(3,3',4,4'-tetraethyl-5,5'-bis-(α-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane | 149911-31-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (3,3',4,4'-tetraethyl-5,5'-bis-(α-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane
• 英文别名: (3,3',4,4'-tetraethyl-5,5'-bis(α-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane
• CAS: 149911-31-9
• 化学式: C₃₃H₄₂N₂O₄
• 分子量: 530.707
• InChiKey: DPVFKNMYNGGWGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 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：
  0.39
• 拓扑面积：
  90.5
• 氢给体数：
  4.0
• 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-(α-hydroxy-2-methoxybenzyl)-2,2'-dipyrryl)methane 在 zinc diacetate 、 三溴化硼 、 丙酸 作用下， 反应 7.0h， 生成 {3-Methoxycarbonylmethyl-2-[(1Z,4Z,9Z,15Z)-12,13,17,18-tetraethyl-10,20-bis-(2-hydroxy-phenyl)-porphyrin-5-yl]-phenyl}-acetic acid methyl ester
  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：

  (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

文献信息

• Recognition of chirality and residual groups of amino acid esters using new trifunctional chiral porphyrins with C 2 symmetry
  作者：Tadashi Mizutani、Tadashi Ema、Takashi Tomita、Yasuhisa Kuroda、Hisanobu Ogoshi

  DOI：10.1039/c39930000520

  日期：——

  An intrinsic chiral recognition host, [trans-5,15-bis(2-hydroxyphenyl)-10-2,6-bis(methoxycarbonylmethyl)phenyl}-2,3,17,18-tetraethylporphyrinato]zinc(II)1, is synthesized and found to show an enantioselectivity of ca. 2 : 1 for L- and D-amino acid esters having non-polar residues, whereas it shows a reversed enantioselectivity of ca. 1 : 2 for L- and D-Ser-OBzl.

  合成了一种本征手性识别宿主--[反式-5,15-双（2-羟基苯基）-10-2,6-双（甲氧羰基甲基）苯基}-2,3,17,18-四乙基卟啉]锌（II）1。对具有非极性残基的 L- 和 D- 氨基酸酯的对映体选择性约为 2:1，而对 L- 和 D-Ser-OBzl 的对映体选择性则相反，约为 1:2。