3-{(S)-2-[3-((S)-2-tert-Butoxycarbonylamino-4-isopropoxycarbonyl-butyrylamino)-benzoylamino]-4-isopropoxycarbonyl-butyrylamino}-benzoic acid benzyl ester | 233692-15-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-{(S)-2-[3-((S)-2-tert-Butoxycarbonylamino-4-isopropoxycarbonyl-butyrylamino)-benzoylamino]-4-isopropoxycarbonyl-butyrylamino}-benzoic acid benzyl ester
• CAS: 233692-15-4
• 化学式: C₄₂H₅₂N₄O₁₁
• 分子量: 788.895
• InChiKey: VRMCLTCTTXIHRP-HEVIKAOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.08
• 重原子数：
  57.0
• 可旋转键数：
  18.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  204.53
• 氢给体数：
  4.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  3-{(S)-2-[3-((S)-2-tert-Butoxycarbonylamino-4-isopropoxycarbonyl-butyrylamino)-benzoylamino]-4-isopropoxycarbonyl-butyrylamino}-benzoic acid benzyl ester 在 palladium on activated charcoal 氢气 、 O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 5.5h， 生成 3-[(S)-2-(3-{(S)-2-[3-((S)-2-Amino-4-isopropoxycarbonyl-butyrylamino)-benzoylamino]-4-isopropoxycarbonyl-butyrylamino}-benzoylamino)-4-isopropoxycarbonyl-butyrylamino]-benzoic acid
  参考文献：
  名称：

  Large Increase in Cation Binding Affinity of Artificial Cyclopeptide Receptors by an Allosteric Effect

  摘要：

  The receptor properties of a cyclopeptide composed of L-glutamic acid and 3-aminobenzoic acid in an alternating sequence are described. H-1 NMR, NOESY Nh LR. and FT-IR spectroscopic investigations show that this cyclic peptide is relatively flexible in solution. Still, it is able to bind cations by cation-pi interactions. For the n-butyltrimethylammonium iodide complex, for example, an association constant of 300 M-1 has been determined in chloroform Besides cations, the cyclopeptide is also able to bind certain anions, such as sulfonates or phosphonates, at a second binding site. Nh IR and FT-IR spectroscopic investigations show that these anions are hydrogen bonded to the peptidic NH groups. Anion complexation results in an increase of the cyclic peptide's cation affinity by a factor of 10(3)-10(4). The cyclopeptide-tosylate complex structure in solution was assigned by FT-IR, H-1 NMR, and NOESY NMR spectroscopic methods as well as molecular modeling, This structure shows that the drastic increase in cation binding affinity can be correlated with a preorganization of the cyclic peptide by the anion as well as electrostatic interactions between anion and cationic substrates in the final complex. Therefore, the influence of the anions on the complexing behavior of the cyclopeptide can be regarded as an allosteric effect. Association constants of the K+-18-crown-6, Na+-15-crown-5, and n-butyltrimethylammonium cation complexes have been determined by dilution and competitive NMR titrations.

  DOI：

  10.1021/ja983970j
• 作为产物：
  描述：

  BOC-(L)-Glu(OiPr)-OH 在 N,N-二异丙基乙胺 、 chlorotri(pyrrolidin-1-yl)phosphonium hexafluorophosphate 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 3-{(S)-2-[3-((S)-2-tert-Butoxycarbonylamino-4-isopropoxycarbonyl-butyrylamino)-benzoylamino]-4-isopropoxycarbonyl-butyrylamino}-benzoic acid benzyl ester
  参考文献：
  名称：

  Large Increase in Cation Binding Affinity of Artificial Cyclopeptide Receptors by an Allosteric Effect

  摘要：

  The receptor properties of a cyclopeptide composed of L-glutamic acid and 3-aminobenzoic acid in an alternating sequence are described. H-1 NMR, NOESY Nh LR. and FT-IR spectroscopic investigations show that this cyclic peptide is relatively flexible in solution. Still, it is able to bind cations by cation-pi interactions. For the n-butyltrimethylammonium iodide complex, for example, an association constant of 300 M-1 has been determined in chloroform Besides cations, the cyclopeptide is also able to bind certain anions, such as sulfonates or phosphonates, at a second binding site. Nh IR and FT-IR spectroscopic investigations show that these anions are hydrogen bonded to the peptidic NH groups. Anion complexation results in an increase of the cyclic peptide's cation affinity by a factor of 10(3)-10(4). The cyclopeptide-tosylate complex structure in solution was assigned by FT-IR, H-1 NMR, and NOESY NMR spectroscopic methods as well as molecular modeling, This structure shows that the drastic increase in cation binding affinity can be correlated with a preorganization of the cyclic peptide by the anion as well as electrostatic interactions between anion and cationic substrates in the final complex. Therefore, the influence of the anions on the complexing behavior of the cyclopeptide can be regarded as an allosteric effect. Association constants of the K+-18-crown-6, Na+-15-crown-5, and n-butyltrimethylammonium cation complexes have been determined by dilution and competitive NMR titrations.

  DOI：

  10.1021/ja983970j

文献信息

• A New Cyclic Pseudopeptide Composed of (<scp>l</scp>)-Proline and 3-Aminobenzoic Acid Subunits as a Ditopic Receptor for the Simultaneous Complexation of Cations and Anions
  作者：Stefan Kubik、Richard Goddard

  DOI：10.1021/jo991087d

  日期：1999.12.1

  The synthesis and receptor properties of a cyclic pseudopeptide composed of (L)-proline and the nonnatural amino acid 3-aminobenzoic acid in an alternating sequence are described. The structure of cyclo[(L)Pro-AB](3) was determined in the solid state by X-ray crystallography and in solution by one- and two-dimensional NMR techniques and FT-IR spectroscopy. The cyclic peptide preferentially adopts conformations comparable with the cone conformation of calixarenes. Similar to calixarenes, cyclo[(L)Pro-AB](3) is able to bind cations by cation-pi interactions with its aromatic subunits. In some complexes, the peptide NH groups interact additionally with anions and the cyclic peptide thus behaves as a ditopic receptor. The structure of the ternary complex between cyclo[(L)Pro-AB](3) and N-methylquinuclidinium iodide was determined by X-ray crystallography. Spectroscopic investigations show that this complex has a similar geometry in solution. Stability constants of complexes of the cyclopeptide with various ion pairs have been determined. Crossover experiments show that electrostatic interactions between cation and anion complexed by cyclo[(L)Pro-AB](3) result in cooperative effects of either ion on the complexation of the corresponding counterion. The binding properties of cyclo[(L)Pro-AB](3) are correlated with its conformation in solution. The properties of related cyclic hexapeptides in which one or two (L)-proline subunits are replaced by (L)-glutamic acid are also described. In comparison with cyclo[(L)Pro-AB](3), these peptides possess a reduced cation and anion affinity. Anion complexation is weakened because the amide NH groups at the glutamic acid subunits are involved in strong intramolecular hydrogen bonds and are not available for interactions with other partners. Consequently, the cation complex stabilities also decrease. The amino acid subunits obviously influence the receptor properties of such cyclopeptides by controlling their solution conformation.