4-Toluenesulfonyl chloride → HCID 10548431, compound

Participants

Reaction Steps

A solution of 3'-O-acetylthymidine 26 (0.511 g, 1.8 mmol) and toluene-4-sulfonyl chloride (0.514 g, 2.7 mmol) in dry pyridine (3 cm3) was stirred at room temperature. After 16 h, saturated aqueous sodium hydrogen carbonate (2 cm3) was added and, after a further 10 min, the products were partitioned between chloroform (50 cm3) and saturated aqueous sodium hydrogen carbonate (50 cm3). The dried (MgSO4) organic layer was concentrated under reduced pressure. The residue was fractionated by short column chromatography on silica gel: the appropriate fractions, eluted with chloroform-methanol (99:1 v/v), were combined and evaporated under reduced pressure. The residue was dissolved in acetonitrile (2.5 cm3) at room temperature and triethylamine (0.90 cm3, 6.5 mmol) and toluene-4-thiol (0.805 g, 6.5 mmol) were added to the stirred solution which was kept under an atmosphere of argon. After 60 h, the products were concentrated under reduced pressure and the residue was fractionated by short column chromatography on silica gel: the appropriate fractions, eluted with chloroform-methanol (99:1 v/v) were combined and evaporated under reduced pressure to give 3'-O-acetyl-5'-S-(4-methylphenyl)-5'-thiothymidine 31 as a colourless glass (0.60 g, 85% based on 3'-O-acetylthymidine) (Found: M+ =390.1249. 12C191H2214N216 O532S requires: 390.1249); Rt 12.05 min (programme 1); δH [(CD3)2SO] 1.76 (3 H, d, JO.9), 2.05 (3 H, s), 2.25 (1 H, m), 2.26 (3 H, s), 2.49 (1 H, m), 3.32 (2 H, m), 4.02 (1 H, m), 5.18 (1 H, m), 6.13 (1 H, dd, J 6.0, 8.6), 7.14 (2 H, d, J7.9), 7.29 (2 H, d, J 8.2), 7.51 (I H, m), 11.38 (1 H, br s); δC [(CD3)2 SO] 12.1, 20.5, 20.8, 35.2, 35.4, 75.7, 81.9, 83.9, 110.0, 129.1, 129.7, 131.6, 135.7, 136.0, 150.5, 163.6, 169.9.

Provenance & Evidence