(3R,5S)-1-((benzyloxy)carbonyl)-5-(tert-butoxycarbonyl)-3-((pyridin-4-yl)methylamino)pyrrolidine-3-carboxylic acid | 1407162-61-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (3R,5S)-1-((benzyloxy)carbonyl)-5-(tert-butoxycarbonyl)-3-((pyridin-4-yl)methylamino)pyrrolidine-3-carboxylic acid
• CAS: 1407162-61-1
• 化学式: C₂₄H₂₉N₃O₆
• 分子量: 455.511
• InChiKey: ATYOQVWTDDOGME-YADARESESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  33.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  118.06
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (3R,5S)-1-((benzyloxy)carbonyl)-5-(tert-butoxycarbonyl)-3-((pyridin-4-yl)methylamino)pyrrolidine-3-carboxylic acid 在 氢溴酸 、 三乙胺 、 N,N-二异丙基乙胺 、 Methanaminium,N-[(dimethylamino)(3H-1,2,3-triazolo[4,5-b]pyridin-3-yloxy)methylene]-N-methyl-, hexafluorophosphate(1-) 作用下， 以 四氢呋喃 、 二氯甲烷 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 27.0h， 生成
  参考文献：
  名称：

  Spiroligozymes for Transesterifications: Design and Relationship of Structure to Activity

  摘要：

  Transesterification catalysts based. on stereochemically defined, modular, functionalized ladder-molecules (named spiroligozymes) were designed, using the "inside-out" design strategy, and mutated synthetically to improve catalysis. A series of stereochemically and regiochemically diverse bifunctional spiroligozymes were first synthesized to identify the best arrangement of a pyridine as a general base catalyst and an alcohol nucleophile to accelerate attack on vinyl trifluoroacetate as an electrophile. The best bifunctional spiroligozyme reacted with vinyl trifluoroacetate to form an acyl-spiroligozyme conjugate 2.7 X 10(3)-fold faster than the background reaction with a benzyl alcohol. Two trifunctional spiroligozymes were then synthesized that combined a urea with the pyridine and alcohol to act as an oxyanion hole and activate the bound acyl-spiroligozyme intermediate to enable acyl-transfer to methanol. The best trifunctional spiroligozyme carries out multiple turnovers and acts as a transesterification catalyst with k(1)/k(uncat) of 2.2 X 10(3) and k(2)/k(uncat) of 1.3 X 10(2). Quantum mechanical calculations identified the four transition states of the catalytic cycle and provided a detailed view of every stage of the transesterification reaction.

  DOI：

  10.1021/ja3069648
• 作为产物：
  描述：

  4-吡啶甲醛 、 (2S,4R)-4-amino-pyrrolidine-1,2,4-tricarboxylic acid 1-benzyl ester 2-tert-butyl ester 在 sodium cyanoborohydride 作用下， 以 甲醇 为溶剂， 反应 12.5h， 以62%的产率得到(3R,5S)-1-((benzyloxy)carbonyl)-5-(tert-butoxycarbonyl)-3-((pyridin-4-yl)methylamino)pyrrolidine-3-carboxylic acid
  参考文献：
  名称：

  Spiroligozymes for Transesterifications: Design and Relationship of Structure to Activity

  摘要：

  Transesterification catalysts based. on stereochemically defined, modular, functionalized ladder-molecules (named spiroligozymes) were designed, using the "inside-out" design strategy, and mutated synthetically to improve catalysis. A series of stereochemically and regiochemically diverse bifunctional spiroligozymes were first synthesized to identify the best arrangement of a pyridine as a general base catalyst and an alcohol nucleophile to accelerate attack on vinyl trifluoroacetate as an electrophile. The best bifunctional spiroligozyme reacted with vinyl trifluoroacetate to form an acyl-spiroligozyme conjugate 2.7 X 10(3)-fold faster than the background reaction with a benzyl alcohol. Two trifunctional spiroligozymes were then synthesized that combined a urea with the pyridine and alcohol to act as an oxyanion hole and activate the bound acyl-spiroligozyme intermediate to enable acyl-transfer to methanol. The best trifunctional spiroligozyme carries out multiple turnovers and acts as a transesterification catalyst with k(1)/k(uncat) of 2.2 X 10(3) and k(2)/k(uncat) of 1.3 X 10(2). Quantum mechanical calculations identified the four transition states of the catalytic cycle and provided a detailed view of every stage of the transesterification reaction.

  DOI：

  10.1021/ja3069648