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Oxidation of 5-Chloro-10-oxa-3-thia-tricyclo[5,2,1,01,5]dec-8-ene with m-CPBA ; Sulphur oxidation, tricycles, Diels-Alder

SyntheticPage 237 (2006)
Submitted 9th Feb 2006, published 9th Feb 2006

A contribution from the Demircan Group, Nigde

Reaction Scheme

Chemicals Used
Meta-chloroperbenzoic acid (Aldrich, 70%, purified in Diethylether), dichloromethane (distilled from CaH2)

5-Chloro-10-oxa-3-thia-tricyclo[5,2,1,0*1,5*]dec-8-ene- 3,3-dioxide: To a solution of m-CPBA (200 mg, 0.8 mmol) in dichloromethane (10 mL), cooled to 0 oC, was added dropwise a solution of 5-chloro-10-oxa-3-thia-tricyclo [, 5] dec-8-ene (150 mg, 0.8 mmol) in dichloromethane (10 mL) over 3 min. The reaction mixture was stirred at room temperature for 4 h and then diluted with cold 4 % sodium bicarbonate solution (4 mL). The organic layer was separated, washed with water (20 mL) and concentrated in vacuo. The crude residue was purified by silica gel column chromatography using EtOAc / n-Hexane (3:7) as eluent to provide pure dioxide. Off white crystals (1:1 Ether / DCM): yield 140 mg (80%).

Author's Comments
Regio selective oxidation is observed. Alkene epoxidation is not observed. Equivalents of m-CPBA can be raised up to 3 equiv. for complete oxidation. X-ray analysis of product structure is available.

m. p. : 146-148 oC; Rf : 0.27; IR(thin film)/cm-1 : 2953 (s,C-H), 1126 (s, S=O), 719 (s, C-Cl). PNMR(400 MHz, CDCl3): 6.59 (dd, 1H, J1 1.8 Hz, J2 5.7 Hz, AB system), 6.33 (d, 1H, Hd, J2 5.7 Hz, AB), 5.12 (dd, 1H, J1 1.8 Hz, J3 4.8 Hz), 3.85 (d, 1H, J4 14.6 Hz, AB), 3.64 (d, 1H, J4 14.6 Hz, AB), 3.78 (d, 1H, J5 14.1 Hz, AB), 3.51 (d, 1H, J5 14.1 Hz, AB), 2,55 (dd, 1H, J3 4.8 Hz, J6 12.6 Hz, AB), 1.89 (d, 1H, J6 12.6 Hz, AB). CNMR (100 MHz, CDCl3 ): 137.7, 135.0, 101.1, 80.7, 77.7, 46.5, 44.3, 29.9. m/z (GC-MS): 184,9 [M+-(Cl), 22,5%], 127,1 [M+-(SO2+C2H4), 5,8%], 121,1 [M+-(SO2+Cl), 43,1%], 81,1 [86,4%], 55,1[100%]. EA(C8H9O3SCl): Calc: C, 43.54%; H, 4.11%, Found: C, 53.78%; H, 3.92%.

Lead Reference
E. Gokturk, MSc Thesis, Nigde University, 2006, Nigde, Turkey.

Other References
I. N. N. Namboothiri, Ganesh, M., Mobin, S. M., Cojocaru, M., J. Org. Chem., 2005, 70, 2235.

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