(3,3',4,4'-tetraethyl-5,5'-bis(2-methoxybenzoyl)-2,2'-dipyrryl)methane | 160503-83-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3,3',4,4'-tetraethyl-5,5'-bis(2-methoxybenzoyl)-2,2'-dipyrryl)methane
• CAS: 160503-83-3
• 化学式: C₃₃H₃₈N₂O₄
• 分子量: 526.676
• InChiKey: IVOSZIXGUSXPNT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.66
• 重原子数：
  39.0
• 可旋转键数：
  12.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  84.18
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (3,3',4,4'-tetraethyl-5,5'-bis(2-methoxybenzoyl)-2,2'-dipyrryl)methane 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 28.0h， 以100%的产率得到(3,3',4,4'-tetraethyl-5,5'-bis-(α-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane
  参考文献：
  名称：

  Design and Synthesis of a Trifunctional Chiral Porphyrin with C2 Symmetry as a Chiral Recognition Host for Amino Acid Esters

  摘要：

  An intrinsic chiral recognition host, (R,R)- or (S,S)-[trans-5,15-bis(2-hydroxyphenyl)-10-{2,6-bis((methoxycarbonyl)methyl)phenyl}-2,3,17,18-tetraethylporphyrinato]zinc(II) (1), was synthesized by the coupling between (3,3',4,4'-tetraethyl-5,5'-bis(alpha-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane (8) and dimethyl 2-(bis(2-pyrryl)-methyl)-1, 3-benzenediacetate (16). This pyrrylmethanol method made it possible to perform the regiospecific coupling between differently functionalized dipyrromethane units. Host 1 was designed to have three recognition elements: metal coordination, hydrogen bond donor, and hydrogen bond acceptor (and/or steric repulsion) groups. These groups are arranged in a convergent fashion, forming a chiral recognition pocket. Host 1 was resolved into two enantiomers, (+)-1 and (-)-1. The binding constants in CHCl3 were determined by UV-vis titration. Host (+)-1 was found to show an enantioselectivity of 2.0-2.8 in respect to L- and D-enantiomers of Ile-OMe, Leu-OMe, Leu-OBzl, Val-OMe, Pro-OMe, and Phe-OMe. Host (+)-1 showed an enantioselectivity of 0.47 in respect to L- and D-enantiomers of serine benzyl ester, indicating that the enantioselectivity was reversed. Reference porphyrins 2-4, which lack some of recognition groups, were also synthesized by the pyrrylmethanol method to clarify the roles of the recognition groups of (+)-1 in thermodynamics of the binding processes. Total free energy change upon binding of L- and D-Ile-OMe to host (+)-1 (Delta G degrees(total) for L, -5.05, and D, -4.46 kcal/mol) was separated into three terms: metal coordination energy (Delta G degrees(Zn)), -4.15 kcal/mol; hydrogen bond energy (Delta Delta G degrees(OH)), -1.30 kcal/mol; and steric repulsion energy (Delta Delta G degrees(COOMe)(L) or Delta Delta G degrees(COOMe)(D)), +0.40 kcal/mol for L- and +0.99 kcal/mol for D-Ile-OMe. The third recognition group (CH(2)CO(2)Me) of (+)-1 was found to destabilize the complexes due to steric repulsions. In contrast, the CH(2)CO(2)Me group was found to stabilize the complex between D-Ser-OBzl and (+)-1, suggesting that hydrogen bonding between the OH group of serine and the C=O group of (+)-1 takes place. On the basis of these thermodynamic studies, chiral recognition was found to be achieved by cooperative functions of these three recognition groups.

  DOI：

  10.1021/ja00089a013
• 作为产物：
  描述：

  甲氧基苯甲酰氯 在 盐酸 、 乙基溴化镁 作用下， 以 乙醇 为溶剂， 反应 9.0h， 生成 (3,3',4,4'-tetraethyl-5,5'-bis(2-methoxybenzoyl)-2,2'-dipyrryl)methane
  参考文献：
  名称：

  Design and Synthesis of a Trifunctional Chiral Porphyrin with C2 Symmetry as a Chiral Recognition Host for Amino Acid Esters

  摘要：

  An intrinsic chiral recognition host, (R,R)- or (S,S)-[trans-5,15-bis(2-hydroxyphenyl)-10-{2,6-bis((methoxycarbonyl)methyl)phenyl}-2,3,17,18-tetraethylporphyrinato]zinc(II) (1), was synthesized by the coupling between (3,3',4,4'-tetraethyl-5,5'-bis(alpha-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane (8) and dimethyl 2-(bis(2-pyrryl)-methyl)-1, 3-benzenediacetate (16). This pyrrylmethanol method made it possible to perform the regiospecific coupling between differently functionalized dipyrromethane units. Host 1 was designed to have three recognition elements: metal coordination, hydrogen bond donor, and hydrogen bond acceptor (and/or steric repulsion) groups. These groups are arranged in a convergent fashion, forming a chiral recognition pocket. Host 1 was resolved into two enantiomers, (+)-1 and (-)-1. The binding constants in CHCl3 were determined by UV-vis titration. Host (+)-1 was found to show an enantioselectivity of 2.0-2.8 in respect to L- and D-enantiomers of Ile-OMe, Leu-OMe, Leu-OBzl, Val-OMe, Pro-OMe, and Phe-OMe. Host (+)-1 showed an enantioselectivity of 0.47 in respect to L- and D-enantiomers of serine benzyl ester, indicating that the enantioselectivity was reversed. Reference porphyrins 2-4, which lack some of recognition groups, were also synthesized by the pyrrylmethanol method to clarify the roles of the recognition groups of (+)-1 in thermodynamics of the binding processes. Total free energy change upon binding of L- and D-Ile-OMe to host (+)-1 (Delta G degrees(total) for L, -5.05, and D, -4.46 kcal/mol) was separated into three terms: metal coordination energy (Delta G degrees(Zn)), -4.15 kcal/mol; hydrogen bond energy (Delta Delta G degrees(OH)), -1.30 kcal/mol; and steric repulsion energy (Delta Delta G degrees(COOMe)(L) or Delta Delta G degrees(COOMe)(D)), +0.40 kcal/mol for L- and +0.99 kcal/mol for D-Ile-OMe. The third recognition group (CH(2)CO(2)Me) of (+)-1 was found to destabilize the complexes due to steric repulsions. In contrast, the CH(2)CO(2)Me group was found to stabilize the complex between D-Ser-OBzl and (+)-1, suggesting that hydrogen bonding between the OH group of serine and the C=O group of (+)-1 takes place. On the basis of these thermodynamic studies, chiral recognition was found to be achieved by cooperative functions of these three recognition groups.

  DOI：

  10.1021/ja00089a013

文献信息

• Design and Synthesis of a Trifunctional Chiral Porphyrin with C2 Symmetry as a Chiral Recognition Host for Amino Acid Esters
  作者：Tadashi Mizutani、Tadashi Ema、Takashi Tomita、Yasuhisa Kuroda、Hisanobu Ogoshi

  DOI：10.1021/ja00089a013

  日期：1994.5

  An intrinsic chiral recognition host, (R,R)- or (S,S)-[trans-5,15-bis(2-hydroxyphenyl)-10-2,6-bis((methoxycarbonyl)methyl)phenyl}-2,3,17,18-tetraethylporphyrinato]zinc(II) (1), was synthesized by the coupling between (3,3',4,4'-tetraethyl-5,5'-bis(alpha-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane (8) and dimethyl 2-(bis(2-pyrryl)-methyl)-1, 3-benzenediacetate (16). This pyrrylmethanol method made it possible to perform the regiospecific coupling between differently functionalized dipyrromethane units. Host 1 was designed to have three recognition elements: metal coordination, hydrogen bond donor, and hydrogen bond acceptor (and/or steric repulsion) groups. These groups are arranged in a convergent fashion, forming a chiral recognition pocket. Host 1 was resolved into two enantiomers, (+)-1 and (-)-1. The binding constants in CHCl3 were determined by UV-vis titration. Host (+)-1 was found to show an enantioselectivity of 2.0-2.8 in respect to L- and D-enantiomers of Ile-OMe, Leu-OMe, Leu-OBzl, Val-OMe, Pro-OMe, and Phe-OMe. Host (+)-1 showed an enantioselectivity of 0.47 in respect to L- and D-enantiomers of serine benzyl ester, indicating that the enantioselectivity was reversed. Reference porphyrins 2-4, which lack some of recognition groups, were also synthesized by the pyrrylmethanol method to clarify the roles of the recognition groups of (+)-1 in thermodynamics of the binding processes. Total free energy change upon binding of L- and D-Ile-OMe to host (+)-1 (Delta G degrees(total) for L, -5.05, and D, -4.46 kcal/mol) was separated into three terms: metal coordination energy (Delta G degrees(Zn)), -4.15 kcal/mol; hydrogen bond energy (Delta Delta G degrees(OH)), -1.30 kcal/mol; and steric repulsion energy (Delta Delta G degrees(COOMe)(L) or Delta Delta G degrees(COOMe)(D)), +0.40 kcal/mol for L- and +0.99 kcal/mol for D-Ile-OMe. The third recognition group (CH(2)CO(2)Me) of (+)-1 was found to destabilize the complexes due to steric repulsions. In contrast, the CH(2)CO(2)Me group was found to stabilize the complex between D-Ser-OBzl and (+)-1, suggesting that hydrogen bonding between the OH group of serine and the C=O group of (+)-1 takes place. On the basis of these thermodynamic studies, chiral recognition was found to be achieved by cooperative functions of these three recognition groups.