(S)-3-[(Z)-isobutylidene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione | 114673-62-0

• 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: (S)-3-[(Z)-isobutylidene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione
• 英文别名: 3-isobutylidene-hexahydro-pyrrolo[1,2-a]pyrazine-1,4-dione；(3Z,8aS)-3-(2-methylpropylidene)-6,7,8,8a-tetrahydropyrrolo[1,2-a]pyrazine-1,4-dione
• CAS: 114673-62-0
• 化学式: C₁₁H₁₆N₂O₂
• 分子量: 208.26
• InChiKey: WGYMBICRYIOULT-XZLDQRQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  49.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-3-[(Z)-isobutylidene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 反应 17.0h， 以100%的产率得到环(L-脯氨酰-L-亮氨酰)
  参考文献：
  名称：

  Unexpected Hydrogenation of C?C-Double Bonds withtert-Butyl Iodide

  摘要：

  Heating of 3-isobutylidene-2,5-diketopiperazines 1 or 4, maleinimide or 2,3-dichloro-5,6-dicyano-p-benzoquinone with tert-butyl iodide in toluene gave rise to hydrogenation of the conjugated C-C-double bond affording 3-isobutyldiketopiperazines 2(rac) and 3(rac), succinimide, or 2,3-dichloro-5,6-dicyanohydroquinone, respectively. Furthermore, an interesting N-O-migration of a benzoyl group as well as reductive aromatization to pyrazines 5 and 6, respectively, were observed.

  DOI：

  10.1002/prac.19983400415
• 作为产物：
  描述：

  2-benzoyl-3-isobutylidene-hexahydro-pyrrolo[1,2-a]pyrazine-1,4-dione 在 碘代叔丁烷 作用下， 以 甲苯 为溶剂， 反应 0.08h， 以17.8%的产率得到(S)-3-[(Z)-isobutylidene]hexahydropyrrolo[1,2-a]pyrazine-1,4-dione
  参考文献：
  名称：

  Unexpected Hydrogenation of C?C-Double Bonds withtert-Butyl Iodide

  摘要：

  Heating of 3-isobutylidene-2,5-diketopiperazines 1 or 4, maleinimide or 2,3-dichloro-5,6-dicyano-p-benzoquinone with tert-butyl iodide in toluene gave rise to hydrogenation of the conjugated C-C-double bond affording 3-isobutyldiketopiperazines 2(rac) and 3(rac), succinimide, or 2,3-dichloro-5,6-dicyanohydroquinone, respectively. Furthermore, an interesting N-O-migration of a benzoyl group as well as reductive aromatization to pyrazines 5 and 6, respectively, were observed.

  DOI：

  10.1002/prac.19983400415

文献信息

• Intermolecular and Intramolecular Diels−Alder Cycloadditions of 3-Ylidenepiperazine-2,5-diones and 5-Acyloxy-2(1<i>H</i>)-pyrazinones
  作者：Shangde Jin、Pablo Wessig、Jürgen Liebscher

  DOI：10.1021/jo0100897

  日期：2001.6.1

  Diels-Alder reactions of alkenes and alkynes to the piperazine ring, under acidic conditions or in the presence of acetyl chloride, to afford tricyclic piperazine-2,5-diones 19, 20, 23-25, 27, 44, and 45. Intramolecular cycloadditions occur if 3-ylidenepiperazine-2,5-diones 30 and 32 are used as the starting materials. This procedure is a convenient path to bridged bicyclo[2.2.2]diazaoctane ring systems such

  3-亚烷基哌嗪-2,5-二酮16和39和5-酰氧基-2（1H）-吡嗪酮17可以用作烯烃和炔烃在酸性条件下或在酸性条件下Diels-Alder反应的原料。存在乙酰氯，得到三环哌嗪-2,5-二酮19、20、23-25、27、44和45。如果使用3-亚苯基哌嗪-2,5-二酮30和32作为分子，则发生分子内环加成。起始材料。此程序是连接双环[2.2.2]二氮辛烷环系统（例如31和33）的便捷途径，前者存在于具有生物活性的二次霉菌代谢产物中，例如VM55599（1）或brevianamide A（5）。从各种真菌中分离出来。吲哚化合物31的合成为拟议的以Diels-Alder反应为关键步骤的生化途径提供了证据。
• Unusual CC Bond Migration in 3-Ylidene-2,5-piperazinediones
  作者：Shangde Jin、Pablo Wessig、Jürgen Liebscher

  DOI：10.1002/(sici)1099-0690(200005)2000:10<1993::aid-ejoc1993>3.0.co;2-i

  日期：2000.5

  Treatment of 3-alkylidene or 3-benzylidene-2,5-piperazinediones 6 with catalytic amounts of acid gives rise to the formation of isomers 7 by migration of the CC bond into the alkyl substituent at position 6, or results in mixtures of racemic 7 and E isomers 8. The existence of tautomeric equilibria is discussed.

  用催化量的酸处理 3-亚烷基或 3-亚苄基-2,5-哌嗪二酮 6，通过 CC 键迁移到 6 位的烷基取代基中形成异构体 7，或导致外消旋体 7 的混合物和 E 异构体 8. 讨论了互变异构平衡的存在。
• Stereoselective Epoxidation and Bromoalkoxylation with 3-Ylidenepyrazine-2,5-diones
  作者：Jürgen Liebscher、Annett Bartels、Peter G. Jones

  DOI：10.1055/s-2003-36259

  日期：——

  were stereoselectively epoxidsed by dimethyldioxirane giving access to spirooxiranes 2 and diols 3. Bromohydroxylation and bromoalkoxylation of 3-ylidenepyrazine-2,5-diones 1 produced high yields of optically active 3-(1-bromoalkyl)pyrazine-2,5-diones 4 with a 3-hydroxy or 3-alkoxy function, respectively. Whereas direct hydrogenation of epoxides 2 afforded epimeric mixtures of 3-( 1-hydroxyalkyl)pyrazine-2

  3-Ylidenepyrazine-2,5-diones 1 被二甲基二环氧乙烷立体选择性环氧化，得到螺环氧乙烷 2 和二醇 3。 3-ylidenepyrazine-2,5-diones 1 的溴羟基化和溴烷氧基化产生高产率的光学活性 3-(1-bromoalkyl) )pyrazine-2,5-diones 4 分别具有 3-羟基或 3-烷氧基官能团。虽然环氧化物 2 的直接氢化提供了 3-(1-羟基烷基)吡嗪-2,5-二酮 5 和 6 的差向异构体混合物，但通过环氧乙烷环的伯酸裂解随后氢化所得的氢化可高度立体选择性地转化为 5酮-烯醇混合物 7/8。
• Asymmetric syntheses of 1-amino-2-phenyl(alkyl)cyclopropanecarboxylic acids by diastereoselective cyclopropanation of highly functionalized monochiral olefines
  作者：Carmen Alcaraz、Ma Dolores Fernández、Ma Pilar de Frutos、Joseé L. Marco、Manuel Bernabé、Concepción Foces-Foces、Félix H. Cano

  DOI：10.1016/s0040-4020(01)89550-8

  日期：1994.1

  Monochiral alpha-benzamidocinnamic esters of N-methylephedrine or mandelic derivatives and benzylidene or alkylidene diketopiperazines, all obtained from oxazolones, react with diazomethane to give moderate to high diastereomeric excess (d.e) of pyrazoline derivatives which after photolysis and acid hydrolysis of the resulting cyclopropyl compounds, gave (1R,2R)-, (1S,2S)- or (1S,2R)-1-amino-2-phenyl(alkyl)cyclopropanecarboxylic acids. The enantiomerically pure dipeptide of the (1R,2R) enantiomer with S-proline was also obtained by selective cleavage of the diketopiperazine moiety. The structure of all compounds has been assessed by NMR studies and by X-ray crystallography analysis of an intermediate spiroderivative.
• What is the structure of barettin? Novel synthesis of unsaturated diketopiperazines.
  作者：Albrecht Lieberknecht、Helmut Griesser

  DOI：10.1016/s0040-4039(00)96483-9

  日期：1987.1