1-((2R,3aR,9aR)-5,5,7,7-Tetraisopropyl-3-oxo-2-phenylselanyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl)-1H-pyrimidine-2,4-dione | 288103-32-2

• 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: 1-((2R,3aR,9aR)-5,5,7,7-Tetraisopropyl-3-oxo-2-phenylselanyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl)-1H-pyrimidine-2,4-dione
• 英文别名: 1-[(6aR,8R,9aR)-9-oxo-8-phenylselanyl-2,2,4,4-tetra(propan-2-yl)-6a,9a-dihydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]pyrimidine-2,4-dione
• CAS: 288103-32-2
• 化学式: C₂₇H₄₀N₂O₇SeSi₂
• 分子量: 639.755
• InChiKey: SFKWYYPRFHHIKW-LSCGWGKXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  39
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  103
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-((2R,3aR,9aR)-5,5,7,7-Tetraisopropyl-3-oxo-2-phenylselanyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl)-1H-pyrimidine-2,4-dione 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 1-[(6aR,8S,9aR)-9-oxo-8-phenylselanyl-2,2,4,4-tetra(propan-2-yl)-6a,9a-dihydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]pyrimidine-2,4-dione
  参考文献：
  名称：

  Synthesis of a 1′-α-phenylselenouridine derivative as a synthetic precursor for various 1′-modified nucleosides, via enolization at the 1′-position of 3′,5′-O-TIPDS-2′-ketouridine

  摘要：

  Synthesis of the 1'-alpha-phenylselenouridine derivative 1 alpha, a potentially useful precursor for the synthesis of a variety of 1'-modified nucleosides, was achieved via enolization of the 3',5'-O-TIPDS-2'-ketouridine 2. Successive treatment of 2 with LiHMDS and PhSeCl at less than or equal to 70 degrees C in THF gave the corresponding 1'-phenylseleno product, which was reduced stereoselectively with NaBH4/CeCl3 in MeOH to give the target compound 1 alpha. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00432-9
• 作为产物：
  描述：

  苯基氯化硒 、 3',5'-O-(四异丙基二硅氧烷-1,3-二基)-2'-氧代尿苷 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以5%的产率得到1-((2R,3aR,9aR)-5,5,7,7-Tetraisopropyl-3-oxo-2-phenylselanyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl)-1H-pyrimidine-2,4-dione
  参考文献：
  名称：

  Synthesis of a 1′-α-phenylselenouridine derivative as a synthetic precursor for various 1′-modified nucleosides, via enolization at the 1′-position of 3′,5′-O-TIPDS-2′-ketouridine

  摘要：

  Synthesis of the 1'-alpha-phenylselenouridine derivative 1 alpha, a potentially useful precursor for the synthesis of a variety of 1'-modified nucleosides, was achieved via enolization of the 3',5'-O-TIPDS-2'-ketouridine 2. Successive treatment of 2 with LiHMDS and PhSeCl at less than or equal to 70 degrees C in THF gave the corresponding 1'-phenylseleno product, which was reduced stereoselectively with NaBH4/CeCl3 in MeOH to give the target compound 1 alpha. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00432-9

文献信息

• An Efficient Method for the Preparation of 1′α-Branched-Chain Sugar Pyrimidine Ribonucleosides from Uridine: The First Conversion of a Natural Nucleoside into 1′-Substituted Ribonucleosides
  作者：Tetsuya Kodama、Satoshi Shuto、Makoto Nomura、Akira Matsuda

  DOI：10.1002/1521-3765(20010601)7:11<2332::aid-chem23320>3.0.co;2-w

  日期：2001.6.1

  18 gave the sugar-protected 1'alpha-vinyluridine. With this procedure, 1'alpha-vinyluridine (22) and -cytidine (25), designed to be potential antitumor agents, were successfully synthesized. This study is the first example of functionalization at the anomeric 1'-position of a nucleoside by starting from a natural nucleoside to produce a ribo-type 1'-modified nucleoside.

  通过3',5'-O-TIPDS-2'-酮尿苷8的烯醇化成功合成了1'α-苯基硒尿苷衍生物13，并与乙烯基甲硅烷基系链进行自由基反应——这是制备1的有效方法'α-支链糖嘧啶核苷。在 < -70 摄氏度的 THF 中用 LiHMDS 和 PhSeCl 连续处理 8 得到所需的 1'-苯基硒代产物，产率为 85%，为 1'α-产物 11 和 1'β-产物 12 的异头混合物（11 /12=2.5:1）。通过在 MeOH 中使用 NaBH4/CeCl3，在 1'α-产物 11 的 2'-羰基处发生高度立体选择性还原，随后在 2'-羟基处引入二甲基乙烯基甲硅烷基系链，得到自由基反应底物 14 . 使用高压汞灯的 14 的光化学自由基原子转移反应在苯中有效进行，得到外环化的 PhSe 转移产物 18，其中证明 (PhSe)2 作为自由基原子的添加剂是必不可少的。转移环化反应。随后 18 的苯基硒基消除得到糖保护的
• Synthesis of a 1′-α-phenylselenouridine derivative as a synthetic precursor for various 1′-modified nucleosides, via enolization at the 1′-position of 3′,5′-O-TIPDS-2′-ketouridine
  作者：Tetsuya Kodama、Satoshi Shuto、Makoto Nomura、Akira Matsuda

  DOI：10.1016/s0040-4039(00)00432-9

  日期：2000.5

  Synthesis of the 1'-alpha-phenylselenouridine derivative 1 alpha, a potentially useful precursor for the synthesis of a variety of 1'-modified nucleosides, was achieved via enolization of the 3',5'-O-TIPDS-2'-ketouridine 2. Successive treatment of 2 with LiHMDS and PhSeCl at less than or equal to 70 degrees C in THF gave the corresponding 1'-phenylseleno product, which was reduced stereoselectively with NaBH4/CeCl3 in MeOH to give the target compound 1 alpha. (C) 2000 Elsevier Science Ltd. All rights reserved.