Oxalyl chloride → Thymine

Participants

Reaction Conditions

Reaction Steps

To a solution of DMSO (170μl, 2.34 mM) and CH2Cl2 (0.5 ml) at -60° C., was added 135 ml of (COCl)2 in 1 ml of CH2Cl2 dropwise over a period of 5 minutes. After 15 minutes, 3'-deoxy-4'-hydroxymethylthymidine (0.3 g, 1.17 mM), prepared, e.g., as described in Preparation 15, in 0.5 ml DMSO/0.5 ml CH2Cl2 was added slowly and the mixture stirred at -55° C. for 3 hours. After the addition of 0.65 ml TEA, the solution was removed from the cooling bath and allowed to warm to 24° C. at which temperature it was stirred for 15 minutes. The solution was filtered and the solvent was removed by evaporation. The residue was dissolved in pyridine; treated with H2NOH HCl (0.2 g, 2.9 mM), and stirred at 24° C. for 48 hours. The solvent was removed by evaporation and the residue was chromatographed on silica gel using 8% CH3OH/CH2Cl2, yielding a mixture of the 4'-α and 4'-β isomers of 3'-deoxy-4'-hydroxyiminomethylthymidine (140 mg, 0.52 mM).

Provenance & Evidence