(8aRS,3Z)-3-[(dimethylamino)methylidene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione | 936628-36-3

• 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: (8aRS,3Z)-3-[(dimethylamino)methylidene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione
• 英文别名: (3Z)-3-[(dimethylamino)methylidene]-hexahydropyrrolo[1,2-a]pyrazine-1,4-dione；(Z)-3-[(dimethylamino)methylene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione；(3Z)-3-(dimethylaminomethylidene)-6,7,8,8a-tetrahydropyrrolo[1,2-a]pyrazine-1,4-dione
• CAS: 936628-36-3
• 化学式: C₁₀H₁₅N₃O₂
• 分子量: 209.248
• InChiKey: ALELXVRJHDLEOD-SREVYHEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (8aRS,3Z)-3-[(dimethylamino)methylidene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione 、 α-prenylindole 以 溶剂黄146 为溶剂， 反应 0.75h， 以30%的产率得到(3Z,8aRS)-3-{[2-(3-methylbut-2-enyl)-1H-indol-3-yl]methylene}hexahydropyrrolo[1,2-a]pyrazine-1,4-dione
  参考文献：
  名称：

  Synthesis of Unsaturated Tryprostatin B Analogues and Determination of Their Enantiomeric Purity with (S)-1-Benzyl-6-methylpiperazine-2,5-dione

  摘要：

  通过一种基于烯胺酮的策略合成了新型外消旋和对映体富集的不饱和胰岛素 B 类似物。该合成方法还采用了新颖的铜（I）催化二肽形成技术。此外，利用我们自己研制的手性溶解剂，通过 1H NMR 光谱测定了对映体富集的类似物的对映体纯度。

  DOI：

  10.1055/s-2008-1072515
• 作为产物：
  描述：

  Bredereck 试剂 、 (8As)-六氢吡咯并[1,2-a]吡嗪-1,4-二酮 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 以43%的产率得到(8aRS,3Z)-3-[(dimethylamino)methylidene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione
  参考文献：
  名称：

  Chiral solvating properties of (S)-1-benzyl-6-methylpiperazine-2,5-dione

  摘要：

  In CDCl3 solution, enantiopure (S)-1-benzyl-6-methylpiperazine-2,5-dione (S)-1a formed diastereomeric C=O...H-N hydrogen-bonded associates with racemic (RS,Z)-1-benzyl-3-[(dimethylamino)methylidene]piperazine-2,5-diones 2a and 2b, (RS)-tert-butyl pyroglutamate (RS)-2c and (RS)-N-benzoylalanine methyl ester (RS)-2d. This resulted in splitting (doubling) of the characteristic signals in the H-1 NMR and C-13 spectra of racemic compounds 2a-d in the presence of 1 equiv of (S)-1a. The formation of hydrogen-bonded dimers in CDCl3 solution was studied by H-1 NMR, C-13 NMR and 2D NMR and confirmed by the intermolecular NOE observed between the hydrogen-bonded amide protons from each of the monomeric units, (S)-1a and 2a-c. On the other hand, a slightly different binding mode was proposed for association of (S)-1a with alaninamide (RS)-2d. Enantiomer compositions of known (weighed) mixtures of both enantiomers of tert-butyl pyroglutamate 2c were re-determined by H-1 NMR in the presence of (S)-1a in CDCl3. The experimental values were in good agreement with the theoretical values, thus indicating the potential applicability of (S)-1a and related diketopiperazines as chiral solvating agents in NMR spectroscopy. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.02.010

文献信息

• Synthesis of (S,Z)-3-[(1H-indol-3-yl)methylidene]hexahydropyrrolo[1,2-a]pyrazin-4(1H)-one: an alternative, enaminone based, route to unsaturated cyclodipeptides
  作者：Jernej Wagger、Uroš Grošelj、Anton Meden、Jurij Svete、Branko Stanovnik

  DOI：10.1016/j.tet.2008.01.045

  日期：2008.3

  A series of racemic and enantiopure (S,Z)-3-[(1H-indol-3-yl)methylidene]hexahydropyrrolo[1,2-a]pyrazin-4(1H)-one (cyclic Pro–ΔTrp) dipeptide analogues were prepared. Racemic analogues 6a–c were prepared by direct coupling of racemic cyclodipeptide enaminone (R,S)-5 with various indole derivatives. On the other hand, enantiopure analogues were prepared through a copper(I) catalyzed vinyl amidation reaction

  一系列外消旋和对映体纯的（S，Z）-3-[（1 H-吲哚-3-基）亚甲基]六氢吡咯并[1,2- a ]吡嗪-4（1 H）-一个（环Pro–ΔTrp）制备了二肽类似物。外消旋类似物6a – c是通过将外消旋环二肽烯胺酮（R，S）-5与各种吲哚衍生物直接偶联制备的。另一方面，通过铜（I）催化的乙烯基酰胺化反应制备了对映纯类似物，其中无环（S）-Pro-ΔTrp二肽类似物20和21形成了。无环二肽被环化为对映体（S）-Pro-ΔTrp二肽类似物24和25。对于偶联反应，分几个步骤制备乙烯基溴。由乙酸乙酯（7）制备烯胺酮8，并与2-甲基吲哚和2-苯基吲哚偶联，得到9和10。3-（吲哚-3-基）丙烯酸酯9和10在位置2上的直接溴化反应生成乙烯基溴化物11和12。乙烯基溴化物11和12中吲哚氮1'上的Boc保护基在进行铜（I）与N- Boc脯氨酰胺18的偶合之前，先引入苯乙二胺。手性中间体和终产物的对映体纯度主要通过HPLC或1
• Synthesis of Unsaturated Tryprostatin B Analogues and Determination of Their Enantiomeric Purity with (<i>S</i>)-1-Benzyl-6-methylpiperazine-2,5-dione
  作者：Branko Stanovnik、Jernej Wagger、Jurij Svete

  DOI：10.1055/s-2008-1072515

  日期：2008.5

  Novel racemic and enantiomerically enriched unsaturated tryprostatin B analogues were synthesised by an enaminone-based strategy. The synthesis also features a novel copper(I)-catalysed dipeptide formation. In addition, the enantiomeric purity of an enantiomerically enriched analogue was determined by 1H NMR spectroscopy by use of our own chiral solvating agent.

  通过一种基于烯胺酮的策略合成了新型外消旋和对映体富集的不饱和胰岛素 B 类似物。该合成方法还采用了新颖的铜（I）催化二肽形成技术。此外，利用我们自己研制的手性溶解剂，通过 1H NMR 光谱测定了对映体富集的类似物的对映体纯度。
• Chiral solvating properties of (S)-1-benzyl-6-methylpiperazine-2,5-dione
  作者：Jernej Wagger、Simona Golič Grdadolnik、Uroš Grošelj、Anton Meden、Branko Stanovnik、Jurij Svete

  DOI：10.1016/j.tetasy.2007.02.010

  日期：2007.3

  In CDCl3 solution, enantiopure (S)-1-benzyl-6-methylpiperazine-2,5-dione (S)-1a formed diastereomeric C=O...H-N hydrogen-bonded associates with racemic (RS,Z)-1-benzyl-3-[(dimethylamino)methylidene]piperazine-2,5-diones 2a and 2b, (RS)-tert-butyl pyroglutamate (RS)-2c and (RS)-N-benzoylalanine methyl ester (RS)-2d. This resulted in splitting (doubling) of the characteristic signals in the H-1 NMR and C-13 spectra of racemic compounds 2a-d in the presence of 1 equiv of (S)-1a. The formation of hydrogen-bonded dimers in CDCl3 solution was studied by H-1 NMR, C-13 NMR and 2D NMR and confirmed by the intermolecular NOE observed between the hydrogen-bonded amide protons from each of the monomeric units, (S)-1a and 2a-c. On the other hand, a slightly different binding mode was proposed for association of (S)-1a with alaninamide (RS)-2d. Enantiomer compositions of known (weighed) mixtures of both enantiomers of tert-butyl pyroglutamate 2c were re-determined by H-1 NMR in the presence of (S)-1a in CDCl3. The experimental values were in good agreement with the theoretical values, thus indicating the potential applicability of (S)-1a and related diketopiperazines as chiral solvating agents in NMR spectroscopy. (c) 2007 Elsevier Ltd. All rights reserved.