9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-4-phenylsulfanyl-α-L-lyxofuranosyl]adenine | 1338464-96-2

• 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: 9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-4-phenylsulfanyl-α-L-lyxofuranosyl]adenine
• 英文别名: 9-[(2R,3R,5S)-3-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-phenylsulfanyloxolan-2-yl]purin-6-amine
• CAS: 1338464-96-2
• 化学式: C₂₈H₄₅N₅O₃SSi₂
• 分子量: 587.934
• InChiKey: WSUHRAHRUDNROW-LQCMOVKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.23
• 重原子数：
  39
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  123
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-β-D-glyceropent-3-enofuranosyl]adenine 、 苯硫酚 在 N-碘代丁二酰亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.05h， 生成 2',5'-bis-O-(tert-butyldimethylsilyl)-4'-phenylsulfanylcordycepin 、 9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-4-phenylsulfanyl-α-L-lyxofuranosyl]adenine
  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

• 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.