(2S,3S)-dimethyl 2-N-(9-phenylfluorenyl)-3-ethyl-L-aspartate | 120230-65-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (2S,3S)-dimethyl 2-N-(9-phenylfluorenyl)-3-ethyl-L-aspartate
• 英文别名: dimethyl 3(S)-ethyl-N-(9-phenylfluoren-9-yl)-L-aspartate；dimethyl (2S,3S)-2-ethyl-3-[(9-phenylfluoren-9-yl)amino]butanedioate
• CAS: 120230-65-1
• 化学式: C₂₇H₂₇NO₄
• 分子量: 429.516
• InChiKey: PPXZPPQLVZQCAY-CYFREDJKSA-N

物化性质

• 沸点：
  569.6±50.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,3S)-dimethyl 2-N-(9-phenylfluorenyl)-3-ethyl-L-aspartate 在 palladium on activated charcoal 盐酸 、 sodium tetrahydroborate 、 草酰氯 、 硫酸 、 氢溴酸 、 银 、 ammonium formate 、 氯化二乙基铝 、 N,N-二甲基甲酰胺 、 potassium bromide 、 copper(I) bromide 、 锌 、 sodium nitrite 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 65.83h， 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 、 三氟甲烷磺酸乙酯 以78%的产率得到
  参考文献：
  名称：

  WOLF, JEAN-PIERRE;RAPOPORT, HENRY, J. ORG. CHEM., 54,(1989) N3, C. 3164-3173

  摘要：

  DOI：

文献信息

• Conformationally constrained peptides. Chirospecific synthesis of 4-alkyl-substituted .gamma.-lactam-bridged dipeptides from L-aspartic acid
  作者：Jean Pierre Wolf、Henry Rapoport

  DOI：10.1021/jo00274a037

  日期：1989.6
• 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).
• WOLF, JEAN-PIERRE;RAPOPORT, HENRY, J. ORG. CHEM., 54,(1989) N3, C. 3164-3173
  作者：WOLF, JEAN-PIERRE、RAPOPORT, HENRY

  DOI：——

  日期：——