(2S,3S,4aS,5S,8aR)-1-(tert-butyloxycarbonyl)-2-methyl-3-hydroxy-5-[(1E,3E)-7,7-(ethylenedioxy)octadien-1-yl]decahydroquinoline | 910030-48-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉类
• 英文名称: (2S,3S,4aS,5S,8aR)-1-(tert-butyloxycarbonyl)-2-methyl-3-hydroxy-5-[(1E,3E)-7,7-(ethylenedioxy)octadien-1-yl]decahydroquinoline
• 英文别名: (2S,3S,4aS,5S,8aR)-1-(tert-butoxycarbonyl)-5-[(1E,3E)-7,7-(ethylenedioxy)-1,3-octadienyl]-3-hydroxy-2-methyldecahydroquinoline；tert-butyl (2S,3S,4aS,5S,8aR)-3-hydroxy-2-methyl-5-[(1E,3E)-6-(2-methyl-1,3-dioxolan-2-yl)hexa-1,3-dienyl]-3,4,4a,5,6,7,8,8a-octahydro-2H-quinoline-1-carboxylate
• CAS: 910030-48-7
• 化学式: C₂₅H₄₁NO₅
• 分子量: 435.604
• InChiKey: FBXVIPPULMJQQZ-MEBYCPAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  68.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,3S,4aS,5S,8aR)-1-(tert-butyloxycarbonyl)-2-methyl-3-hydroxy-5-[(1E,3E)-7,7-(ethylenedioxy)octadien-1-yl]decahydroquinoline 在 4-二甲氨基吡啶 、 三氟化硼乙醚 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 lepadin C
  参考文献：
  名称：

  Facile Entry to Substituted Decahydroquinoline Alkaloids. Total Synthesis of Lepadins A−E and H

  摘要：

  Condensation of a L-alanine derived delta-bromo-beta-silyloxy-propylamine with 1,3-cyclohexadione followed by alkylative cyclization produces a bicyclic enone. Diastereoselective Pt/C-catalyzed hydrogenation of this enone in HOAc provides a 5-oxo-cis-fused decahydroquinoline. Wittig olefination of this decahydroquinoline and subsequent epimerization of the resulting 5-formyl intermediate gives rise to a 5-beta-formyl decahydroquinoline exclusively. In a parallel procedure, Peterson reaction of this decahydroquinoline and subsequent hydrogenation of the generated 5-exo-olefin provides a decahydroquinoline with a 5-alpha-substituent predominantly. For these two diastereoselective processes, using the intermediates without N-protection as the substrates is essential because the corresponding N-Boc intermediates give poor diastereoselectivity. The intermediate with beta-form side chain is further converted into lepadins A-C via carbon chain elongation, while the intermediate with alpha-form side chain is transformed into lepadins D, E, and H and corresponding 5'-epimers via connection with two sulfones generated from two Sharpless epoxidation products. By comparison of the rotations and NMR data, the stereochemistry of lepadins D, E, and H is assigned as 2S, 3R, 4aS, 5S, 8aR, 5'R.

  DOI：

  10.1021/jo061070c
• 作为产物：
  描述：

  6-甲基-5-庚烯-2-酮 在 咪唑 、 sodium tetrahydroborate 、 四溴化碳 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 臭氧 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 乙二醇二甲醚 、 二氯甲烷 、 乙腈 、 苯 为溶剂， 反应 115.6h， 生成 (2S,3S,4aS,5S,8aR)-1-(tert-butyloxycarbonyl)-2-methyl-3-hydroxy-5-[(1E,3E)-7,7-(ethylenedioxy)octadien-1-yl]decahydroquinoline
  参考文献：
  名称：

  Facile Entry to Substituted Decahydroquinoline Alkaloids. Total Synthesis of Lepadins A−E and H

  摘要：

  Condensation of a L-alanine derived delta-bromo-beta-silyloxy-propylamine with 1,3-cyclohexadione followed by alkylative cyclization produces a bicyclic enone. Diastereoselective Pt/C-catalyzed hydrogenation of this enone in HOAc provides a 5-oxo-cis-fused decahydroquinoline. Wittig olefination of this decahydroquinoline and subsequent epimerization of the resulting 5-formyl intermediate gives rise to a 5-beta-formyl decahydroquinoline exclusively. In a parallel procedure, Peterson reaction of this decahydroquinoline and subsequent hydrogenation of the generated 5-exo-olefin provides a decahydroquinoline with a 5-alpha-substituent predominantly. For these two diastereoselective processes, using the intermediates without N-protection as the substrates is essential because the corresponding N-Boc intermediates give poor diastereoselectivity. The intermediate with beta-form side chain is further converted into lepadins A-C via carbon chain elongation, while the intermediate with alpha-form side chain is transformed into lepadins D, E, and H and corresponding 5'-epimers via connection with two sulfones generated from two Sharpless epoxidation products. By comparison of the rotations and NMR data, the stereochemistry of lepadins D, E, and H is assigned as 2S, 3R, 4aS, 5S, 8aR, 5'R.

  DOI：

  10.1021/jo061070c

文献信息

• Enantioselective Synthesis of Lepadins A-D from a Phenylglycinol-Derived Hydroquinolone Lactam
  作者：Mercedes Amat、Alexandre Pinto、Rosa Griera、Joan Bosch

  DOI：10.1002/chem.201501909

  日期：2015.9.1

  The marine alkaloids (−)‐lepadins A–C and (+)‐lepadin D, belonging to two diastereoisomeric series, were synthesized from an (R)‐phenylglycinol‐derived tricyclic lactam via a common cis‐decahydroquinoline intermediate. Crucial aspects of the synthesis are the stereochemical control in the assembly of the cis‐decahydroquinoline platform, in the introduction of the C2 methyl and C3 hydroxy substituents

  属于两个非对映异构系列的海洋生物碱（-）-lepadins A-C和（+）-lepadin D是由（R）-苯甘氨醇衍生的三环内酰胺通过一种常见的顺式-十氢喹啉中间体合成的。合成的关键方面是在顺式十氢喹啉平台的组装，C2甲基和C3羟基取代基的引入以及C5立体中心的生成中的立体化学控制。
• Facile Entry to Substituted Decahydroquinoline Alkaloids. Total Synthesis of Lepadins A−E and H
  作者：Xiaotao Pu、Dawei Ma

  DOI：10.1021/jo061070c

  日期：2006.8.1

  Condensation of a L-alanine derived delta-bromo-beta-silyloxy-propylamine with 1,3-cyclohexadione followed by alkylative cyclization produces a bicyclic enone. Diastereoselective Pt/C-catalyzed hydrogenation of this enone in HOAc provides a 5-oxo-cis-fused decahydroquinoline. Wittig olefination of this decahydroquinoline and subsequent epimerization of the resulting 5-formyl intermediate gives rise to a 5-beta-formyl decahydroquinoline exclusively. In a parallel procedure, Peterson reaction of this decahydroquinoline and subsequent hydrogenation of the generated 5-exo-olefin provides a decahydroquinoline with a 5-alpha-substituent predominantly. For these two diastereoselective processes, using the intermediates without N-protection as the substrates is essential because the corresponding N-Boc intermediates give poor diastereoselectivity. The intermediate with beta-form side chain is further converted into lepadins A-C via carbon chain elongation, while the intermediate with alpha-form side chain is transformed into lepadins D, E, and H and corresponding 5'-epimers via connection with two sulfones generated from two Sharpless epoxidation products. By comparison of the rotations and NMR data, the stereochemistry of lepadins D, E, and H is assigned as 2S, 3R, 4aS, 5S, 8aR, 5'R.