1-benzyl-1,5,6,7-tetrahydroazepin-2-one | 165257-11-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吖庚因类
• 英文名称: 1-benzyl-1,5,6,7-tetrahydroazepin-2-one
• 英文别名: N-benzyl-2-oxoazep-3-ene；1-benzyl-1,5,6,7-tetrahydro-2H-azepin-2-one；1-benzyl-3,4-dihydro-2H-azepin-7-one
• CAS: 165257-11-4
• 化学式: C₁₃H₁₅NO
• 分子量: 201.268
• InChiKey: JGWKMNFFFCNAIO-UHFFFAOYSA-N

物化性质

• 沸点：
  391.7±22.0 °C(Predicted)
• 密度：
  1.097±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-benzyl-1,5,6,7-tetrahydroazepin-2-one 在 2,6-二甲基吡啶 、 四氧化锇 、 sodium azide 、 三氟甲磺酸酐 、 三氟化硼乙醚 、 苄基三甲基溴化铵 、 N-甲基吗啉氧化物 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 水 、 丙酮 、 叔丁醇 为溶剂， 反应 54.0h， 生成 N-benzyl-trans-4-(benzoyloxy)-3-azido-2-oxoazepane
  参考文献：
  名称：

  Total Synthesis of (−)- and (+)-Balanol¹

  摘要：

  Two total syntheses of the potent protein kinase C inhibitory fungal metabolite balanol are described. In the first approach, the core aminohydroxyazepane subunit was prepared in racemic form by stereospecific functionalization of N-benzyl-epsilon-caprolactam. Resolution prior to coupling to the benzophenone subunit provided access to both enantiomers of balanol. In the second approach, an efficient silicon-mediated cyclization of(2S,3R)-3-hydroxylysine followed by reduction provided the azepane subunit in enantiomerically pure form. The sterically congested benzophenone subunit was assembled from two highly substituted aromatic precursors by way of an anionic home-Fries rearrangement.

  DOI：

  10.1021/jo952280k
• 作为产物：
  描述：

  己内酰胺 在 氢氧化钾 、 四丁基溴化铵 、 双氧水 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 2.17h， 生成 1-benzyl-1,5,6,7-tetrahydroazepin-2-one
  参考文献：
  名称：

  共轭内酰胺的制备和环氧化：环大小对环氧化的影响

  摘要：

  摘要 α,β-环氧-内酰胺可以由共轭内酰胺用间氯过氧苯甲酸处理制备。然而，只有使用 2-吡咯烷酮衍生物才能获得良好的产率。随着内酰胺环尺寸的增加，环氧-内酰胺的产率急剧下降。

  DOI：

  10.1080/00397919508012690

文献信息

• Bifunctional Iminophosphorane-Catalyzed Enantioselective Sulfa-Michael Addition to Unactivated α,β-Unsaturated Amides
  作者：Daniel Rozsar、Michele Formica、Ken Yamazaki、Trevor A. Hamlin、Darren J. Dixon

  DOI：10.1021/jacs.1c11898

  日期：2022.1.19

  unactivated α,β-unsaturated amides is described. Consistently high enantiomeric excesses and yields were obtained over a wide range of alkyl thiol pronucleophiles and electrophiles under mild reaction conditions, enabled by a novel squaramide-based bifunctional iminophosphorane catalyst. Low catalyst loadings (2.0 mol %) were achieved on a decagram scale, demonstrating the scalability of the reaction. Computational

  描述了第一个无金属催化分子间对映选择性迈克尔加成到未活化的 α,β-不饱和酰胺。在温和的反应条件下，通过一种新型的基于方酰胺的双功能亚氨基正膦催化剂，在各种烷基硫醇亲核试剂和亲电试剂上获得了一致的高对映体过量和产率。在十克规模上实现了低催化剂负载量 (2.0 mol%)，证明了反应的可扩展性。计算分析通过分析相关过渡结构揭示了高对映选择性的来源，并为催化剂对 α,β-不饱和酰胺的羰基的特定非共价活化提供了实质性支持。
• Two efficient syntheses of (±)-anti-N-benzyl-3-amino-4-hydroxyhexahydroazepine
  作者：Hong Hu、G. Erik Jagdmann、Philip F. Hughes、Jeffrey B. Nichols

  DOI：10.1016/0040-4039(95)00623-k

  日期：1995.5

  Functionalization of ε-caprolactam (3) or Beckmann rearrangement of the syn-oxime derivative of 3-ethoxy-2-cyclohexen-1-one (12) provided efficient and high-yielding syntheses of (±)-anti-N-benzyl-3-amino-4-hydroxyhexahydroazepine (2), a key intermediate for the syntheses of racemic balanol and its analogs.

  ε-己内酰胺（3）的功能化或3-乙氧基-2-环己烯-1-酮（12）的肟肟衍生物的贝克曼重排提供了（±）-抗-N-苄基-的高效高产合成3-氨基-4-羟基六氢a庚因（2），是外消旋巴拉诺醇及其类似物合成的关键中间体。
• CAPROLACTAM MGLUR5 RECEPTOR MODULATORS
  申请人：Sisko John T.

  公开号：US20130203735A1

  公开（公告）日：2013-08-08

  The present invention is directed to caprolactams which are positive allosteric modulators of metabotropic glutamate receptors, particularly the mGluR5 receptor, and which are useful in the treatment or prevention of neurological and psychiatric disorders associated with glutamate dysfunction and diseases in which metabotropic glutamate receptors are involved. The invention is also directed to pharmaceutical compositions comprising these compounds and the use of these compounds and compositions in the prevention or treatment of such diseases in which metabotropic glutamate receptors are involved.

  本发明涉及己内酰胺，其为代谢型谷氨酸受体的正向变构调节剂，特别是mGluR5受体，并且在治疗或预防与谷氨酸功能障碍相关的神经和精神障碍以及代谢型谷氨酸受体涉及的疾病中有用。本发明还涉及包含这些化合物的药物组合物以及将这些化合物和组合物用于预防或治疗涉及代谢型谷氨酸受体的这种疾病。
• Verbessertes Verfahren zur Herstellung von Hexahydroazepinonen und Hexahydroazepinolen
  申请人：ASTA Medica Aktiengesellschaft

  公开号：EP0659744B1

  公开（公告）日：2001-02-28
• [EN] CAPROLACTAM MGLUR5 RECEPTOR MODULATORS<br/>[FR] MODULATEURS CAPROLACTAMES DES RÉCEPTEURS MGLUR5
  申请人：MERCK SHARP & DOHME

  公开号：WO2012058128A2

  公开（公告）日：2012-05-03

  The present invention is directed to caprolactams which are positive allosteric modulators of metabotropic glutamate receptors, particularly the mGluR5 receptor, and which are useful in the treatment or prevention of neurological and psychiatric disorders associated with glutamate dysfunction and diseases in which metabotropic glutamate receptors are involved. The invention is also directed to pharmaceutical compositions comprising these compounds and the use of these compounds and compositions in the prevention or treatment of such diseases in which metabotropic glutamate receptors are involved.