Suppr超能文献

寡核苷酸化学合成的机制及其合成结果。

The mechanism of the chemical synthesis of oligonucleotides and its synthetic consequences.

作者信息

Knorre D G, Zarytova V F

出版信息

Nucleic Acids Res. 1976 Oct;3(10):2709-29. doi: 10.1093/nar/3.10.2709.

DOI:10.1093/nar/3.10.2709
PMID:186762
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC343123/
Abstract

The data obtained mainly by pulsed NMR spectroscopy on phosphorus nuclei on the mechanism of the internucleotide phosphodiester (PDE) group formation are summarised. With arylsulphonyl chloride as condensing reagent monomeric nucleotide derivative B (nucleoside metaphosphate or its pyridinium adduct) is the highly reactive intermediate. In the presence of PDE groups in nucleoside or nucleotide component the significantly less reactive derivatives with trisubstituted pyrophosphoryl residues are formed both with arylsulphonyl chloride and dicyclohexylcarbodiimide (DCC). The reactive B form of nucleotide component may be obtained using greater excess of arylsulphonyl chloride with simultaneous convertion of PDE groups to tetrasubstituted pyrophosphates amenable to side reactions. The convertion of PDE groups to easily hydrolysable dicyclohexylurea derivatives by reaction with DCC is proposed to reversible blocking of PDE groups of nucleoside component. The B type derivatives of mononucleotides or oligonucleotides with blocked PDE groups seems to be the best nucleotide components.

摘要

总结了主要通过磷核的脉冲核磁共振光谱法获得的关于核苷酸间磷酸二酯（PDE）基团形成机制的数据。以芳基磺酰氯作为缩合试剂，单体核苷酸衍生物B（核苷偏磷酸或其吡啶鎓加合物）是高反应性中间体。在核苷或核苷酸组分中存在PDE基团的情况下，使用芳基磺酰氯和二环己基碳二亚胺（DCC）都会形成具有三取代焦磷酸残基的反应性明显较低的衍生物。核苷酸组分的反应性B形式可以通过使用过量得多的芳基磺酰氯来获得，同时将PDE基团转化为易于发生副反应的四取代焦磷酸。通过与DCC反应将PDE基团转化为易于水解的二环己基脲衍生物，被认为是对核苷组分的PDE基团进行可逆阻断。具有被阻断的PDE基团的单核苷酸或寡核苷酸的B型衍生物似乎是最佳的核苷酸组分。

相似文献

1
The mechanism of the chemical synthesis of oligonucleotides and its synthetic consequences.寡核苷酸化学合成的机制及其合成结果。
Nucleic Acids Res. 1976 Oct;3(10):2709-29. doi: 10.1093/nar/3.10.2709.
2
The reactivity of phosphomono-and phosphodiester groups in oligonucleotides.寡核苷酸中磷酸单酯和磷酸二酯基团的反应活性。
Nucleic Acids Res. 1978 Apr;5(4):1253-72. doi: 10.1093/nar/5.4.1253.
3
The role of metaphosphate in the activation of the nucleotide by TPS and DCC in the oligonucleotide synthesis.偏磷酸盐在寡核苷酸合成中通过TPS和DCC激活核苷酸的作用。
Nucleic Acids Res. 1986 Mar 25;14(6):2699-706. doi: 10.1093/nar/14.6.2699.
4
The case of sulfonation in the chemical synthesis of oligonucleotides.寡核苷酸化学合成中的磺化反应实例。
Nucleic Acids Res. 1980 May 24;8(10):2301-5. doi: 10.1093/nar/8.10.2301.
5
Investigation of the mechanism of the synthesis of oligonucleotides. IX. 31P NMR spectra of the active dinucleotide derivatives and their analogs.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
Nucleic Acids Res. 1976 May;3(5):1401-18. doi: 10.1093/nar/3.5.1401.
6
Investigation of activation of phosphate groups in mono- and oligonucleotides with mesitoyl chloride.用均三甲苯甲酰氯研究单核苷酸和寡核苷酸中磷酸基团的活化
Nucleic Acids Res. 1978 Jan;5(1):185-93. doi: 10.1093/nar/5.1.185.
7
Synthesis and reactions of a nucleoside derivative of phosphoric sulfonic anhydride. Studies related to the mechanisms of coupling reactions in the chemical synthesis of oligodeoxyribonucleotides by phosphotriester procedures.磷磺酸酐核苷衍生物的合成与反应。与通过磷酸三酯法化学合成寡脱氧核糖核苷酸中偶联反应机制相关的研究。
Nucleic Acids Res. 1984 Dec 11;12(23):9123-35. doi: 10.1093/nar/12.23.9123.
8
The prebiotic synthesis of deoxthymidine oligonucleotides. II. Comparison of condensing agents.脱氧胸苷寡核苷酸的益生元合成。II. 缩合剂的比较。
J Mol Evol. 1975 Nov 4;6(3):199-207. doi: 10.1007/BF01732356.
9
Formation of internucleotide 3'-5' phosphoramidate links by direct coupling of phosphoryl and amino groups.通过磷酰基和氨基的直接偶联形成核苷酸间3'-5'磷酰胺键。
Nucleic Acids Res. 1975 Jul;2(7):1123-7. doi: 10.1093/nar/2.7.1123.
10
3'-H-phosphonate synthesis of chiral benzo[a]pyrene diol epoxide adducts at N(2) of deoxyguanosine in oligonucleotides.在寡核苷酸中，于脱氧鸟苷的N(2)位上通过3'-H-膦酸酯法合成手性苯并[a]芘二醇环氧化物加合物。
Chem Res Toxicol. 2007 Feb;20(2):311-5. doi: 10.1021/tx600282y.

引用本文的文献

1
Rapid synthesis of oligodeoxyribonucleotides. IV. Improved solid phase synthesis of oligodeoxyribonucleotides through phosphotriester intermediates.寡脱氧核糖核苷酸的快速合成。IV. 通过磷酸三酯中间体改进寡脱氧核糖核苷酸的固相合成
Nucleic Acids Res. 1980 Mar 11;8(5):1081-96. doi: 10.1093/nar/8.5.1081.
2
Tendencies of 31P chemical shifts changes in NMR spectra of nucleotide derivatives.核苷酸衍生物核磁共振谱中³¹P化学位移变化的趋势。
Nucleic Acids Res. 1984 Jul 25;12(14):5547-66. doi: 10.1093/nar/12.14.5547.
3
The role of metaphosphate in the activation of the nucleotide by TPS and DCC in the oligonucleotide synthesis.偏磷酸盐在寡核苷酸合成中通过TPS和DCC激活核苷酸的作用。
Nucleic Acids Res. 1986 Mar 25;14(6):2699-706. doi: 10.1093/nar/14.6.2699.
4
Rapid synthesis of oligodeoxyribonucleotides: a new solid-phase method.寡脱氧核糖核苷酸的快速合成：一种新的固相方法。
Nucleic Acids Res. 1977 Apr;4(4):1135-58. doi: 10.1093/nar/4.4.1135.
5
Investigation of activation of phosphate groups in mono- and oligonucleotides with mesitoyl chloride.用均三甲苯甲酰氯研究单核苷酸和寡核苷酸中磷酸基团的活化
Nucleic Acids Res. 1978 Jan;5(1):185-93. doi: 10.1093/nar/5.1.185.
6
The reactivity of phosphomono-and phosphodiester groups in oligonucleotides.寡核苷酸中磷酸单酯和磷酸二酯基团的反应活性。
Nucleic Acids Res. 1978 Apr;5(4):1253-72. doi: 10.1093/nar/5.4.1253.

本文引用的文献

1
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.
2
Synthesis of oligothymidylates and nucleoside cyclic phosphates by oxidation-reduction condensation.通过氧化还原缩合合成寡聚胸苷酸和核苷环磷酸酯。
J Am Chem Soc. 1972 Nov 29;94(24):8528-32. doi: 10.1021/ja00779a039.
3
Reaction of a nucleoside 2, 4-dinitrophenyl phosphate with fluoride; a convenient method for the preparation of the nucleoside phosphorfluoridate.核苷2,4-二硝基苯磷酸酯与氟化物的反应；一种制备核苷磷酰氟化物的简便方法。
Nucleic Acids Res. 1975 Oct;2(10):1745-9. doi: 10.1093/nar/2.10.1745.

文献AI研究员

20分钟写一篇综述，助力文献阅读效率提升50倍。

立即体验

用中文搜PubMed

大模型驱动的PubMed中文搜索引擎

马上搜索

文档翻译

学术文献翻译模型，支持多种主流文档格式。

立即体验