euphococcinine | 15486-23-4

• 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: euphococcinine
• 英文别名: (1s,5r)-1-Methyl-9-azabicyclo[3.3.1]nonan-3-one
• CAS: 15486-23-4
• 化学式: C₉H₁₅NO
• 分子量: 153.224
• InChiKey: BWXDELRNNYLLKB-APPZFPTMSA-N

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

• 作为反应物：
  描述：

  聚合甲醛 、 euphococcinine 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 生成 N-methyleuphococcinine
  参考文献：
  名称：

  来自云杉属（云杉）物种的4-羟基化哌啶和N-甲基大磷球菌碱（1-甲基-3-格拉纳酮）。鉴定和综合。

  摘要：

  通过合成和GC-MS比较，鉴定了科罗拉多蓝云杉中的三种痕量生物碱，分别为4-α-羟基-顺式-2-甲基-6-（2-氧丙基）哌啶（1），4α-羟基-顺式-2 -甲基-6-丙基哌啶（11）和1-甲基格拉纳酮（15）（N-甲基-9-氮杂-1-甲基双环[3.3.1]壬烷或N-甲基大环球菌碱）。生物碱1和11是众多已知的松树和云杉哌啶中第一个含有环氧化取代基的化合物。

  DOI：

  10.1021/np9802769
• 作为产物：
  描述：

  (7S)-7-isocyanato-7-methylcyclooct-2-en-1-one 在 copper(l) chloride 、 potassium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 46.5h， 以63%的产率得到euphococcinine
  参考文献：
  名称：

  Stereoselective Synthesis of (+)-Euphococcinine and (−)-Adaline

  摘要：

  We describe the syntheses of (+)-euphococcinine and (-)-adaline, two naturally occurring alkaloids containing a quaternary carbon bearing a nitrogen atom. Key features of the syntheses are a 3,3-sigmatropic rearrangement to give an all-carbon quaternary center, a ring-closing alkene metathesis to give an 8-membered ring, and the use of a single enantiomer of p-menthane-3-carboxaldehyde to make two natural alkaloids of opposite configuration.

  DOI：

  10.1021/jo9001992

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。
• An efficient, asymmetric synthesis of (+)-euphococcinine
  作者：Mark F Mechelke、A.I Meyers

  DOI：10.1016/s0040-4039(00)00665-1

  日期：2000.6

  The enantioselective synthesis of (+)-euphococcinine (1), a homotropane alkaloid, has been achieved in five steps from bicyclic lactam 5. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Synthesis of Homochiral b-Sulfinyl Nitrones and Their Application for Enantioselective Synthesis of (+)-Euphococcinine
  作者：Shun-ichi Murahashi、Shun-Ichi Murahashi、Jun Sun、Hiroyuki Kurosawa、Yasushi Imada

  DOI：10.3987/com-99-s81

  日期：——

  Homochiral beta-sulfinyl nitrones can be prepared from secondary amines in three steps. Enantioselective synthesis of defensive alkaloid (+)-euphococcinine (9) has been accomplished by means of diastereoselective allylation of homochiral beta-sulfinyl nitrone (13) followed by intramolecular 1,3-dipolar cycloaddition reaction.
• Stereoselective Synthesis of (+)-Euphococcinine and (−)-Adaline
  作者：Mélissa Arbour、Stéphanie Roy、Cédrickx Godbout、Claude Spino

  DOI：10.1021/jo9001992

  日期：2009.5.15

  We describe the syntheses of (+)-euphococcinine and (-)-adaline, two naturally occurring alkaloids containing a quaternary carbon bearing a nitrogen atom. Key features of the syntheses are a 3,3-sigmatropic rearrangement to give an all-carbon quaternary center, a ring-closing alkene metathesis to give an 8-membered ring, and the use of a single enantiomer of p-menthane-3-carboxaldehyde to make two natural alkaloids of opposite configuration.
• 4-Hydroxylated Piperidines and <i>N</i>-Methyleuphococcinine (1-Methyl-3-granatanone) from <i>Picea</i> (Spruce) Species. Identification and Synthesis
  作者：Jeanne N. Tawara、Peter Lorenz、Frank R. Stermitz

  DOI：10.1021/np9802769

  日期：1999.2.1

  Three trace alkaloids from Colorado blue spruce, Picea pungens, were identified by synthesis and GC-MS comparisons as 4alpha-hydroxy-cis-2-methyl-6-(2-oxopropyl)piperidine (1), 4alpha-hydroxy-cis-2-methyl-6-propylpiperidine (11), and 1-methylgranatanone (15) (N-methyl-9-aza-1-methylbicyclo[3.3. 1]nonane or N-methyleuphococcinine). Alkaloids 1 and 11 are the first among numerous known pine and spruce

  通过合成和GC-MS比较，鉴定了科罗拉多蓝云杉中的三种痕量生物碱，分别为4-α-羟基-顺式-2-甲基-6-（2-氧丙基）哌啶（1），4α-羟基-顺式-2 -甲基-6-丙基哌啶（11）和1-甲基格拉纳酮（15）（N-甲基-9-氮杂-1-甲基双环[3.3.1]壬烷或N-甲基大环球菌碱）。生物碱1和11是众多已知的松树和云杉哌啶中第一个含有环氧化取代基的化合物。