dimethyl (2S,3S)-2-bromo-3-ethyl-1,4-butanedioate | 146499-99-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: dimethyl (2S,3S)-2-bromo-3-ethyl-1,4-butanedioate
• 英文别名: dimethyl (2S,3R)-2-bromo-3-ethylbutanedioate
• CAS: 146499-99-2
• 化学式: C₈H₁₃BrO₄
• 分子量: 253.093
• InChiKey: AANDAQACUDSAOF-WDSKDSINSA-N

物化性质

• 沸点：
  249.4±20.0 °C(Predicted)
• 密度：
  1.394±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-甲基-1氢-5-醛基-咪唑 、 dimethyl (2S,3S)-2-bromo-3-ethyl-1,4-butanedioate 在 银 、 二甲基氯化铝 、 copper(I) bromide 、 锌 作用下， 以94%的产率得到(3S,4RS,5RS)-3-ethyl-4-(methoxycarbonyl)-5-(1-methyl-1H-imidazol-5-yl)dihydro-2(3H)-furanone
  参考文献：
  名称：

  An effective chirospecific synthesis of (+)-pilocarpine from L-aspartic acid

  摘要：

  A short and efficient synthesis of (+)-pilocarpine (1) has been accomplished in 10 steps and 51 % overall yield from L-aspartic acid. The synthesis features a diastereoselective alkylation of a protected aspartic acid diester derivative and a selective hydrolysis of the alpha-methyl ester to give the corresponding amino acid. Subsequent replacement of the amino group with bromo, esterification, and a modified Reformatsky reaction with 1-methylimidazole-5-carboxaldehyde (8) afforded imidazole-substituted lactone 28. Details concerning this novel lactone synthesis are also described. Finally, hydrogenolysis of the lactone carbon-oxygen bond and selective reduction of the resulting monoester afforded pure (+)-pilocarpine (1).

  DOI：

  10.1021/jo00057a031
• 作为产物：
  描述：

  (2S,3S)-dimethyl 2-N-(9-phenylfluorenyl)-3-ethyl-L-aspartate 在 硫酸 、 氢溴酸 、 potassium bromide 、 sodium nitrite 作用下， 反应 8.0h， 生成 dimethyl (2S,3S)-2-bromo-3-ethyl-1,4-butanedioate
  参考文献：
  名称：

  An effective chirospecific synthesis of (+)-pilocarpine from L-aspartic acid

  摘要：

  A short and efficient synthesis of (+)-pilocarpine (1) has been accomplished in 10 steps and 51 % overall yield from L-aspartic acid. The synthesis features a diastereoselective alkylation of a protected aspartic acid diester derivative and a selective hydrolysis of the alpha-methyl ester to give the corresponding amino acid. Subsequent replacement of the amino group with bromo, esterification, and a modified Reformatsky reaction with 1-methylimidazole-5-carboxaldehyde (8) afforded imidazole-substituted lactone 28. Details concerning this novel lactone synthesis are also described. Finally, hydrogenolysis of the lactone carbon-oxygen bond and selective reduction of the resulting monoester afforded pure (+)-pilocarpine (1).

  DOI：

  10.1021/jo00057a031

文献信息

• An effective chirospecific synthesis of (+)-pilocarpine from L-aspartic acid
  作者：Jeffrey M. Dener、Lin Hua Zhang、Henry Rapoport

  DOI：10.1021/jo00057a031

  日期：1993.2

  A short and efficient synthesis of (+)-pilocarpine (1) has been accomplished in 10 steps and 51 % overall yield from L-aspartic acid. The synthesis features a diastereoselective alkylation of a protected aspartic acid diester derivative and a selective hydrolysis of the alpha-methyl ester to give the corresponding amino acid. Subsequent replacement of the amino group with bromo, esterification, and a modified Reformatsky reaction with 1-methylimidazole-5-carboxaldehyde (8) afforded imidazole-substituted lactone 28. Details concerning this novel lactone synthesis are also described. Finally, hydrogenolysis of the lactone carbon-oxygen bond and selective reduction of the resulting monoester afforded pure (+)-pilocarpine (1).