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
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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.
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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).
For ring closing metathesis to α,β-unsaturated
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