(3'S,4S,9'S,11'S)-3-benzyl-3''-{[2-(hydroxymethyl)phenyl]methyl}-1''-(naphthalen-1-yl)-1-phenyldispiro[imidazolidine-4,5'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-11',4''-imidazolidine]-2,2'2'',5,5'',8'-hexone | 1407162-73-5

• 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: (3'S,4S,9'S,11'S)-3-benzyl-3''-{[2-(hydroxymethyl)phenyl]methyl}-1''-(naphthalen-1-yl)-1-phenyldispiro[imidazolidine-4,5'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-11',4''-imidazolidine]-2,2'2'',5,5'',8'-hexone
• CAS: 1407162-73-5
• 化学式: C₄₅H₃₈N₆O₇
• 分子量: 774.833
• InChiKey: KKWLGIFKOSFYBL-ZRXPYKPHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.66
• 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：
  0.24
• 拓扑面积：
  142.09
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  三氟乙酸乙烯酯 、 (3'S,4S,9'S,11'S)-3-benzyl-3''-{[2-(hydroxymethyl)phenyl]methyl}-1''-(naphthalen-1-yl)-1-phenyldispiro[imidazolidine-4,5'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-11',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：

  7-O-benzyl 8-O-tert-butyl (8S)-2,4-dioxo-1,3,7-triazaspiro[4.4]nonane-7,8-dicarboxylate 在 4-二甲氨基吡啶 、 四(三苯基膦)钯 、 三异丙基硅烷 、 二碳酸二叔丁酯 、 palladium on activated charcoal 、 氢气 、 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-) 、 三氟乙酸 、 borane dimethylamine complex 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 71.0h， 生成 (3'S,4S,9'S,11'S)-3-benzyl-3''-{[2-(hydroxymethyl)phenyl]methyl}-1''-(naphthalen-1-yl)-1-phenyldispiro[imidazolidine-4,5'-[1,7]diazatricyclo[7.3.0.0^3,7]dodecane-11',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