(3aS,6aR)-3,3a,4,6a-tetramethyl-6-(3-oxohexanoyl)-1H-imidazo[4,5-d]imidazole-2,5-dione | 146496-95-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (3aS,6aR)-3,3a,4,6a-tetramethyl-6-(3-oxohexanoyl)-1H-imidazo[4,5-d]imidazole-2,5-dione
• CAS: 146496-95-9
• 化学式: C₁₄H₂₂N₄O₄
• 分子量: 310.353
• InChiKey: VUAWZMAZTAWUET-KGLIPLIRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  90
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  在 正丁基锂 、 L-Selectride 、 三乙胺 、 lithium tert-amoxide 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.83h， 生成 (3aS,6aR)-3,3a,4,6a-tetramethyl-6-(3-oxohexanoyl)-1H-imidazo[4,5-d]imidazole-2,5-dione
  参考文献：
  名称：

  甘脲†是分子内克莱森型缩合反应的有效分子模板

  摘要：

  易于制备的3,4,7,8-四甲基甘脲1用作模板，以促进连接至N -1和N -6位置的两个酰基之间有效的分子内Claisen样缩合。因此，两个连续的1的酰化反应会以高收率得到对称或不对称的二酰基甘氨酰9-18。用叔醇锂处理9-18可以在温和的条件下以高收率获得N-（β-酮酰基）甘脲19-27。限速去质子化主要发生在两个酰基的最少取代基上，然后发生快速的分子内克莱森型缩合。还原19和26中的酮基，然后消除水，得到烷基-2-烯丙基甘脲6和7；共轭氢化物加成（然后将L- Selectride生成链烷酰基甘脲糖醇5。化合物5-7经过N-酰化反应后再进行分子内缩合。因此，可以通过酰化-缩合-官能团转化的重复序列在1上构建线性链。N 1-烷基-2-烯丙基-N 6-烷酰基甘露糖醇14-17在用L处理后也能提供高选择性的缩合产物-Selectride，实现了在碱基促进的重排中观察到的区域选择性的净逆转的方法

  DOI：

  10.1039/a706855g

文献信息

• Efficient claisen-type condensation between acyl units bound to a molecular template
  作者：Sengen Sun、Paul Harrison

  DOI：10.1016/0040-4039(93)88025-e

  日期：1992.12

  Acylation of 3,4,7,8-tetramethylglycoluril1 (1) provides the monoacyl derivative 3 which can be acylated further with LDA and acyl chlorides. The resulting symmetric or asymmetric diacyl derivatives 4 undergo efficient base-catalyzed acyl transfer to provide 2-(acylacyl)glycolurils 5,6. Thus, 1 acts as a template to allow facile condensations between acyl units.
• A Facile Preparation of Thioglycolurils from Glycolurils, and Regioselectivity in Thioglycoluril Template-Directed Crossed-Claisen Condensations
  作者：Christopher N. Cow、Paul H. M. Harrison

  DOI：10.1021/jo9713823

  日期：1997.12.1

  Mono- (5) and dithio (4) analogues of 3,4,7,8-tetramethylglycoluril (2) are readily prepared using Lawesson's reagent (1 equiv or excess, respectively). This novel application of Lawesson's reagent to glycolurils can be extended to N-acylglycolurils. Thus the N-acetyl and N-butanoyl derivatives of 2 are converted into the monoacyl-monothio analogues 8 and 9 in which thionation occurs at the least hindered urea carbonyl, Compared to the parent glycoluril 2, the thio analogues are more readily acylated; initial acylation of 5 occurs exclusively on the NH site adjacent to sulfur to give 13, while 4 is converted to either the monoacetyl (11) or diacetyl (12) derivative by acetic anhydride, depending on temperature. Unlike 2, acylation of 4 can be accomplished with tert-butoxide as base and then acyl halide. Further acetylation of 11 gives 12, while 8 gives the unsymmetrical diacetyl-monothioglycoluril 15 or acetyl butanoyl thioglycoluril 17, and 9 gives the isomeric acetyl butanoyl thioglycoluril 16. Derivative 12 undergoes a crossed Claisen-like condensation between the two acetyl groups to give acetoacetyldithioglycoluril (18), in a manner similar to the diacetyl derivative of the parent glycoluril, while 15 undergoes selective crossed-Claisen condensation, predominantly by deprotonation of the acetyl group adjacent to oxygen (2.2:1 ratio of 19:20), In crossed-Claisen condensations, both isomers of acetylbutanoylmonothioglycoluril rearranged to 3-ketohexanoyl and 2-ethyl-3-ketobutanoyl thioglycolurils (16 to 24 and 25; 17 to 26 and 27, respectively), When the selectivities for deprotonation of the acetyl moiety over the butanoyl moiety, and for deprotonation of the acyl group adjacent to oxygen over that adjacent to sulfur, reinforced each other, highly selective crossed-Claisen condensation was achieved (26:27 6:1), In contrast, when these two selectivities worked in opposition, reversal of the regiochemical outcome occurred (24:25 0.75:1), The results show that thionation provides a more sophisticated and selective template for development of intramolecular crossed-Claisen methodology using the glycoluril template-directed approach.