(1R,9S)-11-(2,2-dimethylpropionyl)-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-6-one | 474116-10-4

• 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: (1R,9S)-11-(2,2-dimethylpropionyl)-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-6-one
• 英文别名: N-pivaloylcytisine；(1R,9S)-11-(2,2-dimethylpropanoyl)-7,11-diazatricyclo[7.3.1.02,7]trideca-2,4-dien-6-one
• CAS: 474116-10-4
• 化学式: C₁₆H₂₂N₂O₂
• 分子量: 274.363
• InChiKey: DTXOJBGPXJHBQX-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,9S)-11-(2,2-dimethylpropionyl)-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-6-one 在 platinum(IV) oxide 氢气 、 lithium aluminium tetrahydride 作用下， 以 甲醇 、 四氢呋喃 为溶剂， 反应 40.0h， 以89%的产率得到(1R,2S,9S)-11-(2,2-dimethylpropyl)-7,11-diazatricyclo[7.3.1.0^2,7]tridecane
  参考文献：
  名称：

  Evaluation of (+)-Sparteine-like Diamines for Asymmetric Synthesis

  摘要：

  Three new (+)-sparteine-like diamines were prepared from (-)-cytisine and evaluated as sparteine surrogates in the alpha-lithiation rearrangement of cyclooctene oxide and the palladium(II)/diamine catalyzed oxidative kinetic resolution of I-indanol. The new diamines exhibited opposite enantioselectivity to that observed with (-)-sparteine but increasing the steric hindrance of the N-alkyl group beyond N-Et had a detrimental effect on enantioselectivity. The optimal N-Me diamine was evaluated with much success in five other (-)-sparteine-mediated processes involving different metals (lithium, magnesium, and copper) and different types of reaction mechanisms.

  DOI：

  10.1021/jo049182w
• 作为产物：
  描述：

  三甲基乙酰氯 、 cytisine 在 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 5.0h， 以69%的产率得到(1R,9S)-11-(2,2-dimethylpropionyl)-7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-6-one
  参考文献：
  名称：

  Evaluation of (+)-Sparteine-like Diamines for Asymmetric Synthesis

  摘要：

  Three new (+)-sparteine-like diamines were prepared from (-)-cytisine and evaluated as sparteine surrogates in the alpha-lithiation rearrangement of cyclooctene oxide and the palladium(II)/diamine catalyzed oxidative kinetic resolution of I-indanol. The new diamines exhibited opposite enantioselectivity to that observed with (-)-sparteine but increasing the steric hindrance of the N-alkyl group beyond N-Et had a detrimental effect on enantioselectivity. The optimal N-Me diamine was evaluated with much success in five other (-)-sparteine-mediated processes involving different metals (lithium, magnesium, and copper) and different types of reaction mechanisms.

  DOI：

  10.1021/jo049182w

文献信息

• Regio- and diastereoselective functionalization of (−)-cytisine: an unusual N–C acyl migration
  作者：Jacques Rouden、Alexis Ragot、Sonia Gouault、Dominique Cahard、Jean-Christophe Plaquevent、Marie-Claire Lasne

  DOI：10.1016/s0957-4166(02)00271-9

  日期：2002.7

  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.