Acetic acid (2R,3S)-5-(tert-butyl-dimethyl-silanyloxymethyl)-2-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-2,3-dihydro-furan-3-yl ester | 135824-38-3

• 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: Acetic acid (2R,3S)-5-(tert-butyl-dimethyl-silanyloxymethyl)-2-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-2,3-dihydro-furan-3-yl ester
• 英文别名: [(2R,3S)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-(2,4-dioxopyrimidin-1-yl)-2,3-dihydrofuran-3-yl] acetate
• CAS: 135824-38-3
• 化学式: C₁₇H₂₆N₂O₆Si
• 分子量: 382.489
• InChiKey: YTINDLJRJBACAW-DZGCQCFKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  26.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  99.62
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  Acetic acid (2R,3S)-5-(tert-butyl-dimethyl-silanyloxymethyl)-2-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-2,3-dihydro-furan-3-yl ester 在 三甲基铝 作用下， 以29%的产率得到1-[5-(tert-Butyl-dimethyl-silanyloxymethyl)-furan-2-yl]-1H-pyrimidine-2,4-dione
  参考文献：
  名称：

  Stereoselective synthesis of 4′-C-branched 2,′3′-didehydro-2′-dideoxy nucleosides based on SnCl4-promoted allylic rearrangement

  摘要：

  Based on SnCl4-promoted allylic rearrangement between a 3',4'-unsaturated uracil nucleoside and organosilicon reagents, stereoselective introduction of carbon functionalities to the 4'-position has been accomplished, disclosing a new entry for a series of 4'-C-branched nucleosides of biological interests.

  DOI：

  10.1016/s0040-4039(00)78874-5
• 作为产物：
  描述：

  5’-O-三苯甲基尿苷-2’,3’-来苏-环氧化物 在 吡啶 、 sodium tetrahydroborate 、 溶剂黄146 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 15.67h， 生成 Acetic acid (2R,3S)-5-(tert-butyl-dimethyl-silanyloxymethyl)-2-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-2,3-dihydro-furan-3-yl ester
  参考文献：
  名称：

  Selenoxide elimination for the synthesis of unsaturated-sugar uracil nucleosides

  摘要：

  Introduction of a phenylseleno group to the sugar portion of uracil nucleosides and selenoxide elimination reactions of the resulting selenium-containing derivatives are described. A phenylselenide anion prepared by reducing (PhSe)2 with LialH4 was found to be highly reactive. By using this selenide as a nucleophile, ring openings of various types of cyclonucleosides and nucleosides having an anhydro structure in the sugar portion were accomplished. The products, which contain a phenylseleno group in the sugar portion, were oxidized with m-CPBA in CH2Cl2, and their susceptibility to the selenoxide elimination and regiochemistry of the reaction was investigated.

  DOI：

  10.1021/jo00018a038

文献信息

• Allylic Substitution of 3‘,4‘-Unsaturated Nucleosides:  Organosilicon-Based Stereoselective Access to 4‘-<i>C</i>-Branched 2‘,3‘-Didehydro-2‘,3‘-dideoxyribonucleosides
  作者：Kazuhiro Haraguchi、Hiromichi Tanaka、Yoshiharu Itoh、Kentaro Yamaguchi、Tadashi Miyasaka

  DOI：10.1021/jo9516190

  日期：1996.1.1

  Reactions of organosilicon reagents (such as allyltrimethylsilane, silyl enol ethers, cyanotrimethylsilane) with 3',4'-unsaturated nucleosides (of uracil, N-4-acetylcytosine, and hypoxanthine) having an allyl ester structure were investigated in the presence of a Lewis acid in CH2Cl2. In the cases of uracil and N-4-acetylcytosine derivatives, SnCl4 appeared to be suitable, whereas the use of EtAlCl(2) was necessary for the hypoxanthine derivatives. The main pathway of these reactions was found to be a-face-selective S(N)2' allylic substitution, irrespective of the configuration of 2'-0-acyl leaving group. As a result, a new stereoselective operation for C-C bonds formation leading to 4'-carbon-substituted 2',3'-didehydro-2',3'-dideoxyribonucleosides has been disclosed for the first time. Stereochemistry of these 4'-C-branched products can be assigned on the basis of H-1 NMR spectroscopy in terms of the anisotropic shift of H-5 of the pyrimidine base (or H-8 of the hypoxanthine), which is caused by the 5'-0-(tert-butyldiphenylsilyl) protecting group.