5'-O-tert-butyldiphenylsilyl-8-bromo-2'-deoxyadenosine | 868383-11-3

• 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: 5'-O-tert-butyldiphenylsilyl-8-bromo-2'-deoxyadenosine
• 英文别名: (2R,3S,5R)-5-(6-amino-8-bromopurin-9-yl)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]oxolan-3-ol
• CAS: 868383-11-3
• 化学式: C₂₆H₃₀BrN₅O₃Si
• 分子量: 568.545
• InChiKey: WTNBYXNYTYIQBU-PWRODBHTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  36
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  108
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5'-O-tert-butyldiphenylsilyl-8-bromo-2'-deoxyadenosine 在 palladium on activated charcoal 、 四(三苯基膦)钯 copper(l) iodide 、 TEA 、 氢气 作用下， 以 甲醇 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 20.0~65.0 ℃ 、275.79 kPa 条件下， 反应 30.0h， 生成 5'-O-tert-butyldiphenylsilyl-8-[(anthraquinon-2-yl)ethyl]-2'-deoxyadenosine
  参考文献：
  名称：

  两种 8-[(Anthraquinone-2-yl)-Linked]-2'-脱氧腺苷 3'-苄基磷酸氢盐的合成用于研究 DNA 中的光诱导空穴传输

  摘要：

  The challenge in working with anthraquinone-2'-deoxyadenosine (AQ-dA) conjugates is that they are insoluble in water and only sparingly soluble in most organic solvents. However, water-soluble AQ-dA conjugates with short linkers are required for study of their electrochemical and intramolecular electron transfer Properties in this solvent prior to their use in laser kinetics investigations of photoinduced hole (cation) transport in DNA. This article first describes the synthesis Of a water-soluble, ethynyl-linked AQ-dA conjugate, 8-[(anthraquinone-2-yl)ethynyl]-2'-deoxyadenosine 3'-benzyl hydrogen phosphate, based on initial formation of a 5-O-(4,4'-dimethoxytrityl) (5'-O-DMTr) intermediate. Because intended H-2 over Pd/C reduction of the ethyryl linker in 5-O-DMTr-protected 2'-deoxyadenosines cleaves the DMTr protecting group and precipitates multiple side products, this work also describes the synthesis Of an ethylenyl-linked AQ-dA conjugate, 8-[2-(anthraquinone-2-yl)ethyl]-2'-deoxyadenosine 3'-benzyl hydrogen phosphate, starting with a 5-O-tert-butyldiphenylsilyl protecting group.

  DOI：

  10.1081/ncn-200051894
• 作为产物：
  描述：

  2'-脱氧腺苷 在 吡啶 、 溴 作用下， 以 acetate buffer 为溶剂， 反应 7.0h， 生成 5'-O-tert-butyldiphenylsilyl-8-bromo-2'-deoxyadenosine
  参考文献：
  名称：

  两种 8-[(Anthraquinone-2-yl)-Linked]-2'-脱氧腺苷 3'-苄基磷酸氢盐的合成用于研究 DNA 中的光诱导空穴传输

  摘要：

  The challenge in working with anthraquinone-2'-deoxyadenosine (AQ-dA) conjugates is that they are insoluble in water and only sparingly soluble in most organic solvents. However, water-soluble AQ-dA conjugates with short linkers are required for study of their electrochemical and intramolecular electron transfer Properties in this solvent prior to their use in laser kinetics investigations of photoinduced hole (cation) transport in DNA. This article first describes the synthesis Of a water-soluble, ethynyl-linked AQ-dA conjugate, 8-[(anthraquinone-2-yl)ethynyl]-2'-deoxyadenosine 3'-benzyl hydrogen phosphate, based on initial formation of a 5-O-(4,4'-dimethoxytrityl) (5'-O-DMTr) intermediate. Because intended H-2 over Pd/C reduction of the ethyryl linker in 5-O-DMTr-protected 2'-deoxyadenosines cleaves the DMTr protecting group and precipitates multiple side products, this work also describes the synthesis Of an ethylenyl-linked AQ-dA conjugate, 8-[2-(anthraquinone-2-yl)ethyl]-2'-deoxyadenosine 3'-benzyl hydrogen phosphate, starting with a 5-O-tert-butyldiphenylsilyl protecting group.

  DOI：

  10.1081/ncn-200051894

文献信息

• Synthesis and Electrochemical Evaluation of Conjugates between 2′-Deoxyadenosine and Modified Anthraquinone: Probes for Hole-Transfer Studies in DNA
  作者：Reham A. I. Abou-Elkhair、Dabney W. Dixon、Thomas L. Netzel

  DOI：10.1021/jo900306g

  日期：2009.7.3

  Photoexcitation of anthraquinones (AQ) in association with DNA results in DNA damage mainly at guanine residues, with products from thymine oxidation also observed. Studies of adenine oxidation will be aided by systems with an increased driving force for charge transfer, achieved by adding electron-withdrawing groups to the AQ ring. Attaching AQ derivatives to adenine via a bridge with two carbon atoms should enable

  蒽醌（AQ）与DNA的光激发导致DNA损伤主要在鸟嘌呤残基，并且还观察到胸腺嘧啶氧化的产物。腺嘌呤氧化的研究将通过在AQ环上添加吸电子基团而实现的，具有增强的电荷转移驱动力的系统来辅助。通过带有两个碳原子的桥将AQ衍生物连接到腺嘌呤上，应该能够在DNA双链体结构内实现预期的区域控制。本文中，我们报道了AQ和腺嘌呤之间共轭物的合成，其中AQ部分已被甲酰基，三氟乙酰基和两个甲基酯基团修饰。这些已经通过钯偶联合成叔-丁基二苯基甲硅烷基5'-保护的8-乙炔基-2'-脱氧腺苷与相应的溴蒽醌中间体。通过2，6-二溴蒽醌的单锂化制备带有甲酰基或三氟乙酰基的溴中间体，该步骤需要保护蒽醌羰基。通过用4-溴苯甲酰氯进行Friedel-Crafts酰化反应，然后氧化成三羧酸，环化形成蒽醌环，最后酯化，从1,2,4-三甲基苯中获得带有两个甲酯基的溴中间体。乙炔基连接基的氢化得到乙炔基连接基。循环伏安法表明，具有两
• Synthesis of Two 8-[(Anthraquinone-2-yl)-Linked]-2'-Deoxyadenosine 3'-Benzyl Hydrogen Phosphates for Studies of Photoinduced Hole Transport in DNA
  作者：Reham Abou-Elkhair、Thomas Netzel

  DOI：10.1081/ncn-200051894

  日期：2005.2.1

  The challenge in working with anthraquinone-2'-deoxyadenosine (AQ-dA) conjugates is that they are insoluble in water and only sparingly soluble in most organic solvents. However, water-soluble AQ-dA conjugates with short linkers are required for study of their electrochemical and intramolecular electron transfer Properties in this solvent prior to their use in laser kinetics investigations of photoinduced hole (cation) transport in DNA. This article first describes the synthesis Of a water-soluble, ethynyl-linked AQ-dA conjugate, 8-[(anthraquinone-2-yl)ethynyl]-2'-deoxyadenosine 3'-benzyl hydrogen phosphate, based on initial formation of a 5-O-(4,4'-dimethoxytrityl) (5'-O-DMTr) intermediate. Because intended H-2 over Pd/C reduction of the ethyryl linker in 5-O-DMTr-protected 2'-deoxyadenosines cleaves the DMTr protecting group and precipitates multiple side products, this work also describes the synthesis Of an ethylenyl-linked AQ-dA conjugate, 8-[2-(anthraquinone-2-yl)ethyl]-2'-deoxyadenosine 3'-benzyl hydrogen phosphate, starting with a 5-O-tert-butyldiphenylsilyl protecting group.