(5R,8R)-3-(naphthalen-1-yl)-2,4-dioxo-7-[(prop-2-en-1-yloxy)carbonyl]-1-{[2-({[(prop-2-en-1-yloxy)carbonyl]oxy}methyl)phenyl]methyl}-1,3,7-triazaspiro[4.4]nonane-8-carboxylic acid | 1407162-71-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (5R,8R)-3-(naphthalen-1-yl)-2,4-dioxo-7-[(prop-2-en-1-yloxy)carbonyl]-1-{[2-({[(prop-2-en-1-yloxy)carbonyl]oxy}methyl)phenyl]methyl}-1,3,7-triazaspiro[4.4]nonane-8-carboxylic acid
• CAS: 1407162-71-3
• 化学式: C₃₃H₃₁N₃O₉
• 分子量: 613.624
• InChiKey: VCSIBKXOIFNOCQ-ZORMNXRFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  45.0
• 可旋转键数：
  10.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  142.99
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  (5R,8R)-3-(naphthalen-1-yl)-2,4-dioxo-7-[(prop-2-en-1-yloxy)carbonyl]-1-{[2-({[(prop-2-en-1-yloxy)carbonyl]oxy}methyl)phenyl]methyl}-1,3,7-triazaspiro[4.4]nonane-8-carboxylic acid 在 四(三苯基膦)钯 、 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-) 、 borane dimethylamine complex 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 28.5h， 生成 (3'S,4R,5'R,9'R)-3-{[2-(hydroxymethyl)phenyl]methyl}-1-(naphthalen-1-yl)-1''-phenyl-3''-(pyridin-4-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
• 作为产物：
  描述：

  (5R,8R)-2,4-dioxo-1,3,7-triaza-spiro[4.4]nonane-7,8-dicarboxylic acid 7-benzyl ester 8-tert-butyl ester 在 4-二甲氨基吡啶 、 三异丙基硅烷 、 二碳酸二叔丁酯 、 palladium on activated charcoal 、 氢气 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 42.5h， 生成 (5R,8R)-3-(naphthalen-1-yl)-2,4-dioxo-7-[(prop-2-en-1-yloxy)carbonyl]-1-{[2-({[(prop-2-en-1-yloxy)carbonyl]oxy}methyl)phenyl]methyl}-1,3,7-triazaspiro[4.4]nonane-8-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