(2S,3S)-2-bromo-3-ethylbutane-1,4-dioic acid 1-tert-butyl 4-methyl diester | 146499-98-1

• 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: (2S,3S)-2-bromo-3-ethylbutane-1,4-dioic acid 1-tert-butyl 4-methyl diester
• 英文别名: 4-O-tert-butyl 1-O-methyl (2R,3S)-3-bromo-2-ethylbutanedioate
• CAS: 146499-98-1
• 化学式: C₁₁H₁₉BrO₄
• 分子量: 295.173
• InChiKey: OJLLTIXDFXQXRQ-YUMQZZPRSA-N

物化性质

• 沸点：
  292.6±20.0 °C(Predicted)
• 密度：
  1.277±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  (2S,3S)-2-bromo-3-ethylbutane-1,4-dioic acid 1-tert-butyl 4-methyl diester 在 palladium on activated charcoal 盐酸 、 sodium tetrahydroborate 、 草酰氯 、 银 、 ammonium formate 、 氯化二乙基铝 、 N,N-二甲基甲酰胺 、 copper(I) bromide 、 锌 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 45.83h， 生成 毛果芸香碱
  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：

  dimethyl (S)-N-(9-phenyl-9H-fluoren-9-yl)aspartate 在 硫酸 、 氢溴酸 、 双(三甲基硅烷基)氨基钾 、 potassium bromide 、 sodium nitrite 作用下， 以 1,4-二氧六环 、 叔丁醇 为溶剂， 反应 20.92h， 生成 (2S,3S)-2-bromo-3-ethylbutane-1,4-dioic acid 1-tert-butyl 4-methyl diester
  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).