寡核苷酸合成机制的研究。IX. 活性二核苷酸衍生物及其类似物的31P核磁共振谱

Investigation of the mechanism of the synthesis of oligonucleotides. IX. 31P NMR spectra of the active dinucleotide derivatives and their analogs.

作者信息

Knorre D G, Lebedev A V, Zarytova V F

出版信息

Nucleic Acids Res. 1976 May;3(5):1401-18. doi: 10.1093/nar/3.5.1401.

DOI:10.1093/nar/3.5.1401

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC342994/

Abstract

The interaction of 3'-O-acetyldithymidilate (pdTpdT(Ac)), thymidine-3',5'-diphosphate (pdTp) and thymidine-3'-phenyl-phosphate-5'-phosphate (pdTpPh) with 2,4,6-triisopropylbenzene sulphonyl chloride (TPS) and N,N'-dicyclohexylcarbodiimide (DCC) in pyridine and dimethylformamide (DMF) was studied by pulsed NMR spectroscopy on phosphorus nuclei. Thymidine cyclic 3',5'-pyrophosphate and dimeric pyrophosphate derivatives were shown to be the main products of the reaction of pdTp with TPS and DCC. The former shows spin AB-system with the unusually large spin-spin coupling constant about 28Hz upfield to the signals of the dimeric pyrophosphates in NMR spectrum. Analogous spin AB-systems with large spin-spin coupling constants (up to 32 Hz) were observed in the spectra of the reaction mixtures of pdTpdT(Ac) with TPS or DCC and of pdTpPh with TPS. These spin AB-systems were ascribed to 3',5'-cyclic pyrophosphate derivatives of pdTpdT(Ac) and pdTpPh.

摘要

通过对磷核的脉冲核磁共振光谱研究了3'-O-乙酰基二胸苷酸（pdTpdT(Ac)）、胸苷-3',5'-二磷酸（pdTp）和胸苷-3'-苯基磷酸-5'-磷酸（pdTpPh）与2,4,6-三异丙基苯磺酰氯（TPS）和N,N'-二环己基碳二亚胺（DCC）在吡啶和二甲基甲酰胺（DMF）中的相互作用。结果表明，胸苷环状3',5'-焦磷酸和二聚体焦磷酸衍生物是pdTp与TPS和DCC反应的主要产物。在核磁共振谱中，前者显示出自旋AB系统，其自旋-自旋耦合常数异常大，约为28Hz，位于二聚体焦磷酸信号的高场。在pdTpdT(Ac)与TPS或DCC以及pdTpPh与TPS的反应混合物光谱中也观察到了具有大自旋-自旋耦合常数（高达32Hz）的类似自旋AB系统。这些自旋AB系统被归因于pdTpdT(Ac)和pdTpPh的3',5'-环状焦磷酸衍生物。

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本文引用的文献

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STUDIES ON POLYNUCLEOTIDES. 43. THE SYNTHESIS OF DEOXRIBOPOLYNUCLEOTIDES CONTAINING REPEATING DINUCLEOTIDE SEQUENCES.多核苷酸的研究。43. 含有重复二核苷酸序列的脱氧核糖多核苷酸的合成。

J Am Chem Soc. 1965 Jul 5;87:2956-70. doi: 10.1021/ja01091a028.

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Studies on polynucleotides. LI. Syntheses of the 64 possible ribotrinucleotides derived from the four major ribomononucleotides.多核苷酸的研究。第一部分。由四种主要核糖单核苷酸衍生而来的64种可能的核糖三核苷酸的合成。

J Am Chem Soc. 1966 Feb 20;88(4):819-29. doi: 10.1021/ja00956a039.

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