9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-4-phenylsulfanyl-α-L-lyxofuranosyl]N6-dimethyladenine | 1338465-03-4

• 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: 9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-4-phenylsulfanyl-α-L-lyxofuranosyl]N6-dimethyladenine
• CAS: 1338465-03-4
• 化学式: C₃₀H₄₉N₅O₃SSi₂
• 分子量: 615.988
• InChiKey: PQZMFAGJZNYHRO-RQELPRGNSA-N

反应信息

• 作为产物：
  描述：

  9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-β-D-glyceropent-3-enofuranosyl]-N6-dimethyladenine 、 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)-N6-dimethyl-4'-phenylsulfanylcordycepin 、 9-[2,5-bis-O-(tert-butyldimethylsilyl)-3-deoxy-4-phenylsulfanyl-α-L-lyxofuranosyl]N6-dimethyladenine
  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