Bromo-acetic acid (2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(4-ethoxy-2-oxo-2H-pyrimidin-1-yl)-3-oxo-tetrahydro-furan-2-ylmethyl ester | 186839-84-9

• 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-(4-ethoxy-2-oxo-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-(4-ethoxy-2-oxopyrimidin-1-yl)-3-oxooxolan-2-yl]methyl 2-bromoacetate
• CAS: 186839-84-9
• 化学式: C₁₉H₂₉BrN₂O₇Si
• 分子量: 505.438
• InChiKey: IWOZNAZKMIHCPM-CSMYWGQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.44
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  104
• 氢给体数：
  0
• 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-(4-ethoxy-2-oxo-2H-pyrimidin-1-yl)-3-oxo-tetrahydro-furan-2-ylmethyl ester 在 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到1-[(2R,3R,3aR,7aR)-3-[tert-butyl(dimethyl)silyl]oxy-3a-hydroxy-5-oxo-3,4,7,7a-tetrahydro-2H-furo[2,3-c]pyran-2-yl]-4-ethoxypyrimidin-2-one
  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
• 作为产物：
  描述：

  4-ethoxy-1-(β-D-ribofuranosyl)-2(1H)-pyrimidinone 在 2,6-二甲基吡啶 、 重铬酸吡啶 、 zinc dibromide 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 62.16h， 生成 Bromo-acetic acid (2R,4S,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(4-ethoxy-2-oxo-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

文献信息

• Nucleosides and Nucleotides. 163. Synthesis of 3‘-β-Branched Uridine Derivatives via Intramolecular Reformatsky-Type Reaction Promoted by Samarium Diiodide¹
  作者：Satoshi Ichikawa、Satoshi Shuto、Noriaki Minakawa、Akira Matsuda

  DOI：10.1021/jo961665f

  日期：1997.3.1

  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).