. Chem.  1995,  60:  6696 
    CrossrefGoogle Scholar
  • 9 Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   3rd ed.:  Wiley; New York: 1999. 
    Google Scholar
  • 10a Grayson EJ. Davis BG. Org. Lett.  2005,  7:  2361 
    Google Scholar
  • 10b Bull SD. Davies SG. Fenton G. Mulvaney AW. Prasad RS. Smith AD. J. Chem. Soc., Perkin Trans. 1  2000,  3765 
    Google Scholar
  • 13 Zappia G. Cancelliere G. Gacs-Baitz E. Delle Monache G. Misiti D. Nevola L. Botta B. Curr. Org. Synth.  2007,  4:  238 
    CrossrefGoogle Scholar
  • 14 Concellón JM. Suárez JR. Del Solar V. Org. Lett.  2006,  8:  349 
    CrossrefGoogle Scholar
  • 15 Davies SG. Long MJC. Smith AD. Chem. Commun.  2005,  4536 
    CrossrefGoogle Scholar
11

General Experimental Procedure for the Preparation of Oxazolidinones from N , N -Dibenzyl Amino Epoxides
To a 0.05 M solution of the amino epoxide in MeCN-H2O (5:1) was added CAN (2.1 equiv) and the reaction was stirred at r.t., following the progress by TLC (approx. 12 h). Then a sat. aq soln of NaHCO3 was added, and the mixture was vigorously stirred for 10 min. After extraction with Et2O, drying over Na2SO4 and concentration, the crude reaction mixture was purified by chromatography to give the pure oxazolidinone.

12

Representative Data
Oxazolidinone 4: [α]D ²0 -67.9 (c 1.2, CHCl3). IR: νmax = 3415, 2927, 1731, 1424, 1052 cm-¹. ¹H NMR (400 MHz, C6D6): δ = 7.27 (m, 5 H), 4.75 (d, J = 15.3 Hz, 1 H), 3.91 (dt, J = 5.0, 8.3 Hz, 1 H), 3.80 (d, J = 15.3 Hz, 1 H), 3.37 (d, J = 5.0 Hz, 2 H), 3.16 (dq, J = 6.6, 8.3 Hz, 1 H), 0.68 (d, J = 6.6 Hz, 1 H). ¹³C NMR (100 MHz, CDCl3): δ = 157.7 (s), 135.7 (s), 128.8 (d), 128.0 (d), 127.9 (d), 76.7 (d), 60.8 (t), 51.8 (d), 45.6 (t), 12.5 (c). LRMS (EI): m/z (%) = 221 (29)[M+], 91 (100). HRMS (EI): m/z calcd for C12H15NO3: 221.1052; found: 221.1043.

16

Each possible isomer was subjected to a conformational search using Molecular Mechanics (PCMODEL v7, Serena Software, Bloomington, IN). The coupling constants in each conformer were calculated and the Boltzmann weighted average was used for the comparison with the experimental values.