Ac(BocApi)8OH | 1246024-73-6

• 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: Ac(BocApi)8OH
• CAS: 1246024-73-6
• 化学式: C₉₀H₁₄₈N₁₆O₂₆
• 分子量: 1870.26
• InChiKey: WJIIPMXNZJOCDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.18
• 重原子数：
  132.0
• 可旋转键数：
  16.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  506.42
• 氢给体数：
  9.0
• 氢受体数：
  25.0

反应信息

• 作为反应物：
  描述：

  Ac(BocApi)8OH 、 盐酸甲胺 在 2,4,6-三甲基吡啶 、 N-羟基-7-氮杂苯并三氮唑 、 Methanaminium,N-[(dimethylamino)(3H-1,2,3-triazolo[4,5-b]pyridin-3-yloxy)methylene]-N-methyl-, hexafluorophosphate(1-) 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以87%的产率得到Ac(BocApi)8NHMe
  参考文献：
  名称：

  Oligo(4-aminopiperidine-4-carboxylic acid): An Unusual Basic Oligopeptide with an Acid-Induced Helical Conformation

  摘要：

  In sharp contrast with helical polypeptides carrying basic side chains, Api(8), a basic oligopeptide containing the non-natural achiral amino acid 4-aminopiperidine-4-carboxylic acid (Api), adopts a helical conformation only in acidic media. Alkaline titration of a protonated Api(8) oligomer appended with a leucine derivative at its N-terminus showed that disruption of its helical conformation occurs in a pH range of 7-10. NMR studies indicated that the piperidine groups in Api(8), when nonprotonated, possibly interact with the proximal amide protons in the peptide backbone and hamper the formation of the H-bonding network responsible for the helical conformation. The helical structure is induced not only by protonation but also by acylation of the piperidine groups.

  DOI：

  10.1021/ja106118w
• 作为产物：
  描述：

  Ac(BocApi)8OBn 在 palladium 10% on activated carbon 、 氢气 作用下， 以 甲醇 为溶剂， 以100%的产率得到Ac(BocApi)8OH
  参考文献：
  名称：

  Oligo(4-aminopiperidine-4-carboxylic acid): An Unusual Basic Oligopeptide with an Acid-Induced Helical Conformation

  摘要：

  In sharp contrast with helical polypeptides carrying basic side chains, Api(8), a basic oligopeptide containing the non-natural achiral amino acid 4-aminopiperidine-4-carboxylic acid (Api), adopts a helical conformation only in acidic media. Alkaline titration of a protonated Api(8) oligomer appended with a leucine derivative at its N-terminus showed that disruption of its helical conformation occurs in a pH range of 7-10. NMR studies indicated that the piperidine groups in Api(8), when nonprotonated, possibly interact with the proximal amide protons in the peptide backbone and hamper the formation of the H-bonding network responsible for the helical conformation. The helical structure is induced not only by protonation but also by acylation of the piperidine groups.

  DOI：

  10.1021/ja106118w

文献信息

• Helical Oligopeptides of a Quaternized Amino Acid with Tunable Chiral-Induction Ability and an Anomalous pH Response
  作者：Joonil Cho、Yasuhiro Ishida、Takuzo Aida

  DOI：10.1002/chem.201605460

  日期：2017.4.6

  8‐mers, and one of the 16‐mers showed helicity at the highest level reported thus far for oligopeptides of a similar length. It was also found that the sensitivity of the helical structure towards the state of the piperidine groups changed drastically depending on the chiral auxiliary position; the N‐terminal chiral peptides were more sensitive than the C‐terminal chiral analogues.

  一系列八聚体（8聚体）和hexadecamer（16聚体）的4-氨基哌啶-4-羧酸（API）与寡肽的升合成了在其N或C末端作为手性助剂的亮氨酸。通过圆二色谱，对肽的构象图谱进行了系统研究，结果表明，肽的α-螺旋形成能力是由包括肽长度，API中哌啶基团状态在内的参数组合决定的单位和手性助剂的位置。当哌啶处于游离碱状态时，这些肽显示出低的形成螺旋结构的倾向。但是，哌啶的质子化和酰化作用增强了螺旋结构的形成，从而使螺旋形成能力的顺序为质子化>酰化>游离碱。就肽长而言，通常16聚物比相应的8聚物具有更高的螺旋形成能力，16聚体之一显示出迄今为止报道的类似长度的寡肽的最高螺旋度。还发现，根据手性辅助位置，螺旋结构对哌啶基团状态的敏感性急剧变化。N末端手性肽比C末端手性类似物更敏感。