Phosphoric acid (2R,3S,4R,5R)-5-(2-amino-6-oxo-1,6-dihydro-purin-9-yl)-4-hydroxy-2-hydroxymethyl-tetrahydro-furan-3-yl ester (2R,3S,4R,5R)-5-(6-amino-purin-9-yl)-3,4-dihydroxy-tetrahydro-furan-2-ylmethyl ester | 6554-00-3

• 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
• 英文名称: Phosphoric acid (2R,3S,4R,5R)-5-(2-amino-6-oxo-1,6-dihydro-purin-9-yl)-4-hydroxy-2-hydroxymethyl-tetrahydro-furan-3-yl ester (2R,3S,4R,5R)-5-(6-amino-purin-9-yl)-3,4-dihydroxy-tetrahydro-furan-2-ylmethyl ester
• 英文别名: GpA；5'-GpA-3'；5'-GA-3'；Guanine ribonucleotidyl-(3'-5')-adenosine；[(2R,3S,4R,5R)-5-(2-amino-6-oxo-1H-purin-9-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2R,3S,4R,5R)-5-(6-aminopurin-9-yl)-3,4-dihydroxyoxolan-2-yl]methyl hydrogen phosphate
• CAS: 6554-00-3
• 化学式: C₂₀H₂₅N₁₀O₁₁P
• 分子量: 612.453
• InChiKey: PBWYGOYNGCCLAU-INFSMZHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -5.8
• 重原子数：
  42
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  310
• 氢给体数：
  8
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  Phosphoric acid (2R,3S,4R,5R)-5-(2-amino-6-oxo-1,6-dihydro-purin-9-yl)-4-hydroxy-2-hydroxymethyl-tetrahydro-furan-3-yl ester (2R,3S,4R,5R)-5-(6-amino-purin-9-yl)-3,4-dihydroxy-tetrahydro-furan-2-ylmethyl ester 在 (tri-[12]aneN₃-functionalized calix[4]arene)*[Cu(II)]3 作用下， 以 水 为溶剂， 生成 guanosine 2',3'-cyclic monophosphate 、 腺苷
  参考文献：
  名称：

  Catalysis of Diribonucleoside Monophosphate Cleavage by Water Soluble Copper(II) Complexes of Calix[4]arene Based Nitrogen Ligands

  摘要：

  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.

  DOI：

  10.1021/ja0632106
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 bismuth Hydroxide 作用下， 生成 Phosphoric acid (2R,3S,4R,5R)-5-(2-amino-6-oxo-1,6-dihydro-purin-9-yl)-4-hydroxy-2-hydroxymethyl-tetrahydro-furan-3-yl ester (2R,3S,4R,5R)-5-(6-amino-purin-9-yl)-3,4-dihydroxy-tetrahydro-furan-2-ylmethyl ester
  参考文献：
  名称：

  Dimroth; Witzel, Justus Liebigs Annalen der Chemie, 1959, vol. 620, p. 109,110,116,118

  摘要：

  DOI：

文献信息

• CESIUM FLUORIDE PROMOTES SYNTHESIS OF RIBOOLIGONUCLEOTIDES VIA PHOSPHOTRIESTER APPROACH
  作者：Hiroshi Takaku、Tadaaki Nomoto、Mitsuho Murata、Tsujiaki Hata

  DOI：10.1246/cl.1980.1419

  日期：1980.11.5

  In the presence of cesium fluoride, the reactions of a fully protected 5′-O-dimethoxytrityl-2′-O-tetrahydropyranyl-N-acylnucleoside 3′-(4-chlorophenyl, 5-chloro-8-quinolyl) phosphates with 5′-hydroxyl nucleosides proceeded rapidly under mild conditions to afford the corresponding ribodinucleoside monophosphates in good yields.

  在氟化铯存在下，完全保护的 5′-O-二甲氧基三苯甲基-2′-O-四氢吡喃-N-酰基核苷 3′-（4-氯苯基，5-氯-8-喹啉基）磷酸酯与 5′-羟基核苷的反应在温和条件下迅速进行，以良好的产率得到相应的核糖核苷单磷酸酯。
• Efficient and Selective Cleavage of RNA Oligonucleotides by Calix[4]arene-Based Synthetic Metallonucleases
  作者：Roberta Cacciapaglia、Alessandro Casnati、Luigi Mandolini、Alessio Peracchi、David N. Reinhoudt、Riccardo Salvio、Andrea Sartori、Rocco Ungaro

  DOI：10.1021/ja0737366

  日期：2007.10.1

  The highest rate acceleration, brought about in the cleavage of the 5'-pCpA bond in hexanucleotide 9 by 50 muM trinuclear complex 5-Cu3 (water solution, pH 7.4, 50 degrees C), amounts to 5 x 105-fold, as based on the estimated background reactivity of the CpA dimer. Selectivity in the cleavage of oligoribonucleotides by copper(II) complexes closely resembles that experienced by ribonuclease A and by

  [12]aneN3 大环的双核和三核铜 (II) 配合物锚定在锥形杯 [4] 芳烃上缘的 1,2-、1,3-和 1,2,3-位被研究为裂解6-、7-和17-聚寡核糖核苷酸试剂。使用凝胶电泳进行裂解反应的动力学研究以分离和分析在末端 5'-位置具有放射性磷酸盐标记的反应物和产物。在与单核对照的切割率比较的基础上评估合作程度。对于所有金属配合物，观察到 CpA 磷酸二酯键裂解的显着选择性，与先前在相同金属配合物裂解二核糖核苷单磷酸酯中观察到的 UpU 和 UpG 选择性形成鲜明对比。最高速率加速度，由 50 μM 三核复合物 5-Cu3（水溶液，pH 7.4，50 摄氏度）在六核苷酸 9 中裂解 5'-pCpA 键时产生，根据估计的背景反应性，达到 5 x 105 倍CpA 二聚体。铜 (II) 复合物切割寡核糖核苷酸的选择性与核糖核酸酶 A 和许多不依赖金属的 RNase A 模拟物所经历的选择性非常相似。讨论了
• Base moiety selectivity in cleavage of short oligoribonucleotides by di- and tri-nuclear Zn(II) complexes of azacrown-derived ligands
  作者：Maarit Laine、Kaisa Ketomäki、Päivi Poijärvi-Virta、Harri Lönnberg

  DOI：10.1039/b904828f

  日期：——

  l]benzene (L1) and the trinuclear Zn2+ complex of 1,3,5-tris[(1,5,9-triazacyclododecan-3-yl)oxymethyl]benzene (L3) has been studied. The dinuclear complex cleaves at sufficiently low concentrations ([(Zn2+)2L1] ≤ 0.1 mmol L−1) the 5′NpU3′ and 5′UpN3′ bonds (N = G, C, A) much more readily than the other phosphodiester bonds, but leaves the 5′UpU3′ site intact. The trinuclear (Zn2+)3L3 complex, in turn

  六聚寡核糖核苷酸的双核Zn 2+配合物的切割。1,3-双[（（1,5,9-三氮杂环十二烷-3-基）氧基甲基]苯（L 1）和三核Zn 2+络合物1,3,5-三[[（1,5,9-三氮杂环十二烷-3-基）氧甲基]苯（L 3）已被研究。在足够低的浓度下的双核配合物裂解（[（锌2+）2大号1 ]≤0.1毫摩尔大号-1）的5' NPU 3'和5' UPN 3'键（N = G，C，A）更容易比其他磷酸二酯键，但叶片5' UPU 3'位点不变。三核（锌2+）3大号3复合物，进而，裂解5' UPU 3'键更容易比其他任何联系，甚至快于5' NPU3'和5' UPN 3'的网站。多少有些出人意料，在5' UPNpU 3'网站是由二和三核配都只能慢慢切割。当六核苷酸通过3个额外的2'- O-甲基核糖核苷酸CG对封闭在发夹环上时，碱基部分的选择性在质量上仍然相似，尽管略微不那么明显。双螺旋杆内磷酸二酯键不断裂，甚
• 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.
• Réactions synthétiques par la ribonucléase T1
  作者：Kimiko Sato-Asano、Fujio Egami

  DOI：10.1016/0006-3002(58)90032-5

  日期：1958.9