3',5'-O-(Tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-6,1'-etheno-β-uridine | 175521-05-8

• 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'-O-(Tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-6,1'-etheno-β-uridine
• 英文别名: 2'-deoxy-3',5'-O-(tetraisopropyldisiloxan-1,3-diyl)-6,1'-ethenouridine；(6aR,8S,9aS)-2,2,4,4-tetra(propan-2-yl)spiro[6,6a,9,9a-tetrahydrofuro[3,2-f][1,3,5,2,4]trioxadisilocine-8,7'-pyrrolo[1,2-c]pyrimidine]-1',3'-dione
• CAS: 175521-05-8
• 化学式: C₂₃H₃₈N₂O₆Si₂
• 分子量: 494.736
• InChiKey: JALXVPGMLUFFIX-MIZPHKNDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.96
• 重原子数：
  33
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.74
• 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：

  3',5'-O-(Tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-6,1'-etheno-β-uridine 在 rhodium on aluminium 氢气 、 三乙胺 作用下， 以 甲醇 为溶剂， 反应 5.0h， 生成 3',5'-O-(Tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-6,1'-ethano-β-uridine
  参考文献：
  名称：

  C-1′ Radical-Based Approaches for the Synthesis of Anomeric Spironucleosides

  摘要：

  DOI：

  10.1002/(sici)1521-3765(19991001)5:10<2866::aid-chem2866>3.0.co;2-6
• 作为产物：
  描述：

  3',5'-O-(1,1,3,3-四异丙基-1,3-DISILOXANEDIYL)-2'-脱氧尿苷 在 偶氮二异丁腈 、 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， 生成 3',5'-O-(Tetraisopropyldisiloxane-1,3-diyl)-2'-deoxy-6,1'-etheno-β-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

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。
• 1,5-Translocation Strategy for Nucleoside Anomeric Radicals
  作者：Atsushi Kittaka、Hiromichi Tanaka、Naoki Yamada、Hajime Kato、Tadashi Miyasaka

  DOI：10.1080/07328319708006197

  日期：1997.7

  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.
• 1,5-Radical Translocation Protocol for the Generation of C-1‘ Radicals in Nucleosides. Synthesis of Spiro Nucleosides through a Rare 5-<i>endo</i>-<i>trig </i>Cyclization
  作者：T. Gimisis、C. Chatgilialoglu

  DOI：10.1021/jo952218n

  日期：1996.1.1
• 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.
• C-1′ Radical-Based Approaches for the Synthesis of Anomeric Spironucleosides
  作者：Chryssostomos Chatgilialoglu、Thanasis Gimisis、Gian Piero Spada

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2866::aid-chem2866>3.0.co;2-6

  日期：1999.10.1