(3'S,4S,5''S,5'''S,9'S,11'S)-4''-[(2,4-dimethoxyphenyl)methyl]-2,2',3'',5,6'',8'-hexaoxo-1-phenyl-1''-{[2-({[(prop-2-en-1-yloxy)carbonyl]oxy}methyl)phenyl]methyl}-3-(pyridin-4-ylmethyl)trispiro[imidazoline-4,5'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-11',2''-piperazine-5'',3'''-pyrrolidine]-5'''-carboxylic acid | 1407162-83-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (3'S,4S,5''S,5'''S,9'S,11'S)-4''-[(2,4-dimethoxyphenyl)methyl]-2,2',3'',5,6'',8'-hexaoxo-1-phenyl-1''-{[2-({[(prop-2-en-1-yloxy)carbonyl]oxy}methyl)phenyl]methyl}-3-(pyridin-4-ylmethyl)trispiro[imidazoline-4,5'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-11',2''-piperazine-5'',3'''-pyrrolidine]-5'''-carboxylic acid
• CAS: 1407162-83-7
• 化学式: C₅₂H₅₂N₈O₁₃
• 分子量: 997.031
• InChiKey: CBFMEWOWLXGRMI-ULUKZOHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.86
• 重原子数：
  73.0
• 可旋转键数：
  14.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  238.07
• 氢给体数：
  2.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  (3'S,4S,5''S,5'''S,9'S,11'S)-4''-[(2,4-dimethoxyphenyl)methyl]-2,2',3'',5,6'',8'-hexaoxo-1-phenyl-1''-{[2-({[(prop-2-en-1-yloxy)carbonyl]oxy}methyl)phenyl]methyl}-3-(pyridin-4-ylmethyl)trispiro[imidazoline-4,5'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-11',2''-piperazine-5'',3'''-pyrrolidine]-5'''-carboxylic acid 、 3-(3-(3,5-bis(trifluoromethyl)phenyl)ureido)benzoic acid 在 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 N,N-二甲基甲酰胺 为溶剂， 反应 8.08h， 生成 C₆₈H₆₀F₆N₁₀O₁₅
  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：

  在 三异丙基硅烷 、 三氟乙酸 作用下， 反应 1.5h， 以290 mg的产率得到(3'S,4S,5''S,5'''S,9'S,11'S)-4''-[(2,4-dimethoxyphenyl)methyl]-2,2',3'',5,6'',8'-hexaoxo-1-phenyl-1''-{[2-({[(prop-2-en-1-yloxy)carbonyl]oxy}methyl)phenyl]methyl}-3-(pyridin-4-ylmethyl)trispiro[imidazoline-4,5'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-11',2''-piperazine-5'',3'''-pyrrolidine]-5'''-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