(4S,5R)-(-)-1-(2-(2-Benzyloxy-3,4-dimethoxyphenyl)-ethyl)-5-ethyl-2-oxo-4-piperidineacetic Acid | 57103-66-9

• 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: (4S,5R)-(-)-1-(2-(2-Benzyloxy-3,4-dimethoxyphenyl)-ethyl)-5-ethyl-2-oxo-4-piperidineacetic Acid
• 英文别名: (4S,5R)-(-)-1-(2-benzyloxy-3,4-dimethoxyphenethyl)-5-ethyl-2-oxo-4-piperidineacetic acid；(4S,5R)-(-)-1-[2-(2-Benzyloxy-3,4-dimethoxyphenyl)-ethyl]-5-ethyl-2-oxo-4-piperidineacetic Acid；2-[(4S,5R)-1-[2-(3,4-dimethoxy-2-phenylmethoxyphenyl)ethyl]-5-ethyl-2-oxopiperidin-4-yl]acetic acid
• CAS: 57103-66-9
• 化学式: C₂₆H₃₃NO₆
• 分子量: 455.551
• InChiKey: SWIAEPJOFUPCLD-FPOVZHCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  85.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4S,5R)-(-)-1-(2-(2-Benzyloxy-3,4-dimethoxyphenyl)-ethyl)-5-ethyl-2-oxo-4-piperidineacetic Acid 生成 [1-(2-benzyloxy-3,4-dimethoxy-phenethyl)-5-ethyl-2-oxo-piperidin-4-yl]-acetic acid
  参考文献：
  名称：

  FUJII, TOZO;OHBA, MASASHI;YOSHIFUJI, SHIGEYUKI;AKIYAMA, SHIGEAKI, HETEROCYCLES, 1984, 21, N 2, 647

  摘要：

  DOI：
• 作为产物：
  描述：

  ethyl cincholoiponate 在 sodium hydroxide 、 sodium tetrahydroborate 、 palladium on activated charcoal 、 高氯酸 、 mercury(II) diacetate 、 氢气 、 EDTA di-sodium salt dihydrate 、 potassium carbonate 作用下， 以 乙醇 、 水 、 溶剂黄146 、 丙酮 、 苯 为溶剂， 反应 45.5h， 生成 (4S,5R)-(-)-1-(2-(2-Benzyloxy-3,4-dimethoxyphenyl)-ethyl)-5-ethyl-2-oxo-4-piperidineacetic Acid
  参考文献：
  名称：

  Quinolizidines. 6. Absolute stereochemistry of ankorine: synthetic incorporation of ethyl cincholoiponate into (-)-ankorine

  摘要：

  DOI：

  10.1021/jo01298a025

文献信息

• Lactams. XXIII. Thermal cis-trans isomerization of the 5-ethyl-2-oxo-4-piperidineacetic acid system: Effect of an N-substituent.
  作者：TOZO FUJII、MASASHI OHBA、SHIGEYUKI YOSHIFUJI、SHIGEAKI AKIYAMA

  DOI：10.1248/cpb.33.1062

  日期：——

  In order to investigate the effect of an N-substituent on thermal cis-trans isomerization of the 5-ethyl-2-oxo-4-piperidineacetic acid system, the N-alkyl analogs (±)-1b, c and (±)-2b, c and the N-(2-arylethyl) analogs (-)-1f, g, i and (+)-2f, g, i were separately heated neat at 180°C, and the propress of their cis-trans isomerization reactions was followed by determining the isomer ratios in the reaction mixtures according to the previously reported C-13 nuclear magnetic resonance spectroscopic method. It has been found that in all cases the reaction comes to equilibrium within 28-130 min, when the cis and trans isomers exist in a ration of 1 : 2. These results together with those obtained previously with the analogs (±)-1a, d, e, (-)-1h, (±)-2a, d, e, and (+)-2h indicate that a higher and/or bulkier N-substituent tends to decrease the rate of cis-trans isomerization of the 5-ethyl-2-oxo-4-piperidineacetic acid system, which is a useful synthon for the synthesis of benzo-[a] quinolizidine-type Alangium alkaloids. Among the substrates used in the present equilibration study, (±)-1b, c and (±)-2b, c were prepared from the corresponding N-unsubstituted lactam esters (±)-3 and (±)-7 by the"lactim ether method."

  为了研究 N-取代基对 5-乙基-2-氧代-4-哌啶乙酸体系热顺反异构化的影响，将 N-烷基类似物 (±)-1b, c 和 (±)-2b, c 以及 N-(2-芳基乙基)类似物 (-)-1f, g, i 和 (+)-2f, g. i 分别在 180°C 下纯净加热，并根据之前报道的 C-13 核磁共振法测定反应混合物中的异构体比率，跟踪它们的顺反异构化反应的进展、i 分别在 180°C 温度下加热，并根据之前报告的 C-13 核磁共振光谱法确定反应混合物中的异构体比率，从而跟踪它们顺反异构化反应的进展情况。结果发现，在所有情况下，当顺式和反式异构体的比例为 1 : 2 时，反应在 28 至 130 分钟内达到平衡。这些结果以及之前在类似物 (±)-1a、d、e、(-)-1h、(±)-2a、d、e 和 (+)-2h 中获得的结果表明，较高和/或较宽松的 N 取代基往往会降低 5-乙基-2-氧代-4-哌啶乙酸体系的顺反异构化速率，而该体系是合成苯并-[a] 喹嗪类阿兰生物碱的有效合成物。在本平衡研究中使用的底物中，(±)-1b, c 和 (±)-2b, c 是通过 "乳醚法 "从相应的 N-未取代内酰胺酯 (±)-3 和 (±)-7 制备的。
• Lactams. XXIV. Alkaline hydrolysis of 1-benzyl-2-piperidone derivatives: Application to cis-trans isomerization of the 5-ethyl-2-oxo-4-piperidineacetic acid system.
  作者：TOZO FUJII、MASASHI OHBA、SHIGEAKI AKIYAMA

  DOI：10.1248/cpb.33.1716

  日期：——

  In boiling 2.5 N solution of KOH in 40% (w/w) aqueous EtOH, the lactams (±)-5a, b, d were hydrolyzed to an extent of 75-98% within 8-20 h, attaining equilibrium with the corresponding ω-amino acid derivatives (±)-6a, b, d. The potassium salt (±)-8, generated in situ from the translactam acid (±)-7, was equilibrated with the ring-opened product (±)-6f and the recyclized cis isomer (±)-5f in a ratio of 57 : 15 : 28 within ca. 45 h under similar reaction conditions. The cis-N-(2-arylethyl) analog (-)-9 was converted into the trans-lactam acid (+)-13, a key synthetic precursor for the 8-hydroxy-9, 10-dimethoxybenzo [a] quinolizidine-type Alangium alkaloids, through application of such alkaline hydrolytic cis-trans equilibration followed by debenzylation.

  在 40% (w/w) EtOH 水溶液中煮沸 2.5 N KOH 溶液中，内酰胺 (±)-5a、b、d 在 8-20 小时内水解至 75-98%，与相应的内酰胺达到平衡。 ω-氨基酸衍生物(±)-6a、b、d。由反式内酰胺酸(±)-7原位生成的钾盐(±)-8与开环产物(±)-6f和回收的顺式异构体(±)-5f以57的比例进行平衡: 15 : 28 内约。在相似的反应条件下45小时。顺式-N-(2-芳基乙基)类似物(-)-9被转化为反式-内酰胺酸(+)-13，这是8-羟基-9, 10-二甲氧基苯并[a]喹里西啶-的关键合成前体。八角豆生物碱，通过应用这种碱性水解顺反平衡，然后脱苄基。
• Quinolizidines. 6. Absolute stereochemistry of ankorine: synthetic incorporation of ethyl cincholoiponate into (-)-ankorine
  作者：Tozo Fujii、Shigeyuki Yoshifuji

  DOI：10.1021/jo01298a025

  日期：1980.5
• FUJII, TOZO;OHBA, MASASHI;YOSHIFUJI, SHIGEYUKI;AKIYAMA, SHIGEAKI, HETEROCYCLES, 1984, 21, N 2, 647
  作者：FUJII, TOZO、OHBA, MASASHI、YOSHIFUJI, SHIGEYUKI、AKIYAMA, SHIGEAKI

  DOI：——

  日期：——