6-[(Z)-2-bromovinyl]-5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylideneuridine | 245671-24-3

• 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-[(Z)-2-bromovinyl]-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-[(Z)-2-bromoethenyl]pyrimidine-2,4-dione
• CAS: 245671-24-3
• 化学式: C₂₀H₃₁BrN₂O₆Si
• 分子量: 503.465
• InChiKey: DXUSYEMGWMAIMT-OZLRCMPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  30
• 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-[(Z)-2-bromovinyl]-5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylideneuridine 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲醇 、 苯 为溶剂， 反应 3.0h， 生成 5'-O-(tert-butyldimethylsilyl)-6-ethyl-2',3'-O-isopropylideneuridine
  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 在 四(三苯基膦)钯 三正丁基氢锡 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 6.0h， 生成 6-[(Z)-2-bromovinyl]-5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylideneuridine
  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

文献信息

• Cyclization Reactions of Nucleoside Anomeric Radical with Olefin Tethered on Base:  Factors That Induce Anomeric Stereochemistry
  作者：Atsushi Kittaka、Takashi Asakura、Tetsuya Kuze、Hiromichi Tanaka、Naoki Yamada、Kazuo T. Nakamura、Tadashi Miyasaka

  DOI：10.1021/jo990611d

  日期：1999.9.1

  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.