1-<3-deoxy-3-(phenylseleno)-5-O-trityl-β-D-arabinofuranosyl>uracil | 135824-30-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 1-<3-deoxy-3-(phenylseleno)-5-O-trityl-β-D-arabinofuranosyl>uracil
• 英文别名: 1-[(2R,3R,4S,5R)-3-hydroxy-4-phenylselanyl-5-(trityloxymethyl)oxolan-2-yl]pyrimidine-2,4-dione
• CAS: 135824-30-5
• 化学式: C₃₄H₃₀N₂O₅Se
• 分子量: 625.583
• InChiKey: NSYUNDINOPULTI-IMRLWEKHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  42.0
• 可旋转键数：
  9.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  93.55
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1-<3-deoxy-3-(phenylseleno)-5-O-trityl-β-D-arabinofuranosyl>uracil 在 吡啶 、 溶剂黄146 作用下， 反应 0.17h， 生成 1-[(2R,3R,4S,5R)-5-(tert-Butyl-dimethyl-silanyloxymethyl)-3-hydroxy-4-phenylselanyl-tetrahydro-furan-2-yl]-1H-pyrimidine-2,4-dione
  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
• 作为产物：
  描述：

  二苯基二硒醚 、 5’-O-三苯甲基尿苷-2’,3’-来苏-环氧化物 在 sodium tetrahydroborate 作用下， 生成 1-((2R,3R,4S,5R)-4-Hydroxy-3-phenylselanyl-5-trityloxymethyl-tetrahydro-furan-2-yl)-1H-pyrimidine-2,4-dione 、 1-<3-deoxy-3-(phenylseleno)-5-O-trityl-β-D-arabinofuranosyl>uracil
  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.