2',3'-di-O-acetylguanosine | 42167-65-7

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: 2',3'-di-O-acetylguanosine
• 英文别名: 2',3'-acetylguanosine；2',3'-diacetylguanosine；[(2R,3R,4R,5R)-4-acetyloxy-5-(2-amino-6-oxo-3H-purin-9-yl)-2-(hydroxymethyl)oxolan-3-yl] acetate
• CAS: 42167-65-7
• 化学式: C₁₄H₁₇N₅O₇
• 分子量: 367.318
• InChiKey: MESNVKGXLMWATF-QYVSTXNMSA-N

物化性质

• 溶解度：
  DMSO：17.86 mg/mL（48.62 mM；超声加热至 80°C）

计算性质

• 辛醇/水分配系数(LogP)：
  -1.3
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  167
• 氢给体数：
  3
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2',3'-di-O-acetylguanosine 在 吡啶 、 ammonium hydroxide 、 lithium sulfide 、 三正丁胺 、 三丁基焦磷酸铵 、 sulfur 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.84h， 生成 guanosine 5'-O-(1,1-dithiotriphosphate)
  参考文献：
  名称：

  Synthesis of nucleoside 5'-O-(1,3-dithiotriphosphates) and 5'-O-(1,1-dithiotriphosphates)

  摘要：

  The synthesis of 3'-deoxy-3'-azidothymidine 5'-O-(1,3-dithiotriphosphate) (5) as the first example of a nucleoside 5'-O-(1,3-dithiotriphosphate) is described. 2-Chloro-4H-1,3,2-benzodioxaphosphorin-4-one phosphitylates the 5'-hydroxy group of 3'deoxy-3'-azidothymidine to form intermediate 1. Reaction of 1 with thiopyrophosphate (9) and sulfur results in the formation of an unseparable mixture of 3'-deoxy-3'-azidothymidine 5'-O-(1,3-dithiotriphosphate) (5) and 3'-deoxy-3'-azidothymidine 5'-O-(1,2-dithiotriphosphate) (3). Selective hydrolysis of 5 allows isolation of 3. However, reaction of 1 with P1-O-(cyanoethyl)-P1-thiopyrophosphate (8) and sulfur produced the diastereomers of 5 in good yield. Compound 8 is prepared by reaction of 3-hydroxyproprionitrile with 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one, pyrophosphate, and sulfur to yield 10, which is ring opened to 8 by reaction with ethylenediamine. Hydrolysis of this compound leads to 9. An alternative route to nucleoside 5'-O-(1,3-dithiotriphosphates) consists of reacting a nucleoside 5'-O-(1-thiocyclotriphosphate) such as 13 with Li2S. This reaction, when performed in pyridine/dioxane, leads to a mixture of the nucleoside 5'-O-(1,3-dithiotriphosphate) and the nucleoside 5'-O-(1,1-dithiotriphosphate). The latter is the only nucleotide product when the reaction is carried out in DMF.

  DOI：

  10.1021/jo00005a023

文献信息

• A practical synthesis of nucleoside 5′-diphosphates from nucleoside 5′-<i>H</i>-phosphonate monoesters
  作者：Marta Rachwalak、Malgorzata Rozniewska、Justyna Golebiewska、Tomasz Jakubowski、Michal Sobkowski、Joanna Romanowska

  DOI：10.1080/00397911.2020.1814817

  日期：2020.12.16

  and convenient synthetic protocols based on H-phosphonate chemistry have been developed for the preparation of nucleoside 5′-diphosphates. It consists of oxidation of the silylated H-phosphonate monoesters in pyridine with iodine to produce the corresponding N-pyridiniumphosphonate intermediates, followed by their reactions with orthophosphoric acid used as a nucleophile. The added value of the method

  摘要 已经开发了一种基于 H-膦酸酯化学的简单方便的合成方案，用于制备核苷 5'-二磷酸。它包括在吡啶中用碘氧化甲硅烷基化的 H-膦酸酯单酯以产生相应的 N-吡啶鎓膦酸酯中间体，然后它们与用作亲核试剂的正磷酸反应。该方法的附加值是反应的底物 H-膦酸酯单酯可以由相应的核苷原位制备，无需分离即可用于下一步。该方法简单，适用于核糖和脱氧核糖核苷的各种二磷酸盐及其类似物的制备。图形概要
• A Simple Enzymatic Preparation of 2’,3’-Di-OAcetylnucleosides Through a Lipase Catalyzed Alcoholysis
  作者：Alejandra Zinni、Alejandro Schmidt、Mariana Gallo、Luis Iglesias、Adolfo Iribarren

  DOI：10.3390/50300533

  日期：——

  Several 2’,3’-di-O-acetylnucleosides (2a-d) were obtained regioselectively through a Candida antarctica B lipase catalyzed alcoholysis.

  几种 2',3'-二-O-乙酰基核苷（2a-d）是通过白色念珠菌 B 脂肪酶催化醇解而获得的。
• Synthesis of α-P-Modified Nucleoside Diphosphates with Ethylenediamine
  作者：Ping Li、Zhihong Xu、Hongyan Liu、Charlotta K. Wennefors、Mikhail I. Dobrikov、János Ludwig、Barbara Ramsay Shaw

  DOI：10.1021/ja055179y

  日期：2005.12.1

  a one-pot synthesis of α-P-borano-, α-P-thio-, and α-P-seleno-modified nucleoside diphosphate analogues that are otherwise difficult to obtain. The key step involves the intramolecular nucleophilic attack by an amino group in 5 to remove the γ-phosphate. The absolute configurations of P-diastereomers were confirmed by analysis of their 1H NMR. Affinity studies revealed that the nucleoside boranodiphosphates

  本报告描述了 α-P-硼烷-、α-P-硫代-和 α-P-硒修饰的核苷二磷酸类似物的一锅合成，否则很难获得。关键步骤涉及 5 中的氨基进行分子内亲核攻击以去除 γ-磷酸盐。P-非对映异构体的绝对构型通过其 1H NMR 分析得到证实。亲和力研究表明，核苷硼二磷酸在抗病毒研究中可能有用。
• Synthesis and Separation of Diastereomers of Ribonucleoside 5‘-(α-P-Borano)triphosphates
  作者：Kaizhang He、Ahmad Hasan、Bozenna Krzyzanowska、Barbara Ramsay Shaw

  DOI：10.1021/jo972002g

  日期：1998.8.1

  synthesize the set of ribonucleoside (A, U, G, and C) 5'-(alpha-P-borano)triphosphates. Phosphitylation of the 2',3'-protected ribonucleoside with 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one gives the 5'-phosphite intermediate 2 which undergoes in situ substitution in the presence of pyrophosphate to give the cyclic intermediate, P(2),P(3)-dioxo-P(1)-ribonucleosidylcyclotriphosphate 3. Immediate oxidation

  核苷硼酸磷酸酯（其中一个磷酸氧原子被一个硼烷基团取代）是天然核苷酸的等离子和等电子类似物。硼酸磷酸酯也是硫代磷酸酯和甲基膦酸酯的生物化学重要同系物。我们已经开发了一种方便的一锅法来合成5'-（α-P-硼烷）三磷酸核糖核苷（A，U，G和C）的集合。2'，3'-保护的核糖核苷被2-氯-4H-1,3,2-苯并二氧杂磷酰基-4-酮进行磷酸化，得到5'-亚磷酸酯中间体2，该中间体在焦磷酸盐存在下进行原位取代，从而得到环状中间体，P（2），P（3）-二氧代-P（1）-核糖苷基环三磷酸酯3。用胺。硼烷络合物立即氧化化合物3产生核糖核苷5' -（α-P-硼烷）环三磷酸酯4。随后将化合物4与水反应，然后使其与氢氧化铵反应，得到的粗产物为核糖核苷5'-（α-P-硼烷）三磷酸酯6的非对映异构体混合物。分离出纯化合物6。使用离子交换色谱法可得到30-45％的总收率。通过反相HPLC分离核糖核苷5'-（α-P-硼烷）三磷酸酯6的两个非对映异构体。
• Synthesis of Boron-Containing ADP and GDP Analogues: Nucleoside 5′-(P-Boranodiphosphates)
  作者：Jinlai Lin、Kaizhang He、Barbara Ramsay Shaw

  DOI：10.1002/1522-2675(20000705)83:7<1392::aid-hlca1392>3.0.co;2-h

  日期：2000.7.5

  New 5′-(Pα-boronated) analogues of the naturally occurring nucleoside diphosphates ADP and GDP were synthesized in good yields, i.e., adenosine 5′-(Pα-boranodiphosphate) (ADPαB; 5a) and guanosine 5′-(Pα-boranodiphosphate) (GDPαB; 5b). Their diastereoisomers were successfully separated by reversed-phase HPLC, and chemical structures were established via spectroscopic methods. The isoelectronic substitution

  以高产率合成了天然存在的二磷酸核苷 ADP 和 GDP 的新 5'-(Pα-硼化) 类似物，即腺苷 5'-(Pα-硼酸二磷酸) (ADPαB; 5a) 和鸟苷 5'-(Pα-硼酸二磷酸) ) (GDPαB; 5b)。通过反相高效液相色谱法成功分离了它们的非对映异构体，并通过光谱方法建立了化学结构。用硼烷 (BH3) 等电子取代磷酸二酯中的一个非桥接 O 原子应该会增加 ADPαB 和 GDPαB 的亲脂性和极性变化。硼化核苷二磷酸可用于研究涉及 ADP 和 GDP 的酶促反应的立体化学过程和金属需求，并作为 10B 的载体用于治疗癌症的硼中子俘获疗法 (BNCT)。