(1S,2R,6S,7R)-4-methyl-4-azatricyclo[5.2.2.02,6]undec-8-ene-3,5-dione

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: (1S,2R,6S,7R)-4-methyl-4-azatricyclo[5.2.2.02,6]undec-8-ene-3,5-dione
• 化学式: C₁₁H₁₃NO₂
• 分子量: 191.23
• InChiKey: RLJWNHYAZXPZFE-SPJNRGJMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2R,6S,7R)-4-methyl-4-azatricyclo[5.2.2.02,6]undec-8-ene-3,5-dione 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 以91%的产率得到
  参考文献：
  名称：

  Structural Investigations into the retro-Diels-Alder Reaction. Experimental and Theoretical Studies

  摘要：

  The manifestations of the retro-Diels Alder reaction in the ground-state structures of a range of cyclopentadiene and cyclohexadiene cycloadducts 9-15 have been investigated by a combination of techniques. These include low-temperature X-ray crystallography, density functional calculations (B3LYP/ 6-31G(d,p)) on both the ground states and transition states, and the measurement of C-13-C-13 coupling constants. We have found that the carbon-carbon bonds (labeled bonds a and b), which break in the rDA, are longer in the cycloadducts 9-15 than in their corresponding saturated analogues 9s-15s, which cannot undergo the rDA reaction. The degree of carbon-carbon bond lengthening appears to be related to the reactivity of the cycloadduct, thus the more reactive benzoquinone cycloadducts 5b and 13 have longer carbon-carbon bonds, Those cycloadducts 14 and 15 which are predicted to undergo asynchronous reactions show differing degrees of carbon-carbon bond lengthening, reflecting the differing degrees of bond breaking at the calculated transition states for the rDA.

  DOI：

  10.1021/ja025634f
• 作为产物：
  描述：

  N-甲基马来酰亚胺 、 1,3-环己二烯 以 二氯甲烷 为溶剂， 反应 5.0h， 以91%的产率得到(1S,2R,6S,7R)-4-methyl-4-azatricyclo[5.2.2.02,6]undec-8-ene-3,5-dione
  参考文献：
  名称：

  Structural Investigations into the retro-Diels-Alder Reaction. Experimental and Theoretical Studies

  摘要：

  The manifestations of the retro-Diels Alder reaction in the ground-state structures of a range of cyclopentadiene and cyclohexadiene cycloadducts 9-15 have been investigated by a combination of techniques. These include low-temperature X-ray crystallography, density functional calculations (B3LYP/ 6-31G(d,p)) on both the ground states and transition states, and the measurement of C-13-C-13 coupling constants. We have found that the carbon-carbon bonds (labeled bonds a and b), which break in the rDA, are longer in the cycloadducts 9-15 than in their corresponding saturated analogues 9s-15s, which cannot undergo the rDA reaction. The degree of carbon-carbon bond lengthening appears to be related to the reactivity of the cycloadduct, thus the more reactive benzoquinone cycloadducts 5b and 13 have longer carbon-carbon bonds, Those cycloadducts 14 and 15 which are predicted to undergo asynchronous reactions show differing degrees of carbon-carbon bond lengthening, reflecting the differing degrees of bond breaking at the calculated transition states for the rDA.

  DOI：

  10.1021/ja025634f

文献信息

• NEW PHENYLALANINE DERIVATIVES
  申请人：SUZUKI Nobuyasu

  公开号：US20090048236A1

  公开（公告）日：2009-02-19

  Specific phenylalanine derivatives or pharmaceutically acceptable salts thereof have an antagonistic effect on the α4 integrins and, therefore, are usable as therapeutic agents or preventive agents for diseases in which α4 integrin-depending adhesion process participates in the pathology, such as inflammatory diseases, rheumatoid arthritis, inflammatory bowel diseases, systemic lupus erythematosus, multiple sclerosis, Sjögren's syndrome, asthma, psoriasis, allergy, diabetes, cardiovascular diseases, arterial sclerosis, restenosis, tumor proliferation, tumor metastasis and transplantation rejection.

  特定的苯丙氨酸衍生物或其药学上可接受的盐具有对α4整合素的拮抗作用，因此可用作治疗剂或预防剂，用于α4整合素依赖性黏附过程参与病理的疾病，如炎症性疾病、类风湿性关节炎、炎症性肠病、系统性红斑狼疮、多发性硬化症、干燥综合症、哮喘、银屑病、过敏、糖尿病、心血管疾病、动脉硬化、再狭窄、肿瘤增殖、肿瘤转移和移植排斥。
• Effects of the Hydrophobicity of the Reactants on Diels−Alder Reactions in Water
  作者：Ale Meijer、Sijbren Otto、Jan B. F. N. Engberts

  DOI：10.1021/jo981359x

  日期：1998.11.1

  To assess the importance of the hydrophobicity of different parts of diene and dienophile on the aqueous acceleration of Diels-Alder reactions, second-order rate constants have been determined for the reactions of cyclopentadiene (1), 2,3-dimethyl-1,3-butadiene(4), and 1,3-cyclohexadiene (6) with N-methyl-, N-ethyl-, N-propyl-, and N-butyhmaleimide (2a-d) in different solvents. All these reactions are accelerated in water relative to organic solvents as a result of enhanced hydrogen bonding and enforced hydrophobic interactions during the activation process. The beneficial influence of water as compared to l-propanol on the rate of the Diels-Alder reaction of 4 with 2a-d increases linearly with the length of the alkyl chain of 2. In contrast, for the reaction of both 1 and 6 with 2a-d, no such effect was observed. This difference can be explained by a hydrophobic interaction between the methyl groups of 4 and the N-alkyl group of 2 during the activation process. In the reactions of I and 6, lacking the methyl substituents, this interaction is not possible and elongation of the alkyl chain from ethyl onward does not result in an additional acceleration by water. The enhanced hydrophobicity near the reaction center of dienes 4 and 6 compared to I results in an increased aqueous acceleration of the Diels-Alder reactions of the former dienes with 2a. These data indicate that an increase in the hydrophobicity close to the reaction center in the diene has a much more pronounced effect on the rate acceleration in water than a comparable increase in hydrophobicity in the dienophile further away from the reaction center. The Gibbs energies of transfer of initial state and activated complex of the Diels-Alder reactions under study have been determined. As expected, for all reactions the initial state in water is destabilized compared to that in l-propanol. This destabilization becomes more pronounced when the nonpolar character of diene (close to the reaction center) or dienophile (distant from the reaction center) is increased. Likewise, an increase in the nonpolar character of 2 results in a destabilization of the activated complex. In contrast, addition of methyl or methylene units to the diene is not accompanied by a significant destabilization of the activated complex in water as compared to I-propanol. We conclude that hydrophobic groups near the reaction center seem to lose their hydrophobic character completely in the activated complex of the Diels-Alder reaction, whereas more distant groups retain their nonpolar character throughout the reaction.
• Goksu, Gokce; Ocal, Nuket, Acta Chimica Slovenica, 2011, vol. 58, # 2, p. 256 - 261
  作者：Goksu, Gokce、Ocal, Nuket

  DOI：——

  日期：——
• US7452905B2
  申请人：——

  公开号：US7452905B2

  公开（公告）日：2008-11-18
• US7759388B2
  申请人：——

  公开号：US7759388B2

  公开（公告）日：2010-07-20