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Synlett 2009(9): 1471-1473  
DOI: 10.1055/s-0029-1217161
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© 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;
Further Information

Publication History

Received 3 February 2009
Publication Date:
13 May 2009 (online)

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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

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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.

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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.

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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.