(3'S,4R,5'R,9'S)-3-{[2-(hydroxymethyl)phenyl]methyl}-1-(naphthalen-1-yl)-1''-phenyl-3''-(pyridin-3-ylmethyl)dispiro[imidazolidine-4,11'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-5',4''-imidazolidine]-2,2'2'',5,5'',8'-hexone | 1407162-76-8

• 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,4R,5'R,9'S)-3-{[2-(hydroxymethyl)phenyl]methyl}-1-(naphthalen-1-yl)-1''-phenyl-3''-(pyridin-3-ylmethyl)dispiro[imidazolidine-4,11'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-5',4''-imidazolidine]-2,2'2'',5,5'',8'-hexone
• CAS: 1407162-76-8
• 化学式: C₄₄H₃₇N₇O₇
• 分子量: 775.82
• InChiKey: SRNAJPAEVSDWSV-RKLUENFDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.06
• 重原子数：
  58.0
• 可旋转键数：
  7.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  154.98
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  三氟乙酸乙烯酯 、 (3'S,4R,5'R,9'S)-3-{[2-(hydroxymethyl)phenyl]methyl}-1-(naphthalen-1-yl)-1''-phenyl-3''-(pyridin-3-ylmethyl)dispiro[imidazolidine-4,11'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-5',4''-imidazolidine]-2,2'2'',5,5'',8'-hexone 以 氘代氯仿 为溶剂， 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：

  在 四(三苯基膦)钯 、 borane dimethylamine complex 、 N-羟基-7-氮杂苯并三氮唑 、 N,N'-二异丙基碳二亚胺 作用下， 以 N,N-二甲基甲酰胺 、 二氯甲烷 为溶剂， 反应 27.0h， 以58 mg的产率得到(3'S,4R,5'R,9'S)-3-{[2-(hydroxymethyl)phenyl]methyl}-1-(naphthalen-1-yl)-1''-phenyl-3''-(pyridin-3-ylmethyl)dispiro[imidazolidine-4,11'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-5',4''-imidazolidine]-2,2'2'',5,5'',8'-hexone
  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