Synthesis of Sultones by Ring Closing Metathesis

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.

Key words

sulfonates - ring closing metathesis - sultones - catalysis - heterocycles

References

• For reviews on sultone chemistry, see:
• 1a Metz P. J. Prakt. Chem.  1998,  340:  1 
• 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 
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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 
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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: [phone]; e-mail: [e-mail]).