Synthesis 2005(14): 2393-2399  
DOI: 10.1055/s-2005-869992
PAPER
© Georg Thieme Verlag Stuttgart · New York

Asymmetric 1,3-Dipolar Cycloaddition Reactions of Nitrones with (S)-(-)-4-Benzyl-N-methacryloyl-2-oxazolidinone

Elizabeth Tyrrell*a, Jackie Allena, Keith Jonesa, Romain Beauchetb
a School of Pharmacy, Kingston University, Penrhyn Road, Kingston, Surrey, KT1 2EE, UK
e-Mail: e.tyrrell@kingston.ac.uk;
b School of Chemistry, University of Poitiers, Poitiers, France
Further Information

Publication History

Received 11 March 2005
Publication Date:
13 July 2005 (eFirst)

Abstract

The [3+2]-nitrone-mediated cycloaddition reaction of (S)-(-)-4-benzyl-N-methacryloyl-2-oxazolidinone has been applied to the synthesis of highly substituted isoxazolidines with controlled stereochemistry. The absolute configuration of the major diastereo­isomer derived from the reaction between N-(p-nitrobenzylidene)methylamine N-oxide and (S)-(-)-4-benzyl-N-methacryloyl-2-oxazolidinone has been deduced from the corresponding X-ray structure.

    References

  • 1 Miyaura N. Yanagi T. Suzuki A. Synth. Commun.  1981,  11:  513 
  • 2 Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
  • 3a Allin SM. Shuttleworth SJ. Tetrahedron Lett.  1996,  37:  8023 
  • 3b Green R. Taylor PJM. Bull SD. James TD. Mahon MF. Merritt AT. Tetrahedron: Asymmetry  2003,  14:  2619 
  • 3c For a review of chiral auxiliaries in polymer-supported organic synthesis: Chung CWY. Toy PH. Tetrahedron: Asymmetry  2004,  15:  387 
  • 4 Gefflaut T. Bauer U. Airola K. Koskinen Ari MP. Tetrahedron: Asymmetry  1996,  7:  3099 
  • 5 Tamura O. Mita N. Kusaka N. Suzuki H. Sakamoto M. Tetrahedron Lett.  1997,  38:  429 
  • 6a Faita G. Paio A. Quadrelli P. Rancati F. Seneci P. Tetrahedron Lett.  2000,  41:  1265 
  • 6b Desmoni G. Faita G. Galbiati A. Pasini D. Paio A. Rancati F. Tetrahedron: Asymmetry  2002,  13:  333 
  • 6c Faita G. Paio A. Quadrelli P. Rancati F. Seneci P. Tetrahedron  2001,  57:  8313 
  • 7 Tyrrell E. PhD Thesis   University of Southampton; UK: 1989. 
  • 8a For an example of 5,5-disubstituted isoxazolidines see: Bouillon J.-P. Janousek Z. Viehe HG. Tinnant B. Declerq J.-P. J. Chem. Soc., Perkin Trans. 1  1996,  1853 
  • 8b Strauss A. Otto H.-H. Helv. Chim. Acta  1997,  80:  1823 
  • 9a Basak A. Bdour HMM. Bhattacharya G. Tetrahedron Lett.  1997,  38:  2535 
  • 9b Anklam S. Liebscher J. Tetrahedron  1998,  54:  6369 
  • 10 Dopp D. Henseleit M. Chem. Ber.  1982,  115:  798 
  • 11a Fornefeld EJ. Pike AJ. J. Org. Chem.  1979,  44:  835 
  • 11b For a discussion on regiochemistry: Ali SA. Senaratne PA. Illig CR. Meckler M. Tufariello JJ. Tetrahedron Lett.  1979,  20:  4167 
  • 12 Katritzky AR. Gregory JH. Xiaohong Z. J. Chem. Soc., Perkin Trans. 1  1990,  2371 
  • 13 Muller P. Eschenmoser A. Helv. Chim. Acta  1969,  52:  1823 
  • 14a Exner O. Collect. Czech. Chem. Commun.  1951,  16:  258 
  • 14b An alternative procedure: Robl JA. Hwu JR. J. Org. Chem.  1985,  50:  5913 
  • The use of NMR studies to establish stereochemistry of comparable molecules is not without precedent see:
  • 15a Fringuelli F. Pizzo F. Taticchi A. Halls TDG. Wenkert E. J. Org. Chem.  1982,  47:  5056 
  • 15b Snider BA. Kirk TC. J. Am. Chem. Soc.  1983,  105:  2364 
  • 15c Smith AB. Toder BH. Branca SJ. Dieter KR. J. Am. Chem. Soc.  1981,  103:  1996 
  • 15d Schnizer D. Ringe K. Synlett  1994,  463 
  • 15e Whitesell JK. Matthews SS. J. Org. Chem.  1977,  42:  3878 
  • 16a Kakisawa H. Kashman Y. Kusumi T. Ohtani I. J. Am. Chem. Soc.  1991,  113:  4092 
  • 16b Heumann A. J. Chem. Soc., Chem. Commun.  1993,  113 
  • 16c Riguera R. Quinoa E. Seco JM. Latypov SK. J. Org. Chem.  1995,  60:  1538 
  • 17a Dale JA. Dull D. Mosher HS. J. Org. Chem.  1969,  34:  2543 
  • 17b Dale JA. Mosher HS. J. Am. Chem. Soc.  1973,  95:  512 
  • 19 Evans DA. Britton TC. Ellman JA. Tetrahedron Lett.  1987,  28:  6141 
  • 22 Evans DA. Chapman KT. Bisaha J. J. Am. Chem. Soc.  1988,  110:  1238 
  • 23 Hamer J. Macaluso A. Chem. Rev.  1964,  64:  473 
  • 24 Abou-Gharbia M. Joulke MM. Synthesis  1977,  318 
  • 25 Bjorgo J. Boyd DR. Neill DC. Jennings WB. J. Chem. Soc., Perkin Trans. 1  1976,  254 
18

All compounds provided satisfactory spectral data that were consistent with the assigned structures.

20

Only one isomer was detectable by 1H NMR studies on the crude isolate.

21

The enantiomeric excess (92%) was determined by chiral GC using a Supercot α-dex 225 column.