2-amino-9-(3',5'-di-O-tert-butyldimethylsilyl-2'-deoxy-β-D-ribofuranosyl)-6-vinylpurine | 188823-57-6

• 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-amino-9-(3',5'-di-O-tert-butyldimethylsilyl-2'-deoxy-β-D-ribofuranosyl)-6-vinylpurine
• 英文别名: 2-amino-9-(3,5-di-O-tert-butyldimethylsilyl-2-deoxy-β-D-ribofuranosyl)-6-vinylpurine；9-[(2R,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-6-ethenylpurin-2-amine
• CAS: 188823-57-6
• 化学式: C₂₄H₄₃N₅O₃Si₂
• 分子量: 505.808
• InChiKey: ZZJYYPZWZAAIPS-IPMKNSEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.75
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  97.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-amino-9-(3',5'-di-O-tert-butyldimethylsilyl-2'-deoxy-β-D-ribofuranosyl)-6-vinylpurine 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以68%的产率得到2-amino-9-(2-deoxy-β-D-ribofuranosyl)-6-vinylpurine
  参考文献：
  名称：

  2-Aminopurine derivatives with C6-substituted olefin as novel cross-linking agents and the synthesis of the corresponding β-phosphoramidite precursors

  摘要：

  The 6-vinylated 2-aminopurine nucleoside (1), which was prepared by the Pd(0)-catalyzed cross-coupling reaction using guanosine 6-O-tosylate and vinyl-tributylstannane, has been demonstrated as a potential cross-linking agent. However, attempts for its incorporation into oligonucleotides were unsuccessful because of the high reactivity toward nucleophiles. In this study, new 2'-deoxy nucleoside derivatives with 6-(2-substituted vinyl)-2-aminopurine were designed to diminish the reactivity of the vinyl group. These new nucleosides have been shown to maintain reactivity toward potent nucleophiles such as butylamine and thiols, suggesting that they would form cross-linking with the target nucleobase due to the proximity within the sense-antisense duplex. Thus, the corresponding beta-phosphoramidite precursors were successfully prepared, and were applied to an automated oligonucletotide synthesizer. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00069-0
• 作为产物：
  描述：

  2'-脱氧鸟苷 在 咪唑 、 4-二甲氨基吡啶 、 四(三苯基膦)钯 、 三乙胺 、 lithium chloride 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 2-amino-9-(3',5'-di-O-tert-butyldimethylsilyl-2'-deoxy-β-D-ribofuranosyl)-6-vinylpurine
  参考文献：
  名称：

  2-Aminopurine derivatives with C6-substituted olefin as novel cross-linking agents and the synthesis of the corresponding β-phosphoramidite precursors

  摘要：

  The 6-vinylated 2-aminopurine nucleoside (1), which was prepared by the Pd(0)-catalyzed cross-coupling reaction using guanosine 6-O-tosylate and vinyl-tributylstannane, has been demonstrated as a potential cross-linking agent. However, attempts for its incorporation into oligonucleotides were unsuccessful because of the high reactivity toward nucleophiles. In this study, new 2'-deoxy nucleoside derivatives with 6-(2-substituted vinyl)-2-aminopurine were designed to diminish the reactivity of the vinyl group. These new nucleosides have been shown to maintain reactivity toward potent nucleophiles such as butylamine and thiols, suggesting that they would form cross-linking with the target nucleobase due to the proximity within the sense-antisense duplex. Thus, the corresponding beta-phosphoramidite precursors were successfully prepared, and were applied to an automated oligonucletotide synthesizer. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00069-0

文献信息

• Hybridization-Promoted and Cytidine-Selective Activation for Cross-Linking with the Use of 2-Amino-6-vinylpurine Derivatives
  作者：Takeshi Kawasaki、Fumi Nagatsugi、Md. Monsur Ali、Minoru Maeda、Kumiko Sugiyama、Kenji Hori、Shigeki Sasaki

  DOI：10.1021/jo048298p

  日期：2005.1.1

  Recently, we have proposed a new concept for cross-linking agents with inducible reactivity, in which the highly reactive cross-linking agent, the 2-amino-6-vinylpurine nucleoside analogue (1), can be regenerated in situ from its stable precursors, the phenylsulfide (4) and the phenylsulfoxide (3) derivatives, by a hybridization-promoted activation process with selectivity to cytidine. The phenylsulfide precursor

  最近，我们提出了具有可诱导反应性的交联剂的新概念，其中可以从其稳定的前体原位再生高反应性的交联剂2-氨基-6-乙烯基嘌呤核苷类似物（1）。苯硫醚（4）和苯亚砜（3）衍生物，通过杂交促进的活化过程，对胞苷具有选择性。尽管苯硫醚前体（4）对强亲核试剂（如胺和硫醇）具有很高的稳定性，但仍显示出交联能力。在这项研究中，我们研究了苯硫基对交联反应的取代作用，并确定了苯硫衍生物的2-羧基取代基（11k）作为具有可诱导反应性的有效交联剂。详细的研究表明，苯亚砜（3）和苯硫醚（4）的前体会产生2-氨基-6-乙烯基嘌呤核苷（1）作为常见的反应性物质。已经得出结论，前体（3和4）的可诱导反应性的性质是通过在ODN中具有胞嘧啶核苷的ODN在双链中的选择性过程，加速了它们对2-氨基-6-乙烯基嘌呤核苷（1）的消除。目标站点。
• A new reactive nucleoside analogue for highly reactive and selective cross-linking reaction to cytidine under neutral conditions
  作者：Fumi Nagatsugi、Natsuko Tokuda、Minoru Maeda、Shigeki Sasaki

  DOI：10.1016/s0960-894x(01)00505-4

  日期：2001.10

  DNA (ODNs) bearing a 2-amino-6-vinylpurine derivative (1) exhibited efficient interstrand cross-linking to cytidine selectively. In this study, a new reactive nucleoside analogue, 2-amino-6-(1-ethylsulfoxy)vinylpurine derivative (7), was designed based on a computational method to achieve high and selective alkylation with cytidine under neutral conditions. It has been demonstrated that the ODN (13)

  我们已经证明带有2-氨基-6-乙烯基嘌呤衍生物（1）的寡核苷酸DNA（ODN）表现出有效的链间选择性交联到胞苷。在这项研究中，基于一种计算方法，设计了一种新的反应性核苷类似物2-氨基-6-（1-乙基硫氧基）乙烯基嘌呤衍生物（7），以在中性条件下实现胞苷的高选择性烷基化。已经证明带有2-氨基-6-（1-乙基亚磺氧基）乙烯基嘌呤的ODN（13）在中性条件下实现了对胞苷的高度选择性和有效的交联。
• Efficient Synthesis of 6-Substituted Purine Derivatives Using Pd-Catalyzed Cross-Coupling Reactions with 2’-Deoxyguanosine O6-Tosylate
  作者：Fumi Nagatsugi、Yuki Ogata、Shuhei Imoto、Shigeki Sasaki

  DOI：10.3987/com-07-s(u)24

  日期：——

  6-Substituted purine analogs function in a variety of biological activities including antiviral pathways. A number of studies have reported on the development of the efficient synthesis of these nucleoside analogs. We previously demonstrated that oligonucleotides containing 2-amino-6-vinylpurine derivatives react with the cytosine at the target site with extreme selectivity. This was the first finding

  6-取代的嘌呤类似物在包括抗病毒途径在内的多种生物活性中起作用。许多研究报告了这些核苷类似物的有效合成的发展。我们之前证明了含有 2-氨基-6-乙烯基嘌呤衍生物的寡核苷酸与靶位点的胞嘧啶反应具有极高的选择性。这是鸟苷的O 6 -甲苯磺酸酯衍生物作为Pd(0)催化的与乙烯基三丁基锡烷的交叉偶联反应产生2-氨基-6-乙烯基嘌呤的有效底物的第一个发现。为了证明甲苯磺酸盐前体的有用性，在本研究中，我们研究了过渡金属催化剂和配体在使用硼酸或格氏试剂作为偶联伙伴来实现交叉偶联反应中。
• Highly Efficient and Selective Cross-Linking to Cytidine Based on a New Strategy for Auto-Activation within a Duplex
  作者：Fumi Nagatsugi、Takeshi Kawasaki、Daisaku Usui、Minoru Maeda、Shigeki Sasaki

  DOI：10.1021/ja990356e

  日期：1999.7.1