methyl (S)-N-(1-aza-6-oxaspiro[2.5]oct-1-en-2-yl)prolinate | 323207-12-1

• 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: methyl (S)-N-(1-aza-6-oxaspiro[2.5]oct-1-en-2-yl)prolinate
• 英文别名: methyl N-(1-aza-6-oxaspiro[2.5]oct-1-en-2-yl)-L-prolinate；azirine；methyl (2S)-1-(6-oxa-1-azaspiro[2.5]oct-1-en-2-yl)pyrrolidine-2-carboxylate
• CAS: 323207-12-1
• 化学式: C₁₂H₁₈N₂O₃
• 分子量: 238.287
• InChiKey: HHENBIHYSGOORK-VIFPVBQESA-N

物化性质

• 熔点：
  211-212 °C(Solv: ethyl acetate (141-78-6))
• 沸点：
  351.7±52.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  51.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (S)-N-(1-aza-6-oxaspiro[2.5]oct-1-en-2-yl)prolinate 在 palladium on activated charcoal 盐酸 、 lithium hydroxide 、 氢气 、 1-羟基苯并三唑 、 三乙胺 、 Methanaminium,N-[(dimethylamino)(3H-1,2,3-triazolo[4,5-b]pyridin-3-yloxy)methylene]-N-methyl-, hexafluorophosphate(1-) 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 42.0h， 生成 Z-Ser(^tBu)-Val-Thp-Pro-Aib-Leu-Thp-Pro-Leuol
  参考文献：
  名称：

  HeterospirocyclicN-(2H-Azirin-3-yl)-L-prolinates: New Dipeptide Synthons

  摘要：

  The synthesis of methyl N-(1-aza-6-oxaspiro[2.5]oct-1-en-2-yl)-L-prolinate (1e) has been performed by consecutive treatment of methyl N-[(tetrahydro-2H-pyran-4-yl)thiocarbonyl]-L-prolinate (5) with COCl2, 1,4-diazabicyclo[2.2.2]octane (DABCO), and NaN3 (Scheme 1). As the first example of a novel class of dipeptide synthons, le has been shown to undergo the expected reactions with carboxylic acids and thioacids (Scheme 2). The successful preparation of the nonapeptide 16, which is an analogue of the C-terminal nonapeptide of the antibiotic Trichovirin 1 1B, proved that 1e can be used in peptide synthesis as a dipeptide building block (Scheme 3). The structure of 7 has been established by X-ray crystal-structure analysis (Figs. 1 and 2).

  DOI：

  10.1002/1522-2675(20001108)83:11<2961::aid-hlca2961>3.0.co;2-s
• 作为产物：
  描述：

  methyl (S)-N-[(tetrahydro-2H-pyran-4-yl)thiocarbonyl]prolinate 在 三乙烯二胺 、 sodium azide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 四氢呋喃 为溶剂， 反应 0.92h， 以74%的产率得到methyl (S)-N-(1-aza-6-oxaspiro[2.5]oct-1-en-2-yl)prolinate
  参考文献：
  名称：

  HeterospirocyclicN-(2H-Azirin-3-yl)-L-prolinates: New Dipeptide Synthons

  摘要：

  The synthesis of methyl N-(1-aza-6-oxaspiro[2.5]oct-1-en-2-yl)-L-prolinate (1e) has been performed by consecutive treatment of methyl N-[(tetrahydro-2H-pyran-4-yl)thiocarbonyl]-L-prolinate (5) with COCl2, 1,4-diazabicyclo[2.2.2]octane (DABCO), and NaN3 (Scheme 1). As the first example of a novel class of dipeptide synthons, le has been shown to undergo the expected reactions with carboxylic acids and thioacids (Scheme 2). The successful preparation of the nonapeptide 16, which is an analogue of the C-terminal nonapeptide of the antibiotic Trichovirin 1 1B, proved that 1e can be used in peptide synthesis as a dipeptide building block (Scheme 3). The structure of 7 has been established by X-ray crystal-structure analysis (Figs. 1 and 2).

  DOI：

  10.1002/1522-2675(20001108)83:11<2961::aid-hlca2961>3.0.co;2-s

文献信息

• Highly Constrained Linear Oligopeptides Containing Heterocyclic<i>α</i>-Amino Carboxylic Acids
  作者：Svetlana A. Stoykova、Anthony Linden、Heinz Heimgartner

  DOI：10.1002/hlca.201300062

  日期：2013.9

  derivative, Tht‐Pro, respectively. By coupling of 4‐bromobenzoic acid with 1f or 1g and saponification, followed by repeating the coupling and saponification steps, oligopeptides of type 4‐BrBz‐(Thp‐Pro)n‐OMe and 4‐BrBz‐(Tht‐Pro)n‐OMe were prepared, and their conformations were evaluated in solution by NMR techniques and in the crystalline state by X‐ray crystallography. All of these sterically highly

  两种螺杂环2 H-叠氮基3-胺1f和1g被证明是二肽N-（4-氨基四氢-2 H-吡喃-4-基）脯氨酸（Thp-Pro）和相应的噻喃的有用合成子派生工具Tht-Pro。通过将4-溴苯甲酸与1f或1g偶联并进行皂化，然后重复偶联和皂化步骤，可制得4-BrBz-（Thp-Pro）n -OMe和4-BrBz-（Tht-Pro）n型寡肽制备了OMe，并通过NMR技术在溶液中评估了其构象，并通过X射线晶体学对其结晶态进行了评估。所有这些在空间上高度拥塞的寡肽都具有相当刚性的螺旋构象。有趣的是，具有Thp的六肽形成3 10螺旋，而Tht类似物具有β弯曲带状螺旋确认。
• Synthesis of Perhydropyrrolo[1,2-a]pyrazine-1,4-diones and Their Sulfur-Analogues by Ring-Enlargement of N-(2H-Azirin-3-yl)-L-prolinates
  作者：Heinz Heimgartner、Artur Budzowski、Anthony Linden

  DOI：10.3987/com-04-s(p)43

  日期：——