N-1-(2,4-dinitrophenyl)-5'-O-(monomethoxytrityl)-2',3'-O-isopropylideneinosine | 239080-21-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: N-1-(2,4-dinitrophenyl)-5'-O-(monomethoxytrityl)-2',3'-O-isopropylideneinosine
• 英文别名: 9-[(3aR,4R,6R,6aR)-6-[[(4-methoxyphenyl)-diphenylmethoxy]methyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-1-(2,4-dinitrophenyl)purin-6-one
• CAS: 239080-21-8
• 化学式: C₃₉H₃₄N₆O₁₀
• 分子量: 746.733
• InChiKey: VGSMJHRUJUSGDA-SPBWOXKUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  55
• 可旋转键数：
  9
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  188
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  N-1-(2,4-dinitrophenyl)-5'-O-(monomethoxytrityl)-2',3'-O-isopropylideneinosine 在 咪唑 、 四氮唑 、 2,4,6-三异丙基苯磺酰氯 、 四丁基氟化铵 、 potassium carbonate 、 溶剂黄146 、 N-溴代乙酰胺 作用下， 以 四氢呋喃 、 吡啶 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.0h， 生成 8-bromo-N-1-[(1R,2S,3R,4R)-2,3-(isopropylidenedioxy)-4-[[(bisphenylthiophosphoryl)oxy]methyl]cyclopentyl]-5'-O-(dianilinophosphoryl)-2',3'-O-isopropylideneinosine
  参考文献：
  名称：

  An Efficient Synthesis of Cyclic IDP- and Cyclic 8-Bromo-IDP-Carbocyclic-Riboses Using a Modified Hata Condensation Method To Form an Intramolecular Pyrophosphate Linkage as a Key Step. An Entry to a General Method for the Chemical Synthesis of Cyclic ADP-Ribose Analogues¹

  摘要：

  An efficient synthesis of cyclic IDP-carbocyclic-ribose (3! and its 8-bromo derivative 6, as stable mimics of cyclic ADP-ribose, was achieved, and a condensation reaction with phenylthiophosphate-type substrate 15 or 16 to form an intramolecular pyrophosphate linkage was a key step. N-1-Carbocyclic-ribosylinosine derivative 28 and the corresponding 8-bromo congener 24 were prepared via condensation between N-1-(2,4-dinitrophenyl)inosine derivative 17 and a known optically active carbocyclic amine 18. Compounds 24 and 28 were then converted to the corresponding 5''-phosphoryl-5'-phenylthiophosphate derivatives 15 and 16, respectively, which were substrates for the condensation reaction to form an intramolecular pyrophosphate linkage. Treatment of 8-bromo substrate 15 with It or AgNO3 in the presence of molecular sieves 3A (MS 3A) in pyridine at room temperature gave the desired cyclic product 12 quantitatively, while the yield was quite low without MS. The similar reaction of 8-unsubstituted substrate 16 gave the corresponding cyclized product 32 in 81% yield. Acidic treatment of these cyclic pyrophosphates 12 and 32 readily gave the targets 6 and 3, respectively. This result suggests that the construction of N-1-substituted hypoxanthine nucleoside structures from N-1-(2, 4-dinitrophenyl)ino sine derivatives and the intramolecular condensation by activation of the phenylthiophosphate group with I-2 or AgNO3/MS 3A combine to provide a very efficient route for the synthesis of analogues of cyclic ADP-ribose such as 3 and 6. Thus, this may be an entry to a general method for synthesizing biologically important cyclic nucleotides of this type.

  DOI：

  10.1021/jo0000877
• 作为产物：
  描述：

  2',3'-O-异丙叉肌苷 在 potassium carbonate 作用下， 以 吡啶 、 N,N-二甲基甲酰胺 为溶剂， 反应 42.5h， 生成 N-1-(2,4-dinitrophenyl)-5'-O-(monomethoxytrityl)-2',3'-O-isopropylideneinosine
  参考文献：
  名称：

  An Efficient Synthesis of Cyclic IDP- and Cyclic 8-Bromo-IDP-Carbocyclic-Riboses Using a Modified Hata Condensation Method To Form an Intramolecular Pyrophosphate Linkage as a Key Step. An Entry to a General Method for the Chemical Synthesis of Cyclic ADP-Ribose Analogues¹

  摘要：

  An efficient synthesis of cyclic IDP-carbocyclic-ribose (3! and its 8-bromo derivative 6, as stable mimics of cyclic ADP-ribose, was achieved, and a condensation reaction with phenylthiophosphate-type substrate 15 or 16 to form an intramolecular pyrophosphate linkage was a key step. N-1-Carbocyclic-ribosylinosine derivative 28 and the corresponding 8-bromo congener 24 were prepared via condensation between N-1-(2,4-dinitrophenyl)inosine derivative 17 and a known optically active carbocyclic amine 18. Compounds 24 and 28 were then converted to the corresponding 5''-phosphoryl-5'-phenylthiophosphate derivatives 15 and 16, respectively, which were substrates for the condensation reaction to form an intramolecular pyrophosphate linkage. Treatment of 8-bromo substrate 15 with It or AgNO3 in the presence of molecular sieves 3A (MS 3A) in pyridine at room temperature gave the desired cyclic product 12 quantitatively, while the yield was quite low without MS. The similar reaction of 8-unsubstituted substrate 16 gave the corresponding cyclized product 32 in 81% yield. Acidic treatment of these cyclic pyrophosphates 12 and 32 readily gave the targets 6 and 3, respectively. This result suggests that the construction of N-1-substituted hypoxanthine nucleoside structures from N-1-(2, 4-dinitrophenyl)ino sine derivatives and the intramolecular condensation by activation of the phenylthiophosphate group with I-2 or AgNO3/MS 3A combine to provide a very efficient route for the synthesis of analogues of cyclic ADP-ribose such as 3 and 6. Thus, this may be an entry to a general method for synthesizing biologically important cyclic nucleotides of this type.

  DOI：

  10.1021/jo0000877

文献信息

• Concise synthesis of novel acyclic analogues of cADPR with an ether chain as the northern moiety
  作者：Huimin Wu、Zhenjun Yang、Liangren Zhang、Lihe Zhang

  DOI：10.1039/b9nj00595a

  日期：——

  To study the properties of hydrolysates of cyclic adenosine diphosphate ribose (cADPR), a series of novel acyclic analogues of cADPR with an ether chain as the northern moiety and 8-substituted adenine or hypoxanthine as the base moiety were synthesized via an N1 substitution construction, followed by bisphosphorylation, phosphoramidition or pyrophosphorylation. These compounds also provide various precursors for synthesizing cADPR analogues.

  为了研究环腺苷二磷酸核糖（cADPR）水解产物的性质，合成了一系列以醚链作为北基团，8取代腺嘌呤或次黄嘌呤作为碱基团的新型无环类cADPR类似物，合成过程包括N1取代反应，随后进行双磷酸化、磷酰胺化或焦磷酸化。这些化合物还提供了合成cADPR类似物的多种前体。
• INTRACELLULAR Ca²⁺-MOBILIZING ADENINE NUCLEOTIDES. SYNTHESIS AND BIOLOGICAL ACTIVITY OF CYCLIC ADP-CARBOCYCLIC-RIBOSE AND<i>C</i>-GLYCOSIDIC ANALOG OF ADENOPHOSTIN A
  作者：Satoshi Shuto、Masayoshi Fukuoka、Hiroshi Abe、Akira Matsuda

  DOI：10.1081/ncn-100002320

  日期：2001.3.31

  We designed novel Ca(2+)-mobilizing purine nucleotides, cyclic ADP-carbocyclicribose 4, and its inosine congener 5, and C-glycosidic adenophostin A 6. In the synthesis of cADPR analogs, the intramolecular condensation to form the pyrophosphate linkage should be the key step. We developed an efficient method for forming such an intramolecular pyrophosphate linkage by the activation of the phenylthiophosphate

  我们设计了新颖的Ca（2+）动员嘌呤核苷酸，环ADP-碳环核糖4，其肌苷同源物5和C-糖苷腺苷A6。在合成cADPR类似物时，分子内缩合形成焦磷酸酯键应为关键步骤。我们开发了一种通过用I2或AgNO3活化苯硫代磷酸酯基团来形成分子内焦磷酸酯键的有效方法。使用该方法，我们合成了目标化合物4和5。使用暂时的硅链自由基偶联反应来构建（3'alpha，1“ alpha）-C，可以合成腺磷素A的C-糖苷类似物6。 -糖苷结构为关键步骤。
• Alternative synthesis of cyclic IDP-carbocyclic ribose. Efficient cyclization of an 8-bromo-N1-[5-(phosphoryl)carbocyclic-ribosyl]inosine 5′-phenylthiophosphate derivative mediated by iodine
  作者：Masayoshi Fukuoka、Satoshi Shuto、Noriaki Minakawa、Yoshihito Ueno、Akira Matsuda

  DOI：10.1016/s0040-4039(99)00977-6

  日期：1999.7

  An efficient synthesis of cyclic IDP-carbocyclic-ribose, as a stable mimic for cyclic ADP-ribose, was achieved. N-1-Carbocyclic-ribosylinosine derivative 15, prepared from N-1-(2,4-dinitrophenyl)inosine derivative 10 and an optically active carbocyclic amine 11, was converted to 8-bromo-N-1-carbocyclic-ribosylinosine bis-phosphate derivative 20. Treatment of 20 with I-2 in the presence of molecular sieves in pyridine gave the desired cyclic product 8 quantitatively, which was deprotected and reductively debrominated to give the target cyclic IDP-carbocyclic ribose (3). (C) 1999 Elsevier Science Ltd. All rights reserved.
• An Efficient Synthesis of Cyclic IDP- and Cyclic 8-Bromo-IDP-Carbocyclic-Riboses Using a Modified Hata Condensation Method To Form an Intramolecular Pyrophosphate Linkage as a Key Step. An Entry to a General Method for the Chemical Synthesis of Cyclic ADP-Ribose Analogues¹
  作者：Masayoshi Fukuoka、Satoshi Shuto、Noriaki Minakawa、Yoshihito Ueno、Akira Matsuda

  DOI：10.1021/jo0000877

  日期：2000.8.1

  An efficient synthesis of cyclic IDP-carbocyclic-ribose (3! and its 8-bromo derivative 6, as stable mimics of cyclic ADP-ribose, was achieved, and a condensation reaction with phenylthiophosphate-type substrate 15 or 16 to form an intramolecular pyrophosphate linkage was a key step. N-1-Carbocyclic-ribosylinosine derivative 28 and the corresponding 8-bromo congener 24 were prepared via condensation between N-1-(2,4-dinitrophenyl)inosine derivative 17 and a known optically active carbocyclic amine 18. Compounds 24 and 28 were then converted to the corresponding 5''-phosphoryl-5'-phenylthiophosphate derivatives 15 and 16, respectively, which were substrates for the condensation reaction to form an intramolecular pyrophosphate linkage. Treatment of 8-bromo substrate 15 with It or AgNO3 in the presence of molecular sieves 3A (MS 3A) in pyridine at room temperature gave the desired cyclic product 12 quantitatively, while the yield was quite low without MS. The similar reaction of 8-unsubstituted substrate 16 gave the corresponding cyclized product 32 in 81% yield. Acidic treatment of these cyclic pyrophosphates 12 and 32 readily gave the targets 6 and 3, respectively. This result suggests that the construction of N-1-substituted hypoxanthine nucleoside structures from N-1-(2, 4-dinitrophenyl)ino sine derivatives and the intramolecular condensation by activation of the phenylthiophosphate group with I-2 or AgNO3/MS 3A combine to provide a very efficient route for the synthesis of analogues of cyclic ADP-ribose such as 3 and 6. Thus, this may be an entry to a general method for synthesizing biologically important cyclic nucleotides of this type.