(3R-顺式)-(9CI)-六氢-3-甲氧基吡咯并[1,2-a]吡嗪-1,4-二酮 | 134053-86-4

• 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
• 中文名称: (3R-顺式)-(9CI)-六氢-3-甲氧基吡咯并[1,2-a]吡嗪-1,4-二酮
• 英文名称: (3S,6S)-3-methoxy-1,6-trimethylene-2,5-piperazinedione
• 英文别名: (3R,8AS)-3-Methoxyhexahydropyrrolo[1,2-A]pyrazine-1,4-dione；(3R,8aS)-3-methoxy-2,3,6,7,8,8a-hexahydropyrrolo[1,2-a]pyrazine-1,4-dione
• CAS: 134053-86-4
• 化学式: C₈H₁₂N₂O₃
• 分子量: 184.195
• InChiKey: PZKFPDJUJPYIFG-CAHLUQPWSA-N

物化性质

• 沸点：
  447.8±45.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  58.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  甲基1-{[(2-甲基-2-丙基)氧基]羰基}-L-脯氨酰甘氨酸酯 在 甲酸 、 lithium perchlorate 、 sodium chloride 作用下， 反应 5.0h， 生成 (3R-顺式)-(9CI)-六氢-3-甲氧基吡咯并[1,2-a]吡嗪-1,4-二酮
  参考文献：
  名称：

  Anodic oxidation of N-acyl and N-alkoxycarbonyl dipeptide esters as a key step for the formation of chiral heterocyclic synthetic building blocks

  摘要：

  The anodic oxidation of N-protected dipeptide esters using chloride as a redox catalyst can be performed regioselectively at the C-terminal amino acid. With methanol as solvent, glycine as the C-terminal, and L-valine or L-proline as N-terminal amino acid methoxylation at the glycine residue takes place. Deprotection of this product leads to the (3S,6RS)-6-methoxy-2,5-piperazinedione(3) which can be applied as a chiral cationic glycine equivalent. The exchange of the methoxy group by C-nucleophiles takes place with high trans-diastereoselectivity under steric control by the substituent in 3-position. With branched amino acids at the C-terminus of the dipeptide ester the anodic oxidation in acetonitrile/methanol (95:5) as solvent with tetraethylammonium chloride as supporting electrolyte and redox catalyst leads to methyl imidazolidin-4-one-2-carboxylates. The cyclization takes place via the intermediate formation of the N-acylimino ester of the C-terminal amino acid.

  DOI：

  10.1016/s0040-4020(01)87046-0

文献信息

• 3-Triphenylphosphonio-2,5-piperazinediones as new chiral glycine cation equivalents
  作者：Tadeusz Gorewoda、Roman Mazurkiewicz、Wojciech Simka、Grzegorz Mlostoń、Grzegorz Schroeder、Maciej Kubicki、Nikodem Kuźnik

  DOI：10.1016/j.tetasy.2011.05.002

  日期：2011.4

  3-Triphenylphosphonio-2,5-piperazinediones were effectively synthesized from homochiral valine or proline via Boc-Val-Gly-OMe, Boc-Pro-Gly-OMe or Cbz-Pro-Gly-OMe. Retention of configuration of the primary stereogenic center of the valine and proline moieties was observed. Diastereoselective nucleophilic substitution of the triphenylphosphonium group in 2,5-piperazinediones with S-, N-, P- and C-nucleophiles was observed. The configuration of the substitution products was assigned either by their hydrolysis and decarboxylation or based on the analysis of the H-C(3)-N-H coupling constants of 3-substituted-2,5-piperazinediones derived from proline. The trans-stereoselectivity was predominant in reactions of 3-triphenylphosphonio-1,6-trimethylene-2,5-piperazinediones with the nucleophiles investigated. The stereodifferentiating ability of the proline moiety is much stronger than that of the valine unit and allowed nucleophilic alpha-functionalization of the glycine moiety with good to excellent diastereoselectivity. (C) 2011 Elsevier Ltd. All rights reserved.
• Electrogenerated chiral cationic glycine equivalents — Part 1: The 6-methoxy derivative of cyclo(L-Pro-Gly)
  作者：Georgios Kardassis、Peter Brungs、Eberhard Steckhan

  DOI：10.1016/s0040-4020(98)00081-7

  日期：1998.4

  The cyclic N,O-acetal cyclo(L-Pro-Gly(OMe)OMe (8) has proved to be an effective chiral electrophilic glycine equivalent which is applicable in nucleophilic substitution reactions not only under Broenstedt acid catalysis but also under Lewis acid catalysis with excellent diastereoselectivities. This chiral building block can easily be obtained by electrochemical methoxylative decarboxylation of the cyclic dipeptide 6 generated from L-proline and aminomalonic diester. Thus, enantiomerically pure D-allyl glycine has been generated. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Anodic oxidation of N-acyl and N-alkoxycarbonyl dipeptide esters as a key step for the formation of chiral heterocyclic synthetic building blocks
  作者：Apostolos Papadopoulos、Burhansha Lewall、Eberhard Steckhan、Klaus-Dieter Ginzel、Falk Knoch、Martin Nieger

  DOI：10.1016/s0040-4020(01)87046-0

  日期：1991.1

  The anodic oxidation of N-protected dipeptide esters using chloride as a redox catalyst can be performed regioselectively at the C-terminal amino acid. With methanol as solvent, glycine as the C-terminal, and L-valine or L-proline as N-terminal amino acid methoxylation at the glycine residue takes place. Deprotection of this product leads to the (3S,6RS)-6-methoxy-2,5-piperazinedione(3) which can be applied as a chiral cationic glycine equivalent. The exchange of the methoxy group by C-nucleophiles takes place with high trans-diastereoselectivity under steric control by the substituent in 3-position. With branched amino acids at the C-terminus of the dipeptide ester the anodic oxidation in acetonitrile/methanol (95:5) as solvent with tetraethylammonium chloride as supporting electrolyte and redox catalyst leads to methyl imidazolidin-4-one-2-carboxylates. The cyclization takes place via the intermediate formation of the N-acylimino ester of the C-terminal amino acid.