6-(2,2-dibromovinyl)-5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylideneuridine | 177420-81-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 6-(2,2-dibromovinyl)-5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylideneuridine
• 英文别名: 1-[(3aR,4R,6R,6aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-6-(2,2-dibromoethenyl)pyrimidine-2,4-dione
• CAS: 177420-81-4
• 化学式: C₂₀H₃₀Br₂N₂O₆Si
• 分子量: 582.361
• InChiKey: MXYCJGBGUWORES-BASLNEPJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.06
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  86.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6-(2,2-dibromovinyl)-5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylideneuridine 在 咪唑 、 三氟乙酸 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 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：

  5'-O-(t-butyldimethylsilyl)-2',3'-O-isopropylideneuridine 生成 6-(2,2-dibromovinyl)-5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylideneuridine
  参考文献：
  名称：

  1,5-Translocation Strategy for Nucleoside Anomeric Radicals

  摘要：

  A new method for generating nucleoside anomeric radicals utilizing radical 1,5-translocation was developed. Two kinds of beta-halogenovinyl groups at the C6-position of uracil nucleosides were found to be a good radical source, which subsequently forms a nucleoside anomeric radical. The following 5-endo-trig cyclization gave anomeric spiro nucleosides as products.

  DOI：

  10.1080/07328319708006197

文献信息

• Nucleoside anomeric radicals via 1,5-translocation: Facile access to anomeric spiro nucleosides
  作者：Atsushi Kittaka、Hiromichi Tanaka、Naoki Yamada、Ta-i Miyasaka

  DOI：10.1016/0040-4039(96)00433-9

  日期：1996.4

  generating anomeric radicals of nucleosides was developed based on a 1,5-translocation strategy. A vinyl radical derived from uracil nucleosides having a β,β-dibromovinyl group at the C6 position under-goes the 1,5-translocation to form an anomeric radical, which then cyclizes with the resulting CHCHBr group in a 5-endo-trig manner. The whole sequence has disclosed a facile access to anomeric spiro derivatives

  基于1，5-易位策略，开发了一种产生核苷异头基的方法。衍生自在C6位具有β，β-二溴乙烯基的尿嘧啶核苷的乙烯基经过1,5-移位形成异头基团，然后与所得的CHCHBr基在5-内-基环化。触发方式。整个序列已经公开了容易获得异头螺衍生物。还简要地研究了6-氯-9-（β-d-呋喃呋喃糖基）嘌呤衍生物的类似反应。