isosolenopsin A | 63950-16-3

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: isosolenopsin A
• 英文别名: cis-2-methyl-6-undecylpiperidine；(+/-)-epi-solenopsin A；(+/-)-isosolenopsin；(2S,6R)-2-methyl-6-undecylpiperidine
• CAS: 63950-16-3
• 化学式: C₁₇H₃₅N
• 分子量: 253.472
• InChiKey: AYJGABFBAYKWDX-DLBZAZTESA-N

物化性质

• 熔点：
  140-142 °C
• 沸点：
  320.1±10.0 °C(Predicted)
• 密度：
  0.821±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-methoxytrifluoromethylphenylacetyl chloride 、 isosolenopsin A 在 三乙胺 作用下， 以 吡啶 为溶剂， 反应 29.0h， 生成 (S)-3,3,3-Trifluoro-2-methoxy-1-((2S,6R)-2-methyl-6-undecyl-piperidin-1-yl)-2-phenyl-propan-1-one 、 (S)-3,3,3-Trifluoro-2-methoxy-1-((2R,6S)-2-methyl-6-undecyl-piperidin-1-yl)-2-phenyl-propan-1-one
  参考文献：
  名称：

  Absolute configuration of the solenopsins, venom alkaloids of the fire ants.

  摘要：

  An effective and practical procedure has been developed that allows the assignment of the absolute configuration of solenopsins from diverse origins using only small amounts of material. The method is based on the transformation of the natural secondary amines into diastereoisomeric amides by reaction with (R)-2-methoxy-2-phenyl-2-(trifluoromethyl)acetic acid chloride (MTPA-Cl), followed by comparison of their chromatographic behaviour with those of standards of established absolute configuration, This procedure has been applied to three samples of ants: Solenopsis geminata workers, S. invicta workers and S. invicta alates. It has been found that the absolute configuration of the trans alkaloids is always (2R,6R) while that of the cis alkaloids is (2R,6S). Moreover, a new synthesis of enantiomerically pure solenopsin A (4) and isosolenopsin A (3) starting from L-alanine is presented.

  DOI：

  10.1016/s0040-4020(01)85567-8
• 作为产物：
  描述：

  1-十一烯 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 palladium on activated charcoal 氢气 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 isosolenopsin A
  参考文献：
  名称：

  串联超人重排和分子内酰胺化反应。立体控制合成顺式和反式2,6-二烷基哌啶。

  摘要：

  [反应：见正文]汞（II）介导的串联Overman重排和分子内酰胺化反应被证明为立体选择性合成顺式和反式2,6-二取代哌啶提供了方便的工具。因此，在THF中用Hg（OTFA）（2）处理后，三氯乙酰亚胺酸酯1以几乎排他的选择性选择性直接转化为2，6-二烷基哌啶2。Hg（OTFA）（2）在硝基甲烷中的氨基甲酸酯7的酰胺键固化反应显示出极好的顺式选择性。还报道了solenopsin A和isosolenopsin A的立体选择性合成。

  DOI：

  10.1021/ol048961w

文献信息

• Rapid configuration analysis of the solenopsins
  作者：Adriana Pianaro、Eduardo G.P. Fox、Odair C. Bueno、Anita J. Marsaioli

  DOI：10.1016/j.tetasy.2012.05.005

  日期：2012.5

  A protocol for rapid access to the relative and absolute configurations of the solenopsins, the venom alkaloids of fire ants (Solenopsis spp.), was developed based on chiral capillary gas chromatography. The synthesis of racemic mixtures of 2-methyl-6-alkylpiperidines and the isolation of natural (2R,6R)- and (2R,6S)-2-methyl-6-undecylpiperidines allowed for the standardization of the chromatographic

  一种用于快速访问solenopsins，火蚁的毒液生物碱的相对和绝对构型（协议红火属物种），基于手性毛细管气相色谱法的开发。2-甲基-6-烷基哌啶外消旋混合物的合成以及天然（2 R，6 R）-和（2 R，6 S）-2-甲基-6-十一烷基哌啶的分离可实现色谱方法的标准化。该协议的应用透露毒液样品中的2-甲基-6- undecylpiperidine的四种立体异构体的先前未知的天然发生率从工人和的gynes红火saevissima。
• Hydrogenation of Pyridines Using a Nitrogen-Modified Titania-Supported Cobalt Catalyst
  作者：Feng Chen、Wu Li、Basudev Sahoo、Carsten Kreyenschulte、Giovanni Agostini、Henrik Lund、Kathrin Junge、Matthias Beller

  DOI：10.1002/anie.201803426

  日期：2018.10.26

  Novel heterogeneous catalysts were prepared by impregnation of titania with a solution of cobalt acetate/melamine and subsequent pyrolysis. The resulting materials show an unusual nitrogen‐modified titanium structure through partial implementation of nitrogen into the support. The optimal catalyst displayed good activity and selectivity for challenging pyridine hydrogenation under acid free conditions

  通过用乙酸钴/三聚氰胺溶液浸渍二氧化钛并随后进行热解来制备新型的非均相催化剂。所得材料通过将氮部分引入载体中而显示出不同寻常的氮改性钛结构。最佳的催化剂显示出良好的活性和选择性，可以在无酸条件下以水为溶剂，挑战吡啶的氢化反应。
• Synthesis of enantiomerically pure fire ant venom alkaloids: Solenopsins and isosolenopsins A, B and C
  作者：H. M. T. Bandara Herath、N. P. Dhammika Nanayakkara

  DOI：10.1002/jhet.5570450112

  日期：2008.1

  Concise and efficient methods for the synthesis of enantiomers of fire ant venom alkaloids solenopsin and isosolenopsin A, B, and C are described. These syntheses are based on diastereoselective electrophilic substitution of enatiomerically-pure α-lithiated 2-alkylpiperidine.

  描述了一种简单有效的合成火蚁毒生物碱slenoppsin和isosolenopsin A，B和C对映异构体的方法。这些合成基于对映体纯的α-锂化的2-烷基哌啶的非对映选择性亲电取代。
• Anodic Cyanation of (−)‐<i>N</i>‐Phenyl‐2‐Methylpiperidine: A Short Synthesis of (+)‐Solenopsin A and (+)‐Isosolenopsin A
  作者：Nicolas Girard、Jean‐Pierre Hurvois、Loic Toupet、Claude Moinet

  DOI：10.1081/scc-200050370

  日期：2005.3.1

  Abstract A convenient method for the preparation of (+)‐Solenopsin A 1 (5 steps, 21%) involving regiospecific anodic cyanation of (−)‐N‐phenyl‐2‐methylpiperidine 4 is described.

  摘要描述了一种制备 (+)-Solenopsin A 1 (5 步，21%) 的简便方法，包括 (-)-N-苯基-2-甲基哌啶 4 的区域特异性阳极氰化。
• Dearomatization of <i>N</i>-Phenyl-2,6-dialkylpiperidines: Practical Synthesis of (±)-Solenopsin A and (±)-Dihydropinidine
  作者：Jean-Pierre Hurvois、Nicolas Girard、Cyrille Gautier、Richard Malassene、Claude Moinet、Loic Toupet

  DOI：10.1055/s-2004-830884

  日期：——

  The fire ant venom alkaloid (′)-solenopsin A was prepared in 4 steps (34%) starting from the N-phenyl-2-undecyl piperidine (1c). The key step in this synthesis involved the dearomatization of the phenyl group of N-phenyl-2-methyl-6-undecyl-piperidine (9c), which was carried out under Birch conditions.

  从 N-苯基-2-十一烷基哌啶 (1c) 开始，通过 4 个步骤 (34%) 制备了火蚁毒液生物碱 (')-solenopsin A。该合成的关键步骤涉及 N-苯基-2-甲基-6-十一烷基-哌啶 (9c) 的苯基基团的脱芳构化，该步骤在 Birch 条件下进行。