Synlett 2002(12): 2019-2022
DOI: 10.1055/s-2002-35560
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Sultones by Ring Closing Metathesis

Sandra Karsch, Pia Schwab, Peter Metz*
Institut für Organische Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany
Fax: +49(351)46333162; e-Mail: peter.metz@chemie.tu-dresden.de;
Further Information

Publication History

Received 11 September 2002
Publication Date:
20 November 2002 (online)

Abstract

Unsaturated sultones with normal, medium and large ring sizes were efficiently synthesized by ring closing metathesis of sulfonates. The required substrates were readily derived from alkenols and olefinic sulfonyl chlorides.

    References

  • For reviews on sultone chemistry, see:
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  • 1b Buglass AJ. Tillett JG. In The Chemistry of Sulfonic Acids, Esters and their Derivatives   Patai S. Rappoport Z. Wiley; New York: 1991.  p.789 
  • 1c Roberts DW. Williams DL. Tetrahedron  1987,  43:  1027 
  • Selected recent synthetic applications of sultones:
  • 2a Wang Y. Bernsmann H. Gruner M. Metz P. Tetrahedron Lett.  2001,  42:  7801 
  • 2b Plietker B. Seng D. Fröhlich R. Metz P. Eur. J. Org. Chem.  2001,  3669 
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  • 2e Doye S. Hotopp T. Wartchow R. Winterfeldt E. Chem.-Eur. J.  1998,  4:  1480 
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  • 6 For preparation of 4e, see: Brunel Y. Rousseau G. J. Org. Chem.  1996,  61:  5793 
  • 7 For a similar preparation of 5b, see: King JF. Loosmore SM. Aslam M. Lock JD. McGarrity MJ. J. Am. Chem. Soc.  1982,  104:  7108 
  • 8 For an alternative preparation of 5f and 5g, see: Visgert RV. Skrypnik YG. Russ. J. Org. Chem.  1970,  6:  2068 
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9

General Procedure: To an ice-cooled soln of alcohol 4 (1 mmol), DMAP (0.1 mmol) and triethylamine (1.2 mmol) in CH2Cl2 (10 mL) was added dropwise sulfonyl chloride 3 (1.2 mmol). Stirring was continued at 0 °C for the time indicated in Table [1] . The mixture was washed with cold water (7.5 mL), 1 N HCl (7.5 mL) and sat. aq NaHCO3 (7.5 mL). After drying the organic layer over MgSO4, the solvent was evaporated and the residue was subjected to bulb to bulb distillation to give the pure sulfonate 5. To a stirred soln of sulfonate 5 in CH2Cl2 was added catalyst 2 in small portions at 40 °C. The reaction conditions are listed in Table [2] . After the reaction had stopped, the solvent was evaporated and the residue was purified by flash chromatography. Compound 6j: 1H NMR (500 MHz, CDCl3): δ = 1.71-1.76 (m, 2 H, 5-H), 1.80-1.84 (m, 2 H, 6-H), 2.37-2.41 (m, 2 H, 4-H), 3.89 (d, J 1,2 = 7.9 Hz, 2 H, 1-H), 4.36-4.38 (m, 2 H, 7-H), 5.60-5.65 (m, 1 H, 2-H), 5.86-5.92 (m, 1 H, 3-H). 13C NMR (125.8 MHz, CDCl3): δ = 24.85 (t, C-5), 25.98 (t, C-4), 26.47 (t, C-6), 49.43 (t, C-1), 73.51 (t, C-7), 115.96 (d, C-2), 139.57 (d, C-3).

10

Sultones 6a (see ref. [2c] and ref. [11a] ), 6f (see ref. [11b] ) and 6g (see ref. [11c] ) are known compounds.

12

Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-187416. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk).