Rapid and Efficient Synthesis of Nucleoside 5'-O-(1-Thiotriphosphates), 5'-Triphosphates and 2',3'-Cyclophosphorothioates Using 2-Chloro-4H-1,3,2-benzodioxaphosphorin-4-one

Article abstract of DOI:10.1021/jo00264a024

2-Chloro-4H-1,3,2-benzodioxaphosphorin-4-one phosphitylates the 5'-hydroxy group of a nucleoside to form an intermediate (2), which on subsequent reaction with pyrophosphate produces, in a double displacement process, a P²,P³-dioxo-P¹-5'-nucleosidylcyclotriphophite (3).Oxidation with sulfur gives a nucleoside 5'-(1-thiocyclotriphosphate) (4), which is hydrolyzed to the diastereomeric mixture of a nucleoside 5'-O-(1-thiotriphosphate) (5).Alternatively, 3 can be oxidized with iodine/water to furnish nucleoside 5'-triphosphates 6.This reagent can also be applied to the synthesis of nucleoside 2',3'-cyclic phosphorothioates.Protection of nucleobase functional groups is not required.