8-Bromo-3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxy-6,1'-etheno-α-uridine | 155490-22-5

• 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: 8-Bromo-3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxy-6,1'-etheno-α-uridine
• 英文别名: (2R,4S,5R)-6'-bromo-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]spiro[oxolane-2,7'-pyrrolo[1,2-c]pyrimidine]-1',3'-dione
• CAS: 155490-22-5
• 化学式: C₂₃H₃₉BrN₂O₅Si₂
• 分子量: 559.648
• InChiKey: BWQXDDPJDSJGKE-YGKZAACZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.14
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  77.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  8-Bromo-3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxy-6,1'-etheno-α-uridine 在 四丁基氟化铵 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 以88.8%的产率得到8-Bromo-2'-deoxy-6,1'-etheno-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
• 作为产物：
  描述：

  3-[(2R,3S)-3-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,3-dihydrofuran-5-yl]-2,6-dioxopyrimidine-4-carbaldehyde 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 4.0h， 生成 8-Bromo-3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxy-6,1'-etheno-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

文献信息

• Vinyl Radical-Based Cyclization of 6-Substituted 1-(2-Deoxy-D-erythro-pent-1-enofuranosyl)uracils: Synthesis of Anomeric Spiro Nucleosides
  作者：Atsushi Kittaka、Hiromichi Tanaka、Yuki Odanaka、Kazuyo Ohnuki、Kentaro Yamaguchi、Tadashi Miyasaka

  DOI：10.1021/jo00092a024

  日期：1994.7

  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.