一种用于核苷多磷酸合成的 P(V)-N 激活策略。

A P(V)-N activation strategy for the synthesis of nucleoside polyphosphates.

机构信息

Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, 605 Fenglin Avenue, Nanchang, Jiangxi 330013, P. R. China.

出版信息

J Org Chem. 2013 Sep 6;78(17):8417-26. doi: 10.1021/jo4011156. Epub 2013 Aug 22.

DOI:10.1021/jo4011156

PMID:23915427

Abstract

A general and high-yielding synthesis of nucleoside 5'-triphosphates (NTPs) and nucleoside 5'-diphosphates (NDPs) from protected nucleoside 5'-phosphoropiperidates promoted by 4,5-dicyanoimidazole (DCI) has been developed. (31)P NMR tracing experiments showed that the sequential deprotection and coupling reactions were exceptionally clean. The phosphoropiperidate exhibited superior reactivity to the conventional phosphoromorpholidate toward DCI-promoted NTP/NDP synthesis. The experimental results suggested that the mechanism of DCI activation could be distinctive for NTP and NDP synthesis, depending on the different nucleophilicity of pyrophosphate and phosphate.

摘要

已开发出一种由保护的核苷 5′-磷酸哌啶酯在 4,5-二氰基咪唑（DCI）作用下合成核苷 5′-三磷酸（NTP）和核苷 5′-二磷酸（NDP）的通用且高产的方法。（31）P NMR 跟踪实验表明，顺序脱保护和偶联反应非常干净。与传统的磷酰胺相比，哌啶酯对 DCI 促进的 NTP/NDP 合成表现出更高的反应性。实验结果表明，DCI 活化的机制可能因 NTP 和 NDP 合成而有所不同，这取决于焦磷酸根和磷酸根的不同亲核性。