Bromo-acetic acid (2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-3-oxo-tetrahydro-furan-2-ylmethyl ester | 186839-94-1

• 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: Bromo-acetic acid (2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-3-oxo-tetrahydro-furan-2-ylmethyl ester
• 英文别名: [(2R,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-(2,4-dioxopyrimidin-1-yl)-3-oxooxolan-2-yl]methyl 2-bromoacetate
• CAS: 186839-94-1
• 化学式: C₁₇H₂₅BrN₂O₇Si
• 分子量: 477.384
• InChiKey: VTPPQUQINKYJBG-VCTAVGKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.33
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  111
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Bromo-acetic acid (2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-3-oxo-tetrahydro-furan-2-ylmethyl ester 在 咪唑 、 samarium diiodide 、 氨 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 2-[(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(2,4-dioxopyrimidin-1-yl)-3-hydroxyoxolan-3-yl]acetamide
  参考文献：
  名称：

  Synthesis of 3′-β-carbamoylmethylcytidine (CAMC) and its derivatives as potential antitumor agents

  摘要：

  以 SmI2 促进的分子内 Reformatsky 型反应为关键步骤，合成了 3â²-β-Carbamoylmethylcytidine (CAMC) 及其衍生物。对体外肿瘤细胞生长抑制活性进行了评估，发现 CAMC 对多种人类肿瘤细胞株具有很强的细胞毒性。根据结构与活性关系研究推测，CAMC 的细胞毒性作用机制不需要 5²-羟基上的磷酸化。这项研究为开发新型抗肿瘤核苷提供了一种新策略。

  DOI：

  10.1039/b517602f
• 作为产物：
  描述：

  溴乙酰氯 、 1-[2-O-(tert-butyldimethylsilyl)-β-D-erythro-pentofuran-3-ulosyl]uracil 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到Bromo-acetic acid (2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-3-oxo-tetrahydro-furan-2-ylmethyl ester
  参考文献：
  名称：

  Nucleosides and Nucleotides. 163. Synthesis of 3‘-β-Branched Uridine Derivatives via Intramolecular Reformatsky-Type Reaction Promoted by Samarium Diiodide¹

  摘要：

  A novel efficient method for the synthesis of 3'-beta-branched uridines starting from uridine was developed, in which a SmI2-promoted intramolecular Reformatsky-type reaction was effectively used. 5'-O-(Bromoacetyl)-3'-ketouridine derivatives 12, 26, and 27 were synthesized from uridine and were subjected to an intramolecular Reformatsky-type reaction. When 12, 26, and 27 were treated with 2.0 equiv of SmI2 in THF at -78 degrees C, intramolecular carbon-carbon bond formation at the 3'-beta-position proceeded smoothly to give the corresponding 3',5'-lactones 14, 28, and 29 in high yields, respectively. Treatment of 28 with NH3/MeOH gave the 3'-beta-branched uridine derivative 32 quantitatively, which was then deprotected to give 3'-C-(carbamoylmethyl)uridine (33).

  DOI：

  10.1021/jo961665f