(4R,5R)-5-(6-amino-9H-purin-9-yl)-4-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)tetrahydrofuran-2-yl benzoate | 1018978-94-3

• 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: (4R,5R)-5-(6-amino-9H-purin-9-yl)-4-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)tetrahydrofuran-2-yl benzoate
• CAS: 1018978-94-3
• 化学式: C₂₉H₄₅N₅O₅Si₂
• 分子量: 599.878
• InChiKey: NZPSROXNHZIHBA-OOSJUCDLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.29
• 重原子数：
  41.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  123.61
• 氢给体数：
  1.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  (4R,5R)-5-(6-amino-9H-purin-9-yl)-4-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)tetrahydrofuran-2-yl benzoate 、 三甲基氰硅烷 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以58%的产率得到2',5'-bis-O-(tert-butyldimethylsilyl)-4'-cyanocordycepin
  参考文献：
  名称：

  Synthesis of 4′-benzoyloxycordycepin from adenosine

  摘要：

  With an aim to synthesize 4'-substituted cordycepins, the 4'-benzoyloxy precursor (9) was prepared from adenosine through an electrophilic addition (iodo-benzoyloxylation) to the 4',5'-unsaturated derivative (5) and subsequent radical-mediated removal of the 3'-iodine atom of the resulting adducts (6). Usefulness of 9 was briefly verified by synthesizing the 4'-allyl (12) and 4'-cyano (13) analogues of cordycepin. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.01.018
• 作为产物：
  描述：

  (3S,4S,5R)-5-(6-amino-9H-purin-9-yl)-4-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)-3-iodotetrahydrofuran-2-yl benzoate 在 palladium on activated charcoal 氢气 、 三乙胺 作用下， 以 甲醇 为溶剂， 以75%的产率得到9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-β-D-glyceropent-3-enofuranosyl]adenine
  参考文献：
  名称：

  Synthesis of 4′-benzoyloxycordycepin from adenosine

  摘要：

  With an aim to synthesize 4'-substituted cordycepins, the 4'-benzoyloxy precursor (9) was prepared from adenosine through an electrophilic addition (iodo-benzoyloxylation) to the 4',5'-unsaturated derivative (5) and subsequent radical-mediated removal of the 3'-iodine atom of the resulting adducts (6). Usefulness of 9 was briefly verified by synthesizing the 4'-allyl (12) and 4'-cyano (13) analogues of cordycepin. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.01.018

文献信息

• Solvent Effect Observed in Nucleophilic Substitution of 4′-(Benzoyloxy)cordycepin with AlMe₃: Stereochemical Evidence for S_Ni Mechanism
  作者：Yutaka Kubota、Mayumi Kunikata、Kazuhiro Haraguchi、Hiromichi Tanaka

  DOI：10.1021/jo900289h

  日期：2009.5.1

  Nucleophilic substitution between the 4′-benzoyloxy derivative of cordycepin (3′-deoxyadenosine) and AlMe3 proceeds mostly with retention of configuration at the 4′-position: the 4′-benzoyloxy substrate having the β-d-configuration (8a) gave the 4′-methylated β-d-nucleoside (9a) with a high diastereomeric excess, while the substrate 8b having the opposite 4′-configuration gave the corresponding α-l-isomer

  虫草素（3'-脱氧腺苷）的4'-苯甲酰氧基衍生物和AlMe 3之间的亲核取代主要是保留了4'-位置的构型：具有β- d-构型（8a）的4'-苯甲酰氧基底物具有高的非对映异构体过量的4'-甲基化的β- d-核苷（9a），而具有相反的4'-构型的底物8b给出了具有相对较低的立体选择性的相应的α- 1-异构体（9b）。对此反应提出了S N i机理（从8到9）。溶剂的极性对立体选择性有重要影响，尤其是对于9b的形成。