N-<(benzyloxy)carbonyl>-2-<(E)-5-(ethoxycarbonyl)-4-pentenyl>-2,3-dihydro-4-pyridone | 141584-02-3

• 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: N-<(benzyloxy)carbonyl>-2-<(E)-5-(ethoxycarbonyl)-4-pentenyl>-2,3-dihydro-4-pyridone
• 英文别名: benzyl 2-[(E)-6-ethoxy-6-oxohex-4-enyl]-4-oxo-2,3-dihydropyridine-1-carboxylate
• CAS: 141584-02-3
• 化学式: C₂₁H₂₅NO₅
• 分子量: 371.433
• InChiKey: RLVJWKJJNLGYMT-XYOKQWHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-<(benzyloxy)carbonyl>-2-<(E)-5-(ethoxycarbonyl)-4-pentenyl>-2,3-dihydro-4-pyridone 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 xylene 为溶剂， 反应 145.0h， 生成 N-<(benzyloxy)carbonyl>-11-(ethoxycarbonyl)-2-azatricyclo<5.3.1.03,8>undecan-9-one
  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 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 四氢呋喃 为溶剂， 生成 N-<(benzyloxy)carbonyl>-2-<(E)-5-(ethoxycarbonyl)-4-pentenyl>-2,3-dihydro-4-pyridone
  参考文献：
  名称：

  Dihydrolycolucine 全合成的研究。AB 和 CEF 环片段的制备

  摘要：

  已经研究了合成石松生物碱二氢番茄红素 ( 1 )的策略。合成路线是基于N-酰基吡啶盐化学开发的，以制备可最终收敛到天然产物的目标片段3和4。关键反应包括 IMDA 环加成和逆曼尼希开环以形成 AB 和 EF 环片段。使用吡啶取代和定向锂化化学制备环 C 前体。环 C 和 EF 的铃木交叉偶联导致 CEF 环片段。关闭七元 D 环的最初尝试没有成功。

  DOI：

  10.1021/jo500878v

文献信息

• Conversion of N-Acyl-2,3-dihydro-4-pyridones to 4-chloro-1,2-dihydropyridines using the Vilsmeier reagent.
  作者：Rima S. Al-awar、Sajan P. Joseph、Daniel L. Comins

  DOI：10.1016/0040-4039(93)88003-2

  日期：1992.12

  N-Acyl-2,3-dihydro-4-pyridones are converted to 1-acyl-4-chloro-1,2-dihydropyridines in one step using one equivalent of Vilsmeier reagent. This conversion was utilized in an asymmetric synthesis of (−)-coniine.

  使用一当量的Vilsmeier试剂一步将N-酰基-2,3-二氢-4-吡啶酮转化为1-酰基-4-氯-1,2-二氢吡啶。该转化被用于（-）-亚氨酸的不对称合成中。
• Conversion of N-acyl-2,3-dihydro-4-pyridones to 4-chloro-1,2-dihydropyridines using the Vilsmeier Reagent. Synthesis of (-)-coniine and (±)-lupinine
  作者：Rima S. Al-awar、Sajan P. Joseph、Daniel L. Comins

  DOI：10.1021/jo00079a018

  日期：1993.12

  The full details are given of a study on the conversion of dihydropyridones of the type 3 to 4-chloro-1,2-dihydropyridines 4 using a Vilsmeier reagent. The use of 1 equiv of Vilsmeier reagent under mild conditions (ClCHCCl2, rt) transformed several racemic N-acyl-2,3-dihydro-4-pyridones 3 to dihydropyridines 4 in very good to excellent yields (83-96%). A C-3 methyl group can be tolerated as was demonstrated in the preparation of 4-chloro-3-methyl-1,2-dihydropyridine 7 from dihydropyridone 6 in 90 % yield. The utility of this conversion was demonstrated in the synthesis of the piperidine alkaloid, (-)-coniine. The synthesis of (-)-coniine was completed in five steps from 4-methoxy-3-(triisopropylsilyl)pyridine in 54% overall yield. When 2,3-dihydro-4-pyridones are treated with excess Vilsmeier reagent, good yields of 4-chloro-3-formyl-1,2-dihydropyridines result. These heterocycles are useful intermediates for alkaloid preparation, as was shown by two syntheses of the quinolizidine alkaloid, (+/-)-lupinine, carried out in three and five steps, respectively.