Concise synthesis of 5-methyl-, 5-formyl, and 5-carboxy analogues of 2′-deoxycytidine-5′-triphosphate

We describe a concise and efficient synthesis of 5-methyl-, 5-formyl-, and 5-carboxy-analogues of 2′-deoxycytidine-5′-triphosphate which are well known for their various biological applications. A protection-free one-pot synthesis was used to convert 5-methyl-2′-deoxycytidine into 5-methyl-2′-deoxycytidine-5′-triphosphate in high yield. 5-Formyl-2′-deoxycytidine-5′-triphosphate was obtained upon photosensitized oxidation (UV-A irradiation, λ ∼365 nm) of an aerated aqueous solution of 5-methyl-2′-deoxycytidine-5′-triphosphate with the use of menadione as the photosensitizer. 5-Formyl-2′-deoxycytidine-5′-triphosphate was converted into 5-carboxy-2′-deoxycytidine-5′-triphosphate by using biphasic TEMPO/BAIB oxidation method in high yield.