4-((tert-butoxycarbonyl)amino)-1,2-dithiolane-4-carboxylic acid | 406199-53-9

• 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: 4-((tert-butoxycarbonyl)amino)-1,2-dithiolane-4-carboxylic acid
• 英文别名: N-Boc-Adt-OH；4-[(2-Methylpropan-2-yl)oxycarbonylamino]dithiolane-4-carboxylic acid
• CAS: 406199-53-9
• 化学式: C₉H₁₅NO₄S₂
• 分子量: 265.354
• InChiKey: SCWJNCOWEIBSAG-UHFFFAOYSA-N

物化性质

• 沸点：
  444.9±45.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  126
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-((tert-butoxycarbonyl)amino)-1,2-dithiolane-4-carboxylic acid 在 氨 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.0h， 生成 tert-butyl (4-carbamoyl-1,2-dithiolan-4-yl)carbamate
  参考文献：
  名称：

  Total synthesis of kottamide E

  摘要：

  报告首次合成了一种海洋天然产物 Kottamide E，它含有一个通过 (Z) 烯酰胺与不寻常的含 1,2 二硫环戊烷的氨基酸连接的 5,6 二溴吲哚。

  DOI：

  10.1039/c3cc39062d
• 作为产物：
  描述：

  N-tert-butyloxycarbonyl-2,2-bis(benzylthiomethyl)glycine methyl ester 在 sodium hydroxide 、 氨 、 sodium 作用下， 以 甲醇 为溶剂， 反应 6.17h， 生成 4-((tert-butoxycarbonyl)amino)-1,2-dithiolane-4-carboxylic acid
  参考文献：
  名称：

  Exploring the interest of 1,2-Dithiolane ring system in peptide chemistry. Synthesis of a chemotactic tripeptide and x-ray crystal structure of a 4-amino-1,2-dithiolane-4-carboxylic acid derivative

  摘要：

  Due to their relevant biological functions and specific chemical reactivity 1,2-dithiolanes (five-membered cyclic disulfides) represent an emerging class of heterocyclic compounds. However, despite the extensive research centered on lipoic acid and its analogues, only very few data are at the present available on peptides containing this ring system. We report here synthesis, conformation and bioactivity of a fMLF-OMe analogue, namely For-Met-Adt-Phe-OMe (7), in which the residue of the 4-amino-1,2-dithiolane-4-carboxylic acid (Adt) (4) replaces the central L-leucine. The crystal conformation of the synthetic intermediate Boc-Adt-OMe (5) is also described and compared to that of lipoic acid (R-1,2-dithiolane-3-pentanoic acid) (3) and asparagusic acid (1,2-dithiolane-4-carboxylic acid) (2). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(01)00256-5

文献信息

• Peptide backbone folding induced by the C^α-tetrasubstituted cyclic α-amino acids 4-amino-1,2-dithiolane-4-carboxylic acid (Adt) and 1-aminocyclopentane-1-carboxylic acid (Ac₅c). A joint computational and experimental study
  作者：Massimiliano Aschi、Gino Lucente、Fernando Mazza、Adriano Mollica、Enrico Morera、Marianna Nalli、Mario Paglialunga Paradisi

  DOI：10.1039/b212247b

  日期：——

  The conformational study of a new group of synthetic peptides containing 4-amino-1,2-dithiolane-4-carboxylic acid (Adt), a cysteine-related achiral residue, has been carried out through a joint application of computational and experimental methodologies. Molecular Dynamics simulations clearly suggest the tendency of this molecule to adopt a γ-turn conformation in vacuum and help in analyzing the complex and crucial conformational behaviour of the dithiolane ring which appears to preferentially adopt a Cs-like structure. Electronic structure calculations carried out in solution using the Density Functional Theory also indicate the preservation of the γ-like folding in apolar solvents and the helix-like one in more polar solvents. A comparison with the achiral 1-aminocycloalkane-1-carboxylic acid (Ac5c) has been carried out using the same computational tools. NMR and IR data on dipeptide derivatives containing the Adt or Ac5c residue show that in chloroform solution all the models prefer a γ-turn structure, centered at the cyclic residue, stabilized by an intramolecular H-bond, whereas in a more polar solvent, i.e. dimethyl sulfoxide, this folding is not maintained. The experimental conformational studies, extended to N-Boc protected tripeptides, clearly indicate the remarkable tendency of both the five-membered Cα-tetrasubstituted cyclic amino acids Adt and Ac5c to induce the γ-turn structure also in models able to adopt the β-bend conformation.

  对含有4-氨基-1,2-二硫杂环戊烷-4-羧酸（Adt）这一与半胱氨酸相关的无喹啉残基的新型合成肽群体的构象研究，通过计算方法与实验方法的联合应用得以进行。分子动力学模拟清楚地表明该分子在真空中倾向于采用γ-转构象，并有助于分析二硫杂环的复杂而关键的构象行为，该环似乎更倾向于采用Cs类似的结构。使用密度泛函理论在溶液中进行的电子结构计算同样表明，在非极性溶剂中形成的γ-like折叠保持，而在更极性的溶剂中则表现出螺旋状结构。使用相同的计算工具与无喹啉的1-氨基环烷基-1-羧酸（Ac5c）进行了比较。含有Adt或Ac5c残基的二肽衍生物在氯仿溶液中的NMR和IR数据表明，所有模型都更倾向于在环状残基中心形成由分子内氢键稳定的γ-转构象，而在更极性的溶剂（如二甲基亚砜）中这一折叠并未维持。扩展到N-Boc保护的三肽的实验构象研究清楚地显示，五元Cα-四取代环氨基酸Adt和Ac5c都显著倾向于在能够采用β-弯曲构象的模型中诱导γ-转构象。