3',5'-Bis-O-(tert-butyldimethylsilyl)-2'-deoxy-6,1'-etheno-8-(methoxycarbonyl)uridine | 155450-99-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯并嘧啶类
• 英文名称: 3',5'-Bis-O-(tert-butyldimethylsilyl)-2'-deoxy-6,1'-etheno-8-(methoxycarbonyl)uridine
• 英文别名: methyl (2S,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-1',3'-dioxospiro[oxolane-2,7'-pyrrolo[1,2-c]pyrimidine]-6'-carboxylate
• CAS: 155450-99-0
• 化学式: C₂₅H₄₂N₂O₇Si₂
• 分子量: 538.789
• InChiKey: JVVOYJJTQQUKEA-CEYNDMKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.96
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  103
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3',5'-Bis-O-(tert-butyldimethylsilyl)-2'-deoxy-6,1'-etheno-8-(methoxycarbonyl)uridine 在 二异丁基氢化铝 作用下， 以 乙醚 、 甲苯 为溶剂， 以51.7%的产率得到3',5'-Bis-O-(tert-butyldimethylsilyl)-2'-deoxy-8-(hydroxymethyl)-6,1'-ethenouridine
  参考文献：
  名称：

  Vinyl Radical-Based Cyclization of 6-Substituted 1-(2-Deoxy-D-erythro-pent-1-enofuranosyl)uracils: Synthesis of Anomeric Spiro Nucleosides

  摘要：

  The preparation of 6-bromovinyl derivatives,of 1-(2-deoxy-D-erythro-pent-1-enofuranosyl)uracils (10-13) and their radical-mediated reactions leading to the formation of cyclized products were investigated with the aim of developing a new method for the synthesis of anomeric spiro nucleosides. Treatment of O-2,2'-anhydrouridine 5 with LDA followed by HCO(2)Me gave 1-(2-deoxy-D-erythro-pent-1-enofuranosyl)-6-formyluracil (9). The 6-bromovinyl derivatives 10-13 were prepared by Wittig reaction of 9. Compounds 10, 12, and 13 underwent a vinyl radical-mediated cyclization (Bu(3)SnH/AIBN, in refluxing benzene) preferentially in a 5-exo-trig manner to give 2'-deoxy-6,1'-ethenouridines 14a and 17 and the corresponding a-anomers 15a and 18 with preponderance of the former. The anomeric stereochemistry of these spiro nucleosides was unambiguously determined based on X-ray crystallography and their chemical reactions. Conversion of 14a to 2'-deoxy-6,1'-ethanouridine (26) was also carried out. The present method offers a straightforward synthesis of certain anomeric spiro nucleosides.

  DOI：

  10.1021/jo00092a024
• 作为产物：
  描述：

  6-(Z)-<2-Bromo-2-(methoxycarbonyl)vinyl>-1-<3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pent-1-enofuranosyl>uracil 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 7.0h， 以2.1%的产率得到3',5'-Bis-O-(tert-butyldimethylsilyl)-2'-deoxy-6,1'-etheno-8-(methoxycarbonyl)-α-uridine
  参考文献：
  名称：

  Vinyl Radical-Based Cyclization of 6-Substituted 1-(2-Deoxy-D-erythro-pent-1-enofuranosyl)uracils: Synthesis of Anomeric Spiro Nucleosides

  摘要：

  The preparation of 6-bromovinyl derivatives,of 1-(2-deoxy-D-erythro-pent-1-enofuranosyl)uracils (10-13) and their radical-mediated reactions leading to the formation of cyclized products were investigated with the aim of developing a new method for the synthesis of anomeric spiro nucleosides. Treatment of O-2,2'-anhydrouridine 5 with LDA followed by HCO(2)Me gave 1-(2-deoxy-D-erythro-pent-1-enofuranosyl)-6-formyluracil (9). The 6-bromovinyl derivatives 10-13 were prepared by Wittig reaction of 9. Compounds 10, 12, and 13 underwent a vinyl radical-mediated cyclization (Bu(3)SnH/AIBN, in refluxing benzene) preferentially in a 5-exo-trig manner to give 2'-deoxy-6,1'-ethenouridines 14a and 17 and the corresponding a-anomers 15a and 18 with preponderance of the former. The anomeric stereochemistry of these spiro nucleosides was unambiguously determined based on X-ray crystallography and their chemical reactions. Conversion of 14a to 2'-deoxy-6,1'-ethanouridine (26) was also carried out. The present method offers a straightforward synthesis of certain anomeric spiro nucleosides.

  DOI：

  10.1021/jo00092a024