1,4,4a,5,6,7,8,8a-octahydro-1-<(benzyloxy)carbonyl>-5-<1-(ethoxycarbonyl)methyl>quinoline | 141584-07-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,4,4a,5,6,7,8,8a-octahydro-1-<(benzyloxy)carbonyl>-5-<1-(ethoxycarbonyl)methyl>quinoline
• 英文别名: benzyl (4aR,5S,8aS)-5-(2-ethoxy-2-oxoethyl)-4a,5,6,7,8,8a-hexahydro-4H-quinoline-1-carboxylate
• CAS: 141584-07-8
• 化学式: C₂₁H₂₇NO₄
• 分子量: 357.45
• InChiKey: XMCSJYHPSNDQCM-OTWHNJEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4,4a,5,6,7,8,8a-octahydro-1-<(benzyloxy)carbonyl>-5-<1-(ethoxycarbonyl)methyl>quinoline 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 4.0h， 以97%的产率得到1,2,3,4,4a,5,6,7,8,8a-decahydro-5-<1-(ethoxycarbonyl)methyl>quinoline
  参考文献：
  名称：

  An intramolecular Diels-Alder/retro-Mannich approach to the cis-perhydroquinoline ring system. Model studies toward the synthesis of Lycopodium alkaloids

  摘要：

  Model studies toward the preparation of cis-decahydroquinoline derivatives using an IMDA/retro-Mannich strategy were carried out. Tricyclic amino ester 13, prepared via an IMDA reaction of 1,2-dihydropyridine 11, was ring-opened on treatment with excess LDA. Trapping the intermediate dianion 17 with TMSCl gave the polysilylated derivatives 18. Subsequent N-acylation with benzyl chloroformate provided ene carbamate 19, which on catalytic hydrogenation gave the desired decahydroquinoline 21. In a similar manner, 1,2-dihydropyridine 22 was cyclized and ring-opened in two steps to give the desired cis-hexahydroquinolone 25. N-Acylation of 25 with LDA and benzyl chloroformate provided the benzyl carbamate 26 in quantitative yield. The target model compounds, 21 and 26, were prepared with complete control of relative stereochemistry at their three contiguous stereogenic centers. The mechanisms for the retro-Mannich ring-openings are discussed.

  DOI：

  10.1021/jo00041a011
• 作为产物：
  描述：

  氯甲酸苄酯 、 11-(ethoxycarbonyl)-2-azatricyclo<5.3.1.03,8>undecane 生成 1,4,4a,5,6,7,8,8a-octahydro-1-<(benzyloxy)carbonyl>-5-<1-(ethoxycarbonyl)methyl>quinoline 、 (1R,4aS,5R,6R,8aR)-Decahydro-1,6-epiazano-naphthalene-5,9-dicarboxylic acid 9-benzyl ester 5-ethyl ester
  参考文献：
  名称：

  An intramolecular Diels-Alder/retro-Mannich approach to the cis-perhydroquinoline ring system. Model studies toward the synthesis of Lycopodium alkaloids

  摘要：

  Model studies toward the preparation of cis-decahydroquinoline derivatives using an IMDA/retro-Mannich strategy were carried out. Tricyclic amino ester 13, prepared via an IMDA reaction of 1,2-dihydropyridine 11, was ring-opened on treatment with excess LDA. Trapping the intermediate dianion 17 with TMSCl gave the polysilylated derivatives 18. Subsequent N-acylation with benzyl chloroformate provided ene carbamate 19, which on catalytic hydrogenation gave the desired decahydroquinoline 21. In a similar manner, 1,2-dihydropyridine 22 was cyclized and ring-opened in two steps to give the desired cis-hexahydroquinolone 25. N-Acylation of 25 with LDA and benzyl chloroformate provided the benzyl carbamate 26 in quantitative yield. The target model compounds, 21 and 26, were prepared with complete control of relative stereochemistry at their three contiguous stereogenic centers. The mechanisms for the retro-Mannich ring-openings are discussed.

  DOI：

  10.1021/jo00041a011