1',2'-didehydro-2'-deoxy-3',5'-bis-O-[(1,1-dimethylethyl)dimethylsilyl]adenosine | 201677-03-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: 1',2'-didehydro-2'-deoxy-3',5'-bis-O-[(1,1-dimethylethyl)dimethylsilyl]adenosine
• 英文别名: 9-[(2R,3S)-3-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,3-dihydrofuran-5-yl]purin-6-amine
• CAS: 201677-03-4
• 化学式: C₂₂H₃₉N₅O₃Si₂
• 分子量: 477.754
• InChiKey: IFLXBKCCWXSFEE-JKSUJKDBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 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：

  1',2'-didehydro-2'-deoxy-3',5'-bis-O-[(1,1-dimethylethyl)dimethylsilyl]adenosine 以 邻二甲苯 为溶剂， 反应 6.0h， 以90%的产率得到9-[5-(tert-Butyl-dimethyl-silanyloxymethyl)-furan-2-yl]-9H-purin-6-ylamine
  参考文献：
  名称：

  Furanyl nucleosides: synthesis and kinetics of their formation

  摘要：

  The thermal reaction (at 140degreesC) of various 1',2'-didehydro-2'-deoxynucleosides afforded the corresponding furanyl nucleosides in good yields. The reaction kinetics were monitored by H-1 NMR and the mechanism in terms of 'four-center complex fission' is discussed. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.04.045
• 作为产物：
  描述：

  3',5'-bis-O-(tert-butyldimethylsilyl)-β-D-adenosine 在 4-二甲氨基吡啶 、 1,5-二氮杂双环[4.3.0]壬-5-烯 、 四丁基碘化铵 、 三乙胺 作用下， 以 吡啶 、 苯 为溶剂， 反应 10.0h， 生成 1',2'-didehydro-2'-deoxy-3',5'-bis-O-[(1,1-dimethylethyl)dimethylsilyl]adenosine
  参考文献：
  名称：

  通过修饰的嘌呤和嘧啶核苷中的β-（酰氧基）烷基重排生成C-1'自由基

  摘要：

  受保护的1'，2'-二氢-2'-脱氧腺苷的合成已通过结合对腺嘌呤氨基官能团的亚磷叉基保护进行了优化。这些不饱和腺苷已用作亲电子碘新戊酰氧基化的底物，导致在异头位置被修饰的新核苷。卤代戊二酸酯10、11和12与氢化三丁基锡的反应通过β-（酰氧基）烷基重排间接产生C-1'自由基。这些重排的速率常数已通过使用自由基时钟方法进行了测量，并将这些数据与先前报道的结果进行比较可提供有关这一重要基团性质的结构信息。

  DOI：

  10.1016/s0040-4020(97)10317-9

文献信息

• Nucleophilic Addition of Benzenethiol to 1‘,2‘-Unsaturated Nucleosides:  1‘-<i>C</i>-Phenylthio-2‘-deoxynucleosides as Anomeric Radical Precursors
  作者：Hiroki Kumamoto、Miki Murasaki、Kazuhiro Haraguchi、Aki Anamura、Hiromichi Tanaka

  DOI：10.1021/jo0201934

  日期：2002.8.1

  The addition reaction of benzenethiol to the glycal portion of 1',2'-unsaturated uridine proceeds efficiently in the presence of Et3N. The mechanism involves nucleophilic attack of thiolate at the anomeric position in the rate-determining step, wherein conjugation between the nucleobase and the glycal portion is crucial. The derivative having a methyl group either at the 2'- or 6-position did not undergo this addition reaction, due to their sterically prohibited coplanarity. The 1',2'-unsaturated derivatives of thymine and adenine can also be used as substrates for this addition reaction. It was also shown that the resulting 1'-C-phenylthio-2'-deoxynucleosides serve as precursors for radical-mediated C-C bond formation at the anomeric position.
• Generation of C-1′ radicals through a β-(acyloxy)alkyl rearrangement in modified purine and pyrimidine nucleosides
  作者：Thanasis Gimisis、Giuseppina Ialongo、Chryssostomos Chatgilialoglu

  DOI：10.1016/s0040-4020(97)10317-9

  日期：1998.1

  12 with tributyltin hydride generates indirectly C-1′ radicals through a β-(acyloxy)alkyl rearrangement. Rate constants for these rearrangements have been measured by using free-radical clock methodology and comparison of these data with previous reported results provides structural information about the nature of this important class of radicals.

  受保护的1'，2'-二氢-2'-脱氧腺苷的合成已通过结合对腺嘌呤氨基官能团的亚磷叉基保护进行了优化。这些不饱和腺苷已用作亲电子碘新戊酰氧基化的底物，导致在异头位置被修饰的新核苷。卤代戊二酸酯10、11和12与氢化三丁基锡的反应通过β-（酰氧基）烷基重排间接产生C-1'自由基。这些重排的速率常数已通过使用自由基时钟方法进行了测量，并将这些数据与先前报道的结果进行比较可提供有关这一重要基团性质的结构信息。
• Furanyl nucleosides: synthesis and kinetics of their formation
  作者：Chryssostomos Chatgilialoglu、Despoina Vrantza、Thanasis Gimisis

  DOI：10.1016/j.tetlet.2004.04.045

  日期：2004.5

  The thermal reaction (at 140degreesC) of various 1',2'-didehydro-2'-deoxynucleosides afforded the corresponding furanyl nucleosides in good yields. The reaction kinetics were monitored by H-1 NMR and the mechanism in terms of 'four-center complex fission' is discussed. (C) 2004 Elsevier Ltd. All rights reserved.