胞苷酰-(3',5')-鸟苷 | 2382-65-2

• 物质功能分类: 分析化学 - 分析试剂 - 常用分析试剂
• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - （3'->5'）-二核苷酸和类似物
• 中文名称: 胞苷酰-(3',5')-鸟苷
• 中文别名: 可控孔径玻璃
• 英文名称: [5']guanylic acid cytidin-3'-yl ester
• 英文别名: 5'-C-G-3'；cytidylyl-(3'->5')-guanosine；[5']Guanylsaeure-cytidin-3'-ylester；Cytidylyl-(3',5')-guanosine；[(2R,3S,4R,5R)-5-(2-amino-6-oxo-1H-purin-9-yl)-3,4-dihydroxyoxolan-2-yl]methyl [(2R,3S,4R,5R)-5-(4-amino-2-oxopyrimidin-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] hydrogen phosphate
• CAS: 2382-65-2
• 化学式: C₁₉H₂₅N₈O₁₂P
• 分子量: 588.428
• InChiKey: CTMZLDSMFCVUNX-VMIOUTBZSA-N

物化性质

• 密度：
  0.4 g/mL at 20 °C (lit.)

计算性质

• 辛醇/水分配系数(LogP)：
  -5.7
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  299
• 氢给体数：
  8
• 氢受体数：
  14

安全信息

• 安全说明：
  S26,S36
• 危险类别码：
  R36/37/38

反应信息

• 作为反应物：
  描述：

  胞苷酰-(3',5')-鸟苷 在 咪唑 、 sodium chloride 、 magnesium chloride 作用下， 以 水 为溶剂， 生成 Phosphoric acid (2R,3S,4R,5R)-5-(2-amino-6-oxo-1,6-dihydro-purin-9-yl)-3,4-dihydroxy-tetrahydro-furan-2-ylmethyl ester (2R,3R,4R,5R)-2-(4-amino-2-oxo-2H-pyrimidin-1-yl)-4-hydroxy-5-hydroxymethyl-tetrahydro-furan-3-yl ester
  参考文献：
  名称：

  Kinetic Analysis of the Cleavage of the Ribose Phosphodiester Bond within Guanine and Cytosine-Rich Oligonucleotides and Dinucleotides at 65–200 °C and Its Implications Concerning the Chemical Evolution of RNA

  摘要：

  一种快速热水解反应的监测方法成功应用于对寡核苷酸和二核苷酸中肋糖磷酸二酯键断裂的动力学分析，研究温度为150-200 °C。确定了在寡核苷酸和二核苷酸中肋糖3′,5′-细胞苷酸-鸟苷酸序列（-C3′pGd-）的降解表观速率常数（kapp），结果表明在寡核苷酸中，-C3′pGd-序列的稳定性低于2′,5′-细胞苷酸-鸟苷酸（C2′pG）和3′,5′-细胞苷酸-鸟苷酸（C3′pG）。令人意外的是，目标序列的稳定性依赖于寡核苷酸的周围序列，尽管研究中使用的温度远高于熔点。2′-脱氧细胞苷酸-2′-脱氧鸟苷酸（CdpGd）的磷酸二酯键在低温下的稳定性远高于肋糖磷酸二酯键，但在200 °C时变得相当。C2′pG或C3′pG降解过程中观察到C2′pG与C3′pG之间的相互转化以及磷酸二酯键的断裂。基于对相互转化程度的分析，C2′pG和C3′pG消失的表观速率常数被分解为水解速率常数（khy）和相互转化速率常数（kint），其中khy的值大于kint。目标序列降解的表观活化能为寡核苷酸100-109 kJ mol−1，C3′pG为90 kJ mol−1，C2′pG为87 kJ mol−1，以及CdpGd为139 kJ mol−1。还确定了目标序列降解的表观活化焓和熵变；五种寡核苷酸的活化参数值为ΔH≠app = 94-105 kJ mol−1和ΔS≠app = −(36-59) J mol−1 T−1，C3′pG为ΔH≠app = 86 kJ mol−1和ΔS≠app = −97 J mol−1 T−1，C2′pG为ΔH≠app = 84 kJ mol−1，ΔS≠app = −105 J mol−1 T−1，CdpGd为ΔH≠app = 135 kJ mol−1，ΔS≠app = +2 J mol−1 T−1。寡核苷酸的活化参数ΔH≠app和ΔS≠app随-C3′pGd-周围序列的长度增加而增加；这一事实清楚地表明，周围序列对目标肋糖磷酸二酯键的稳定性存在影响。基于动力学分析，讨论了高温下肋糖磷酸二酯键降解的反应机制。此外，从生命的水热起源的角度讨论了RNA化学演化的可能途径。

  DOI：

  10.1246/bcsj.76.153
• 作为产物：
  描述：

  在 ammonium hydroxide 、 syn-4-硝基苯甲醛肟 、 四甲基胍 作用下， 生成 胞苷酰-(3',5')-鸟苷
  参考文献：
  名称：

  1' ＃，2'，3'，4' ＃，5'，5” -2 H 6 -β-D-核糖核苷和1' ＃，2'，2”，3'，4' ＃，5的合成'，5″ -2 H 7 -β-D-2'-脱氧核糖核苷用于选择性抑制部分氘化的oligo-DNA，oligo-RNA和2,5A核中的质子共振（1 H-NMR窗口）

  摘要：

  阮内镍-2 H 2 O在甲基α/β-D-呋喃核糖苷[α/β= 〜3：10] 1的差向异构体混合物上的交换反应产生了甲基1 ＃，2,3,4 ＃，5,5'- 2 H 6 -α/β-呋喃核糖苷2 [在C2，C3，C5 / 5'处为97原子％2 H；C 4（C4 ＃）〜85原子％2 H ；在C1（C1 ＃）]处约20个原子％2 H，以60 – 80％的产率获得，同时还得到了差向异构的木糖和阿拉伯糖副产物。在干燥的吡啶中将粗产物2甲苯磺酸化，并在硅胶柱上小心分离，得到纯的1-O-甲基-2,3,5-三-O-（4-甲苯甲酰基）-α/β-D-1＃，2,3,4 ＃，5,5'- 2 H 6-核呋喃糖苷4（48％）。4转化为1-O-乙酰基-2,3,5-三-O-甲苯甲酰基-α/β-D-1 ＃，2,3,4 ＃，5,5'- 2 H 6-核呋喃糖苷6（ 82％的人提供了合成氘核糖核苷用于RNA或DNA合成的关键组成部分。然后将化合物6与甲硅烷基尿嘧啶，N

  DOI：

  10.1016/s0040-4020(01)82001-9
• 作为试剂：
  描述：

  (7-chlorocyclohept-2-en-1-yl)-trimethylsilane 在 胞苷酰-(3',5')-鸟苷 作用下， 生成 1,3-环庚二烯
  参考文献：
  名称：

  Les（triméthylsilyl）bicyclo [ n .1.0]-炔烃，nouveaux silylcyclopropanes bicycliques fonctionnels †

  摘要：

  双环[n.1.0]-硅酮合成的原理和方法，从简单到快速。Elle permet d'accéderdans de bonnes条件是aus deuxisomèresendo et exomonosiliciésainsi qu'aux类似物gem- disiliciés。

  DOI：

  10.1002/recl.19881070322

文献信息

• Catalysis of Diribonucleoside Monophosphate Cleavage by Water Soluble Copper(II) Complexes of Calix[4]arene Based Nitrogen Ligands
  作者：Roberta Cacciapaglia、Alessandro Casnati、Luigi Mandolini、David N. Reinhoudt、Riccardo Salvio、Andrea Sartori、Rocco Ungaro

  DOI：10.1021/ja0632106

  日期：2006.9.1

  Calix[4]arenes functionalized at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with [12]ane-N-3 ligating units were synthesized, and their bi-and trimetallic zinc(II) and copper( II) complexes were investigated as catalysts in the cleavage of phosphodiesters as RNA models. The results of comparative kinetic studies using monometallic controls indicate that the subunits of all of the zinc(II) complexes and of the 1,3-distal bimetallic copper(II) complex 7-Cu-2 act as essentially independent monometallic catalysts. The lack of cooperation between metal ions in the above complexes is in marked contrast with the behavior of the 1,2-vicinal bimetallic copper(II) complex 6-Cu-2, which exhibits high catalytic efficiency and high levels of cooperation between metal ions in the cleavage of HPNP and of diribonucleoside monophosphates NpN'. A third ligated metal ion at the upper rim does not enhance the catalytic efficiency, which excludes the simultaneous cooperation in the catalysis of the three metal ions in 8-Cu-3. Rate accelerations relative to the background brought about by 6-Cu-2 and 8-Cu-3 (1.0 mM catalyst, water solution, pH 7.0, 50 degrees C) are on the order of 10(4)-fold, largely independent of the nucleobase structure, with the exception of the cleavage of diribonucleoside monophosphates in which the nucleobase N is uracil, namely UpU and UpG, for which rate enhancements rise to 10(5)-fold. The rationale for the observed selectivity is discussed in terms of deprotonation of the uracil moiety under the reaction conditions and complexation of the resulting anion with one of the copper(II) centers.
• The p<i>K</i>_a of the Internucleotidic 2‘-Hydroxyl Group in Diribonucleoside (3‘→5‘) Monophosphates
  作者：S. Acharya、A. Földesi、J. Chattopadhyaya

  DOI：10.1021/jo026545o

  日期：2003.3.1

  Ionization of the internucleotidic 2'-hydroxyl group in RNA facilitates transesterification reactions in Group I and II introns (splicing), hammerhead and hairpin ribozymes, self-cleavage in lariat-RNA, and leadzymes and tRNA processing by RNase P RNA, as well as in some RNA cleavage reactions promoted by ribonucleases. Earlier, the pK(a) of 2'-OH in mono- and diribonucleoside (3'-->5') monophosphates had been measured under various nonuniform conditions, which make their comparison difficult. This work overcomes this limitation by measuring the pK(a) values for internucleotidic 2'-OH of eight different diribonucleoside (3'-5') monophosphates under a set of uniform noninvasive conditions by H-1 NMR. Thus the pK(a) is 12.31 (+/-0.02) for ApG and 12.41 (+/-0.04) for ApA, 12.73 (+/-0.04) for GpG and 12.71 (+/-0.08) for GpA, 12.77 (+/-0.03) for CpG and 12.88 (+/-0.02) for CpA, and 12.76 (+/-0.03) for UpG and 12.70 (+/-0.03) for UpA. By comparing the pK(a)s of the respective 2'-OH of monomeric nucleoside 3'-ethyl phosphates with that of internucleotidic 2'-OH in corresponding diribonucleoside (3'-5') monophosphates, it has been confirmed that the aglycons have no significant effect on the pKa values of their 2'-OH under our measurement condition, except for the internucleotidic 2'-OH of 9-adeninyl nucleotide at the 5'-end (ApA and ApG), which is more acidic by 0.3-0.4 pK(a) units.
• Dimroth; Witzel, Justus Liebigs Annalen der Chemie, 1959, vol. 620, p. 109,110,116,118
  作者：Dimroth、Witzel

  DOI：——

  日期：——
• KOMIYAMA, MAKOTO, CARBOHYDR. RES., 192,(1989) C. 97-102
  作者：KOMIYAMA, MAKOTO

  DOI：——

  日期：——
• DEUTERATED NUCLEOSIDES
  申请人：CHATTOPADHYAYA, Jyoti

  公开号：EP0648220A1

  公开（公告）日：1995-04-19