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
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
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DOI：
10.1021/jo00264a024
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发表时间：
1989-02-03
影响因子：
3.6
通讯作者：
ECKSTEIN, F
中科院分区：
文献类型：
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作者：
LUDWIG, J;ECKSTEIN, F
2-氯- 4h -1,3,2-苯二氮磷-4- 1将核苷的5' -羟基磷酸化形成中间体(2)，随后与焦磷酸盐反应，在双置换过程中产生P2， p3 -二氧基p1 -5' -核苷环三磷酸(3)。与硫氧化得到核苷5”-（1-硫环三磷酸）(4)，它被水解成核苷5”- o -（1-硫环三磷酸）(5)的非对映体混合物。或者，可以用碘/水氧化生成核苷5' -三磷酸6。该试剂也可用于核苷2',3' -环硫代酸酯的合成。不需要保护核碱基官能团。
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.