6-(2,2-dibromovinyl)uridine | 245671-30-1

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: 6-(2,2-dibromovinyl)uridine
• 英文别名: 6-(2,2-dibromoethenyl)-1-[(2R,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]pyrimidine-2,4-dione
• CAS: 245671-30-1
• 化学式: C₁₁H₁₂Br₂N₂O₆
• 分子量: 428.034
• InChiKey: IAQKOHQTOFVLLR-UUOKUNOPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  119
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  叔丁基二甲基氯硅烷 、 6-(2,2-dibromovinyl)uridine 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以73%的产率得到2',3',5'-tris-O-(tert-butyldimethylsilyl)-6-(2,2-dibromovinyl)uridine
  参考文献：
  名称：

  Cyclization Reactions of Nucleoside Anomeric Radical with Olefin Tethered on Base:  Factors That Induce Anomeric Stereochemistry

  摘要：

  Nucleoside anomeric radicals were formed through 1,5-translocation of vinyl radicals generated from the 2,2-dibromovinyl group tethered at the uracil 6-position (1, 2, and 4) by tin radical. The anomeric radicals attacked the resulting C-6 vinyl group in a 5-endo-trig manner to afford anomeric spiro nucleosides (11-13, 21, 23, and 24) with the 6,1'-etheno bridge as the major cyclized products. The anomeric stereochemistry of the cyclization was found to be affected by the 2'-substituent. To consider the structure of the intermediate anomeric radical, the reaction using alpha-6-(2,2-dibromovinyl)-2'-deoxyuridine 9 was investigated. The same anomeric beta/alpha-stereoselectivity as the counterpart of 2 showed that the nucleoside anomeric radical would have nearly a planar structure and the C1'-N1. bond rotation in the radical is much faster than cyclization. The origin of the minor spiro nucleosides (14-20, 22, and 25-28) with the 6,1'-ethano bridge has also been investigated and appeared to be (E)-6-(2-bromovinyl)uridine 7E, a reduced form of 1a, but not (Z)-6-(2-bromovinyl)uridine 7Z, which gave a novel type of unstable compound with 6-exomethylene structure 29 through a different reaction pathway. 6-Chloro-8-(2,2-dibromovinyl)purine nucleoside 10 was next studied, and not only 1,5- but also 1,6-translocated products were isolated.

  DOI：

  10.1021/jo990611d
• 作为产物：
  描述：

  6-formyl-5'-O-tert-butyldimethylsilyl-2',3'-O-isopropylideneuridine 在 三氟乙酸 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 6-(2,2-dibromovinyl)uridine
  参考文献：
  名称：

  Cyclization Reactions of Nucleoside Anomeric Radical with Olefin Tethered on Base:  Factors That Induce Anomeric Stereochemistry

  摘要：

  Nucleoside anomeric radicals were formed through 1,5-translocation of vinyl radicals generated from the 2,2-dibromovinyl group tethered at the uracil 6-position (1, 2, and 4) by tin radical. The anomeric radicals attacked the resulting C-6 vinyl group in a 5-endo-trig manner to afford anomeric spiro nucleosides (11-13, 21, 23, and 24) with the 6,1'-etheno bridge as the major cyclized products. The anomeric stereochemistry of the cyclization was found to be affected by the 2'-substituent. To consider the structure of the intermediate anomeric radical, the reaction using alpha-6-(2,2-dibromovinyl)-2'-deoxyuridine 9 was investigated. The same anomeric beta/alpha-stereoselectivity as the counterpart of 2 showed that the nucleoside anomeric radical would have nearly a planar structure and the C1'-N1. bond rotation in the radical is much faster than cyclization. The origin of the minor spiro nucleosides (14-20, 22, and 25-28) with the 6,1'-ethano bridge has also been investigated and appeared to be (E)-6-(2-bromovinyl)uridine 7E, a reduced form of 1a, but not (Z)-6-(2-bromovinyl)uridine 7Z, which gave a novel type of unstable compound with 6-exomethylene structure 29 through a different reaction pathway. 6-Chloro-8-(2,2-dibromovinyl)purine nucleoside 10 was next studied, and not only 1,5- but also 1,6-translocated products were isolated.

  DOI：

  10.1021/jo990611d