4'-allyl-2',5'-bis-O-(tert-butyldimethylsilyl)cordycepin | 1016648-32-0

• 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: 4'-allyl-2',5'-bis-O-(tert-butyldimethylsilyl)cordycepin
• 英文别名: 9-[(2R,3R,5S)-3-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-prop-2-enyloxolan-2-yl]purin-6-amine
• CAS: 1016648-32-0
• 化学式: C₂₅H₄₅N₅O₃Si₂
• 分子量: 519.835
• InChiKey: COSKMTHTLMAHHC-KPCPBYSCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.05
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  97.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  、 烯丙基三丁基锡 在 偶氮二异丁腈 作用下， 以7%的产率得到4'-allyl-2',5'-bis-O-(tert-butyldimethylsilyl)cordycepin
  参考文献：
  名称：

  Phenylsulfanylation of 3′,4′-Unsaturated Adenosine Employing Thiophenol-N-Iodosuccinimide Leads to 4′-Phenylsulfanylcordycepin: Synthesis of 4′-Substituted Cordycepins on the Basis of Substitution of the Phenylsulfanyl Leaving Group

  摘要：

  Upon reaction of the 3',4'-unsaturated adenosine derivative 2 with N-iodosuccinimide (NIS) and thiophenol, an unexpected electrophilic hydrophenylsulfanylation proceeded to provide 4'-phenylsulfanylcordycepin 7 in 79% yield with the ratio 7a/7b = 6.6/1. A study of the reaction mechanism revealed that hydrogen iodide (HI) generated from NIS and PhSH acted as an active species. On the basis of a deuterium experiment using PhSD, initial protonation occurred at the beta face of the double bond to furnish the beta-pi complex III, which underwent anti addition of PhSH as a major pathway. Nucleophilic substitution of N-6-pivaloylated 9 with various alcohols in the presence of N-bromosuccinimide (NBS) gave the respective 4'-alpha-alkoxycordycepins 15a-21a as the major stereoisomers. Use of DAST in place of an alcohol gave the 4'-alpha-fluoro analogue 23a stereoselectively. Radical-mediated carbon carbon bond construction was also applicable to 7, giving 4'-alpha-allylcordycepin (24a) and 4'-alpha-cyanoethylcordycepin (25) derivatives.

  DOI：

  10.1021/jo201246y

文献信息

• Synthesis of 4′-benzoyloxycordycepin from adenosine
  作者：Yutaka Kubota、Mayumi Kunikata、Nobuhide Ishizaki、Kazuhiro Haraguchi、Yuki Odanaka、Hiromichi Tanaka

  DOI：10.1016/j.tet.2008.01.018

  日期：2008.3

  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.
• Phenylsulfanylation of 3′,4′-Unsaturated Adenosine Employing Thiophenol-<i>N</i>-Iodosuccinimide Leads to 4′-Phenylsulfanylcordycepin: Synthesis of 4′-Substituted Cordycepins on the Basis of Substitution of the Phenylsulfanyl Leaving Group
  作者：Yutaka Kubota、Mariko Ehara、Kazuhiro Haraguchi、Hiromichi Tanaka

  DOI：10.1021/jo201246y

  日期：2011.11.4

  Upon reaction of the 3',4'-unsaturated adenosine derivative 2 with N-iodosuccinimide (NIS) and thiophenol, an unexpected electrophilic hydrophenylsulfanylation proceeded to provide 4'-phenylsulfanylcordycepin 7 in 79% yield with the ratio 7a/7b = 6.6/1. A study of the reaction mechanism revealed that hydrogen iodide (HI) generated from NIS and PhSH acted as an active species. On the basis of a deuterium experiment using PhSD, initial protonation occurred at the beta face of the double bond to furnish the beta-pi complex III, which underwent anti addition of PhSH as a major pathway. Nucleophilic substitution of N-6-pivaloylated 9 with various alcohols in the presence of N-bromosuccinimide (NBS) gave the respective 4'-alpha-alkoxycordycepins 15a-21a as the major stereoisomers. Use of DAST in place of an alcohol gave the 4'-alpha-fluoro analogue 23a stereoselectively. Radical-mediated carbon carbon bond construction was also applicable to 7, giving 4'-alpha-allylcordycepin (24a) and 4'-alpha-cyanoethylcordycepin (25) derivatives.