(+)-tetraponerine-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: (+)-tetraponerine-1
• 英文别名: (2S,7R,9R)-7-propyl-1,6-diazatricyclo[7.3.0.02,6]dodecane
• 化学式: C₁₃H₂₄N₂
• 分子量: 208.347
• InChiKey: VJJWHOBPDFRQRH-UPJWGTAASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (2R)-2-(2,2-diethoxyethyl)pyrrolidine 在 盐酸 作用下， 以 乙醚 为溶剂， 反应 3.5h， 生成 (+)-tetraponerine-1
  参考文献：
  名称：

  Concise and Stereoselective Syntheses of the Eight Natural Ant Defense Alkaloids (+)-Tetraponerine-1 to (+)-Tetraponerine-8 According to the CN(R,S) Strategy

  摘要：

  The asymmetric syntheses of all the known defense alkaloids of the ant Tetraponera sp. tetraponerines T-1 to T-8 have been accomplished in five or six steps with 20-45% overall yields. The synthesis involved in the cross-condensation of (R)-piperidin-2-ylacetaldehyde with 4-aminobutyraldehyde which upon quenching by cyanide ion gave a stable tricyclic amino nitrile 3 with both a high yield and complete diastereoselectivity. This amino nitrile is the common precursor of four tetraponerines. A similar synthesis using (R)-pyrrolidine-2-ylacetaldehyde provided the tricyclic amino nitrile 2 precursor of the four other tetraponerines.

  DOI：

  10.1021/jo960398a

文献信息

• Asymmetric Synthesis of the Tetraponerine Alkaloids
  作者：Stephen G. Davies、Ai M. Fletcher、Ian T. T. Houlsby、Paul M. Roberts、James E. Thomson

  DOI：10.1021/acs.joc.7b00837

  日期：2017.7.7

  The asymmetric syntheses of all eight tetraponerine alkaloids (T1–T8) were achieved using the diastereoselective conjugate additions of lithium amide reagents in the key stereodefining steps. Conjugate addition of either lithium (R)-N-allyl-N-(α-methylbenzyl)amide or lithium (R)-N-(but-3-en-1-yl)-N-(α-methylbenzyl)amide to tert-butyl sorbate was followed by ring-closing metathesis of the resultant

  在关键的立体定义步骤中，使用非对映选择性共轭添加的锂酰胺试剂可实现所有八种四ponerine生物碱（T1-T8）的不对称合成。将（R）-N-烯丙基-N-（α-甲基苄基）酰胺锂或（R）-N-（丁-3-烯-1-基）-N-（α-甲基苄基）酰胺共轭加成然后，将山梨酸叔丁酯闭环复分解所得的N-烯基β-氨基酯，还原成相应的醛，然后与叔丁基（三苯基膦亚基）乙酸酯反应。随后共轭添加必要的锂对映体N-苄基-N-（α-甲基苄基）酰胺生成的α，β-不饱和酯给出了一系列二胺，可通过将酯部分还原以给出相应的醛，烯化，串联的方式精制为T1-T8氢化/氢解，与4-溴丁醛反应生成三环骨架后环化。
• Natural Tetraponerines: A General Synthesis and Antiproliferative Activity
  作者：Irene Bosque、Jose C. Gonzalez-Gomez、María Isabel Loza、José Brea

  DOI：10.1021/jo500446f

  日期：2014.5.2

  A stereocontrolled general methodology to access all natural tetraponerines from (+)-T1 to (+)-T8 is detailed. Two consecutive indium-mediated aminoallylations with the appropriate enantiomer of chiral N-tert-butylsulfinamide and a thermodynamic control at the aminal stereocenter allow the formation of each natural tetraponerine with excellent stereoselectivity. The use of 4-bromobutanal in the first aminoallylation leads to the formation of 5-6-5 tetraponerines, while 5-bromopentanal is required to build the scaffold of 6-6-5 tetraponerines. A cross-metathesis reaction of the second aminoallylation product with cis-3-hexene is used to elongate the side chain up to 5 carbons so as to prepare the tetraponerines T5 to T8. The anticancer activity of these heavier tetraponerines against four different carcinoma human cell lines is examined, observing a promising cytotcodc activity of (+)-T7 against breast carcinoma cell line MCF-7.
• Concise and Stereoselective Syntheses of the Eight Natural Ant Defense Alkaloids (+)-Tetraponerine-1 to (+)-Tetraponerine-8 According to the CN(<i>R</i>,<i>S</i>) Strategy
  作者：Chongwei Yue、Isabelle Gauthier、Jacques Royer、Henri-Philippe Husson

  DOI：10.1021/jo960398a

  日期：1996.1.1

  The asymmetric syntheses of all the known defense alkaloids of the ant Tetraponera sp. tetraponerines T-1 to T-8 have been accomplished in five or six steps with 20-45% overall yields. The synthesis involved in the cross-condensation of (R)-piperidin-2-ylacetaldehyde with 4-aminobutyraldehyde which upon quenching by cyanide ion gave a stable tricyclic amino nitrile 3 with both a high yield and complete diastereoselectivity. This amino nitrile is the common precursor of four tetraponerines. A similar synthesis using (R)-pyrrolidine-2-ylacetaldehyde provided the tricyclic amino nitrile 2 precursor of the four other tetraponerines.