(+/-)-Indolizidine 209B

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (+/-)-Indolizidine 209B
• 英文别名: (5S,8S,8aR)-8-methyl-5-pentyl-1,2,3,5,6,7,8,8a-octahydroindolizine
• 化学式: C₁₄H₂₇N
• 分子量: 209.375
• InChiKey: VISJLQLSCZBDKE-MELADBBJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  正戊基溴化镁 以 四氢呋喃 、 乙醚 为溶剂， 反应 2.0h， 生成 (+/-)-Indolizidine 209B
  参考文献：
  名称：

  Asymmetric synthesis from pyridines: use of new chiral 1,4-dihydropyridines in a short synthesis of 5,8-disubstituted indolizidine (+)-209B

  摘要：

  通过由3-皮考啉经1,4-二氢吡啶中间体制备的手性噁唑啉的合成潜力，已经通过一条便捷的途径阐明了合成5,8-双取代吲哚里西定生物碱（+）-209B的方法。

  DOI：

  10.1039/c39910000625

文献信息

• Enantiocontrolled Synthesis of 2,3,6-Trisubstituted Piperidines Using (η³-Dihydropyridinyl)molybdenum Complexes as Chiral Scaffolds. Total Synthesis of (−)-Indolizidine 209B
  作者：Chutian Shu、Ana Alcudia、Jingjun Yin、Lanny S. Liebeskind

  DOI：10.1021/ja011635g

  日期：2001.12.19

  Enantiopure TpMo(CO)2(pyridinyl) complexes were prepared using an efficient and scalable enzymatic kinetic resolution of the precursor to the molybdenum complex. A single TpMo(CO)2(pyridinyl) complex can function as a chiral scaffold for the enantiocontrolled synthesis of either 2,3,6-cis- or 2,6-cis-3-trans-trisubstituted piperidines. The synthetic potential of this methodology was demonstrated by

  Enantiopure TpMo(CO)2(吡啶基)配合物是使用钼配合物前体的有效且可扩展的酶动力学分辨率制备的。单个 TpMo(CO)2(吡啶基) 复合物可以作为手性支架用于 2,3,6-cis- 或 2,6-cis-3-trans-三取代哌啶的对映控制合成。(-)-吲哚里西啶 209B 的全合成证明了该方法的合成潜力。
• A Stereospecific Synthesis of (±)-5,8-Disubstituted Indolizidines and (±)-1,4-Disubstituted Quinolizidines Found in Poison Frog Skins
  作者：Patrick Michel、André Rassat、John W. Daly、Thomas F. Spande

  DOI：10.1021/jo000666b

  日期：2000.12.1

  An efficient, high-yield stereospecific route to three (+/-)-5, 8-disubstituted indolizidines, (209B (I), 209I (II), 223J (III)) and two (+/-)-1,4-disubstituted quinolizidines (207I (IV), 233A (V)), racemates of alkaloids found in the skins of neotropical and Madagascan poison frogs is reported. The structures of the natural alkaloids were thereby established by chiral GC comparison with the exception

  一种高效，高产率的立体定向途径，可产生三个（+/-）-5、8-双取代的吲哚并咪唑（209B（I），209I（II），223J（III））和两个（+/-）-1,4据报道，在新热带和马达加斯加毒蛙的皮肤中发现了生物碱的外消旋体-双取代的喹喔啉类化合物（207I（IV），233A（V））。从而通过手性GC比较来建立天然生物碱的结构，但吲哚并立定209B（I）除外，因为吲哚并立定209B（I）不能再检测到天然209B。
• Vinylogous urethanes in alkaloid synthesis. Applications to the synthesis of racemic indolizidine 209B and its (5R*,8S *,8aS *)-(±) diastereomer, and to (−)-indolizidine 209B †
  作者：Joseph P. Michael、David Gravestock

  DOI：10.1039/b001853h

  日期：——

  indolizidine (indolizidine 209B) (±)-1 and its hitherto unknown (5R*,8S*,8aS*) diastereomer (±)-20 were accomplished in eight steps from pyrrolidine-2-thione and ethyl oct-2-enoate. Key steps included cyclisations exploiting the nucleophilicity of vinylogous urethanes derived from ethyl (2E)-1-[1-(2-hydroxyethyl)hexyl]pyrrolidin-2-ylidene}acetate 8, and stereoselective reduction of the carbon–carbon

  外消旋体（5 R *，8 R *，8a S *）-8-甲基-5-戊基吲哚并咪唑（吲哚并立定209B）（±）-1及其迄今未知的（5 R *，8 S *，8a S *）的合成非对映体（±）-20由8个步骤完成吡咯烷-2-硫酮 和 辛-2-烯酸乙酯。关键步骤包括利用衍生自乙烯基类氨基甲酸酯的亲核性进行环化反应（2 E）-1- [1- [1-（2-羟乙基）己基]吡咯烷-2-亚乙基}乙酸乙酯 8，立体选择减少 双环乙烯基碳-碳双键的合成 氨基甲酸酯 11。对路线的对映体选择性修饰，涉及初始共轭加成（R）-（+）- N-苄基-1-苯基乙胺的阴离子与叔丁基（2E）-辛-2-烯酸叔丁酯的合成导致（-）-吲哚并啶209B的形式合成。
• Stereoselective synthesis of (.+-.)-indolizidines 167B, 205A, and 207A. Enantioselective synthesis of (-)-indolizidine 209B
  作者：Andrew B. Holmes、Adrian L. Smith、Simon F. Williams、Leslie R. Hughes、Zev Lidert、Colin Swithenbank

  DOI：10.1021/jo00004a012

  日期：1991.2

  The first syntheses of the dendrobatid indolizidine alkaloids 167B (3), 205A (4), and 207A (5) are described using as a key step the highly stereoselective intramolecular nitrone cycloaddition of the (Z)-N-alkenylnitrone 10 to prepare the isoxazolidine 11. Mesylate-promoted cyclization of the alcohol 12, followed by reductive cleavage of the resulting mesylate salt, afforded the key axial hydroxymethyl compound 13, which was epimerized via the aldehyde to the equatorial alcohol, and was subsequently reduced to the required 8-methyl-substituted indolizidine. The feasibility of extending this strategy to the enantioselective synthesis of such alkaloids was demonstrated in the first synthesis of (-)-indolizidine 209B (6), whose nitrone precursor 10d was obtained from the (S)-glutamate-derived amine 40.
• A Short Synthesis of Indolizidine (+)-209B from (3R,6S,8AS)-(-)-6-Methyl-3-phenyl-hexahydrooxazolo[3,2-a]pyridin-5-one
  作者：Joel L. Terán、Dino Gnecco、Ana M. Lumbreras、Alberto Galindo、Jorge R. Juárez、María L. Orea、Alejandro Castro、Raúl G. Enríquez、William F. Reynolds

  DOI：10.3987/com-09-11764

  日期：——

  The synthetic potential of enantiopure (3R,6S,8aS)-(-)-6-methyl-3-phenylhexahydrooxazolo[3,2-a]pyridin-5-one 2 is illustrated by a short synthesis of the 5,8-disubstituted indolizidine alkaloid (+)-209B.