(-) epimyrtine | 82111-02-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: (-) epimyrtine
• 英文别名: Epimyrtine；(4R,9aS)-4-methyl-1,3,4,6,7,8,9,9a-octahydroquinolizin-2-one
• CAS: 82111-02-2
• 化学式: C₁₀H₁₇NO
• 分子量: 167.251
• InChiKey: GDQCWCOVKFXWMP-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (R)-tert-butyl (4-diazo-3-oxobutan-2-yl)carbamate 在 silver hexafluoroantimonate 、 正丁基锂 、 三苯基膦氯金 、 四溴化碳 、 palladium on activated charcoal 、 氢气 、 四氯化锡 、 silver nitrate 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， -78.0~40.0 ℃ 、101.33 kPa 条件下， 反应 73.0h， 生成 (-) epimyrtine
  参考文献：
  名称：

  通过金催化加氢胺化方法全合成 (-)-表米碱。

  摘要：

  已经从 D-丙氨酸开发了一种全合成 (-)-表米碱的新方法。获得对映体纯吡啶酮中间体的关键步骤是通过金介导的环化实现的。最后，各种转化在几个步骤中提供了天然产物和良好的总产率。

  DOI：

  10.3762/bjoc.9.242

文献信息

• Iminium ion cascade reactions: stereoselective synthesis of quinolizidines and indolizidines
  作者：Shawn M. Amorde、Ivan T. Jewett、Stephen F. Martin

  DOI：10.1016/j.tet.2008.10.074

  日期：2009.4

  A novel iminium ion cascade reaction has been developed that allows for the stereoselective synthesis of a variety of substituted aza-fused bicycles. The combination of amino allylsilanes and aldehydes (or ketones) was used to synthesize a number of quinolizidines and indolizidines in a one-pot reaction sequence. This technology has been used to effect the facile syntheses of several indolizidine and

  已经开发了一种新型亚胺离子级联反应，可以立体选择性地合成各种取代的氮杂融合双环。氨基烯丙基硅烷和醛（或酮）的组合被用于在一锅反应序列中合成许多喹唑西啶和吲哚里西啶。该技术已被用于实现几种吲哚里西啶和喹诺西啶天然产物的简便合成，包括 (±)-epilupinine、(±)-tashiromine 和 (-)-epimyrtine。已经检查了底物范围，改变氨基烯丙基硅烷（伯、仲和共轭）和羰基化合物（醛和酮）的类型，以提供各种稠环结构。改变选择的组分允许在核心结构的不同位置包含合成有用的官能团。
• Myrtine and epimyrtine, quinolizidine alkaloids from vaccinium myrtillus
  作者：P. Slosse、C. Hootelé

  DOI：10.1016/0040-4020(81)85024-7

  日期：1981.1

  The structures (including conformation and absolute configuration) of myrtine and epimyrtine, quinolizidine alkaloids from Vaccinium myrtillus, are reported. The two bases are obtainable from pelletierine by Mannich condensation with acetaldehyde, or can be derived stereospecifically by 1,4-nucleophilic addition to enaminones. They have been resolved with tartaric acid. The isomerization of myrtine

  报道了来自牛痘越桔的桃金娘碱和表myrine，奎尼嗪核碱生物碱的结构（包括构象和绝对构型）。这两个碱可通过曼尼希与乙醛的曼尼希缩合而从小丸碱中获得，或可通过与烯胺酮的1,4-亲核加成反应立体定向获得。他们已经用酒石酸解决了。讨论了桃金娘碱的异构化。
• Cascade Iminium Ion Reactions for the Facile Synthesis of Quinolizidines. Concise Syntheses of (±)-Epilupinine and (−)-Epimyrtine
  作者：Shawn M. Amorde、Andrew S. Judd、Stephen F. Martin

  DOI：10.1021/ol050544b

  日期：2005.5.1

  Several novel cascade processes have been designed and developed that involve sequential reactions of imines and iminium ions to form substituted quinolizidine ring systems in a single step from simple and readily available starting materials. The utility and promise of these cascade reactions is evident from their application to extraordinarily concise syntheses of the representative quinolizidine alkaloids epilupinine and (-)-epimyrtine.
• Asymmetric Synthesis of the Quinolizidine Alkaloid (−)-Epimyrtine with Intramolecular Mannich Cyclization and <i>N</i>-Sulfinyl δ-Amino β-Ketoesters
  作者：Franklin A. Davis、Yulian Zhang、Gopinathan Anilkumar

  DOI：10.1021/jo030208d

  日期：2003.10.1

  A concise, six-step, enantioselective synthesis of (-)-epimyrtine employing the N-sulfinyl delta-amino beta-ketoester chiral building block is described.
• Stereoselective Synthesis of 2,6-<i>cis</i>- and 2,6-<i>trans</i>-Piperidines through Organocatalytic Aza-Michael Reactions: A Facile Synthesis of (+)-Myrtine and (−)-Epimyrtine
  作者：Yongcheng Ying、Hyoungsu Kim、Jiyong Hong

  DOI：10.1021/ol103064f

  日期：2011.2.18

  Both 2,6-cis- and 2,6-trans-piperidines were prepared from common substrates through organocatalytic aza-Michael reactions promoted by the gem-disubstituent effect in conjunction with dithiane coupling reactions. The organocatalytic aza-Michael reaction enabled a facile synthesis of (+)-myrtine and (-)-epimyrtine from a common substrate.