2-bromo-2-bromomethyl-1-fluoro-1-hydroxymethylcyclopropane | 862578-74-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代醇
• 英文名称: 2-bromo-2-bromomethyl-1-fluoro-1-hydroxymethylcyclopropane
• 英文别名: [2-Bromo-2-(bromomethyl)-1-fluorocyclopropyl]methanol
• CAS: 862578-74-3
• 化学式: C₅H₇Br₂FO
• 分子量: 261.916
• InChiKey: PIESOTDFZJSHKP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-bromo-2-bromomethyl-1-fluoro-1-hydroxymethylcyclopropane 、 乙酸酐 在 二甲基十二/十四烷基叔胺 作用下， 反应 5.0h， 以82%的产率得到1-acetoxymethyl-2-bromo-2-bromomethyl-1-fluorocyclopropane
  参考文献：
  名称：

  A new alkylation–elimination method for synthesis of antiviral fluoromethylenecyclopropane analogues of nucleosides

  摘要：

  A new method for the synthesis of fluoromethylenecyclopropane nucleosides by alkylation-elimination procedure is described. Fluorination of methylenecyclopropane carboxylate 6 gave fluoroester 7. Treatment of 7 with phenylselenenyl bromide afforded the desired ethyl (E)-2-bromomethyl-1-fluoro-2-phenylselenenylcyclopropane-1-carboxylate 11 in 85% yield. DIBALH reduction of 11 gave 13, which after acetylation to 14 was reacted with 2-amino-6-chloropurine to give the 9-alkylated product 15 in 87% yield. Se-oxidation of 15 with hydrogen peroxide afforded 16, which underwent smooth elimination in a mixture of THF-DMF at 60 degrees C giving rise to a Z,E mixture of protected nucleosides 17. Deacetylation gave Z-1a and E-1a which were separated on a silica gel column. Both Z-1a and E-la were converted into the respective guanine analogues Z-1b and E-1b. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.05.054
• 作为产物：
  描述：

  2-methylene-cyclopropanecarboxylic acid ethyl ester 在 溴 、 二异丁基氢化铝 、 lithium chloride 作用下， 以 四氢呋喃 、 四氯化碳 、 正己烷 为溶剂， 反应 1.01h， 生成 2-bromo-2-bromomethyl-1-fluoro-1-hydroxymethylcyclopropane
  参考文献：
  名称：

  A new alkylation–elimination method for synthesis of antiviral fluoromethylenecyclopropane analogues of nucleosides

  摘要：

  A new method for the synthesis of fluoromethylenecyclopropane nucleosides by alkylation-elimination procedure is described. Fluorination of methylenecyclopropane carboxylate 6 gave fluoroester 7. Treatment of 7 with phenylselenenyl bromide afforded the desired ethyl (E)-2-bromomethyl-1-fluoro-2-phenylselenenylcyclopropane-1-carboxylate 11 in 85% yield. DIBALH reduction of 11 gave 13, which after acetylation to 14 was reacted with 2-amino-6-chloropurine to give the 9-alkylated product 15 in 87% yield. Se-oxidation of 15 with hydrogen peroxide afforded 16, which underwent smooth elimination in a mixture of THF-DMF at 60 degrees C giving rise to a Z,E mixture of protected nucleosides 17. Deacetylation gave Z-1a and E-1a which were separated on a silica gel column. Both Z-1a and E-la were converted into the respective guanine analogues Z-1b and E-1b. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.05.054

文献信息

• A new alkylation–elimination method for synthesis of antiviral fluoromethylenecyclopropane analogues of nucleosides
  作者：Shaoman Zhou、Jiri Zemlicka

  DOI：10.1016/j.tet.2005.05.054

  日期：2005.7

  A new method for the synthesis of fluoromethylenecyclopropane nucleosides by alkylation-elimination procedure is described. Fluorination of methylenecyclopropane carboxylate 6 gave fluoroester 7. Treatment of 7 with phenylselenenyl bromide afforded the desired ethyl (E)-2-bromomethyl-1-fluoro-2-phenylselenenylcyclopropane-1-carboxylate 11 in 85% yield. DIBALH reduction of 11 gave 13, which after acetylation to 14 was reacted with 2-amino-6-chloropurine to give the 9-alkylated product 15 in 87% yield. Se-oxidation of 15 with hydrogen peroxide afforded 16, which underwent smooth elimination in a mixture of THF-DMF at 60 degrees C giving rise to a Z,E mixture of protected nucleosides 17. Deacetylation gave Z-1a and E-1a which were separated on a silica gel column. Both Z-1a and E-la were converted into the respective guanine analogues Z-1b and E-1b. (c) 2005 Elsevier Ltd. All rights reserved.