N-benzyl-6α-methoxycarbonylcytisine | 474116-12-6

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 羽扇豆生物碱
• 英文名称: N-benzyl-6α-methoxycarbonylcytisine
• 英文别名: methyl (1R,8S,9S)-11-benzyl-6-oxo-7,11-diazatricyclo[7.3.1.02,7]trideca-2,4-diene-8-carboxylate
• CAS: 474116-12-6
• 化学式: C₂₀H₂₂N₂O₃
• 分子量: 338.406
• InChiKey: UCCGQSVOUNTPPO-GJYPPUQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  49.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-benzyl-6α-methoxycarbonylcytisine 在 18-冠醚-6 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 72.0h， 以57%的产率得到N-benzyl-6β-methoxycarbonylcytisine
  参考文献：
  名称：

  Regio- and diastereoselective functionalization of (−)-cytisine: an unusual N–C acyl migration

  摘要：

  In order to test (-)-cytisine as a potential chiral inductor, N-propionyl cytisine was treated with LDA and then with benzyl bromide. Instead of the expected alpha-benzyl substituted propionamide, (-)-N-benzyl 6alpha-propionyl cytisine was formed, arising from an unusual diastereoselective nitrogen to carbon acyl migration. Using LDA in the presence of an excess of LiCl, the 6-substituted cytisine was isolated in yields of up to 79%. The efficiency of the N-C acyl transfer was shown to be dependent on the nature of the N-acyl group. Complete epimerization of the newly created stereocenter was observed under basic conditions. This methodology allows the stereoelective functionalization of the C-6 position of cytisine, an important agonist of nicotinic receptors. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00271-9
• 作为产物：
  描述：

  cytisine 在 三乙胺 、 lithium chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 N-benzyl-6α-methoxycarbonylcytisine
  参考文献：
  名称：

  Regio- and diastereoselective functionalization of (−)-cytisine: an unusual N–C acyl migration

  摘要：

  In order to test (-)-cytisine as a potential chiral inductor, N-propionyl cytisine was treated with LDA and then with benzyl bromide. Instead of the expected alpha-benzyl substituted propionamide, (-)-N-benzyl 6alpha-propionyl cytisine was formed, arising from an unusual diastereoselective nitrogen to carbon acyl migration. Using LDA in the presence of an excess of LiCl, the 6-substituted cytisine was isolated in yields of up to 79%. The efficiency of the N-C acyl transfer was shown to be dependent on the nature of the N-acyl group. Complete epimerization of the newly created stereocenter was observed under basic conditions. This methodology allows the stereoelective functionalization of the C-6 position of cytisine, an important agonist of nicotinic receptors. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00271-9