Oxidation of 5-Chloro-10-oxa-3-thia-tricyclo[5,2,1,0^1,5]dec-8-ene with m-CPBA ; Sulphur oxidation, tricycles, Diels-Alder

AYDIN DEMIRCAN ([email protected]),
A contribution from the Demircan Group, Nigde

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

Procedure
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 [5.2.1.01, 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.

Data
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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