(1R,5S)-1-methyl-9-azabicyclo[3.3.1]nonan-3-one | 84026-78-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (1R,5S)-1-methyl-9-azabicyclo[3.3.1]nonan-3-one
• 英文别名: (+)-1-methyl-9-azabicyclo(3.3.1)nonan-3-one；(-)-Euphococcinine
• CAS: 84026-78-8
• 化学式: C₉H₁₅NO
• 分子量: 153.224
• InChiKey: BWXDELRNNYLLKB-IONNQARKSA-N

物化性质

• 熔点：
  31-32 °C
• 沸点：
  238.9±15.0 °C(Predicted)
• 密度：
  1.035±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (-)-2-氰-6-苯基恶唑哌啶 在 palladium on activated charcoal 盐酸 、 叔丁基二甲硅基三氟甲磺酸酯 、 氢气 、 lithium diisopropyl amide 作用下， 以 甲醇 为溶剂， 反应 5.17h， 生成 (1R,5S)-1-methyl-9-azabicyclo[3.3.1]nonan-3-one
  参考文献：
  名称：

  Asymmetric synthesis. 26. An expeditious enantioselective synthesis of the defense alkaloids (-)-euphococcinine and (-)-adaline via the CN(R,S) method

  摘要：

  The unnatural enantiomer (-)-euphococcinine (2) and the natural enantiomer of (-)-adaline (3), two homotropane alkaloids, were each prepared in three steps from chiral (-)-2-cyano-6-oxazolopiperidine synthon 8 by the CN(R,S) method. The key steps of these syntheses are the formation of a chiral quaternary center alpha to the piperidine nitrogen with complete stereocontrol and a subsequent intramolecular Mannich reaction. The previously unknown absolute configuration of natural (+)-euphococcinine was deduced from the synthesis of its enantiomer (-)-2.

  DOI：

  10.1021/jo00041a028

文献信息

• Assymetric syntheses of the ladybug alkaloid adaline and 1-methyl-9-azabicyclo [3.3.1]nonan-3-one
  作者：Richard K. Hill、Louis A. Renbaum

  DOI：10.1016/0040-4020(82)80045-8

  日期：1982.1

  The double Michael addition of benzylamine to 3-alkyl-2,7-cyclooctadienones, followed by hydrogenolysis, affords bridgehead substituted 9-azabicyclo[3.3.1]nonan-3-ones. Use of (+)-α-methylbenzylamine in the addition leads to mixtures of diastereomeric adducts in unequal amounts. Although the degree of asymmetric induction is low (10–20% ee), the diastereonomers can be easily separated, affording pure

  将苄胺双迈克尔加成至3-烷基-2,7-环辛二烯酮，然后进行氢解，得到桥头取代的9-氮杂双环[3.3.1]壬基-3-酮。在加成物中使用（+）-α-甲基苄基胺会导致不等量的非对映异构体加合物的混合物。尽管不对称诱导的程度很低（10–20％ee），但非对映异构体可以轻松分离，从而提供了瓢虫生物碱阿达林1和大戟生物碱3的纯对映体形式。
• Asymmetric Synthesis of Substituted Homotropinones from <i>N</i>-Sulfinyl β-Amino Ketone Ketals. (−)-Euphococcinine and (−)-Adaline
  作者：Franklin A. Davis、Ram Edupuganti

  DOI：10.1021/ol902910w

  日期：2010.2.19

  Sulfinimine-derived N-sulfinyl β-amino ketone ketals on heating with NH4OAc:HOAc undergo a four-step intramolecular Mannich cyclization cascade reaction to give homotropinones, such as (−)-euphococcinine, in excellent yields as single isomers.

  在与NH 4 OAc：HOAc加热的条件下，亚砜胺衍生的N-亚磺酰基β-氨基酮缩酮经过四个步骤的分子内曼尼希环化级联反应，以单异构体形式以优异的收率得到高纯肌酮，如（-）-大磷霉素。
• WO2020163405A5
  申请人：——

  公开号：WO2020163405A5

  公开（公告）日：2023-02-13
• A tandem synthesis of (±)-euphococcinine and (±)-adaline
  作者：Edwin C. Davison、Andrew B. Holmes、Ian T. Forbes

  DOI：10.1016/0040-4039(95)01908-z

  日期：1995.12

  Intramolecular hydroxylamine-alkyne cyclisation of the hydroxylamines 8 and 9 afforded six-membered cyclic nitrones which without isolation underwent a tandem intramolecular dipolar cycloaddition to produce the tricyclic isoxazolidines 6 and 7 respectively. These were converted in two steps into the ladybird defence alkaloids (+/-)-euphococcinine 4 and (+/-)-adaline 5.
• Asymmetric synthesis. 26. An expeditious enantioselective synthesis of the defense alkaloids (-)-euphococcinine and (-)-adaline via the CN(R,S) method
  作者：Chongwei Yue、Jacques Royer、Henri Philippe Husson

  DOI：10.1021/jo00041a028

  日期：1992.7

  The unnatural enantiomer (-)-euphococcinine (2) and the natural enantiomer of (-)-adaline (3), two homotropane alkaloids, were each prepared in three steps from chiral (-)-2-cyano-6-oxazolopiperidine synthon 8 by the CN(R,S) method. The key steps of these syntheses are the formation of a chiral quaternary center alpha to the piperidine nitrogen with complete stereocontrol and a subsequent intramolecular Mannich reaction. The previously unknown absolute configuration of natural (+)-euphococcinine was deduced from the synthesis of its enantiomer (-)-2.