(2S,3R,4aS,8aR)-3-(tert-Butyl-dimethyl-silanyloxy)-5-formyl-2-methyl-octahydro-quinoline-1-carboxylic acid tert-butyl ester | 782498-17-3

• 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,3R,4aS,8aR)-3-(tert-Butyl-dimethyl-silanyloxy)-5-formyl-2-methyl-octahydro-quinoline-1-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl (2S,3R,4aS,8aR)-3-[tert-butyl(dimethyl)silyl]oxy-5-formyl-2-methyl-3,4,4a,5,6,7,8,8a-octahydro-2H-quinoline-1-carboxylate
• CAS: 782498-17-3
• 化学式: C₂₂H₄₁NO₄Si
• 分子量: 411.657
• InChiKey: RJLHMEOQCWVLSX-DHVPZBTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.39
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 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：

  (2S,3R,4aS,8aR)-3-(tert-Butyl-dimethyl-silanyloxy)-5-formyl-2-methyl-octahydro-quinoline-1-carboxylic acid tert-butyl ester 在 四丁基氟化铵 、 双(三甲基硅烷基)氨基钾 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 二氯甲烷 、 苯 为溶剂， 反应 115.0h， 生成 (2S,4aS,5S,8aR)-2-Methyl-5-[(1E,3E)-6-(2-methyl-[1,3]dioxolan-2-yl)-hexa-1,3-dienyl]-3-oxo-octahydro-quinoline-1-carboxylic acid tert-butyl ester
  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：

  (2S,3R,4aR,8aR)-1-(tert-butoxycarbonyl)-2-methyl-3-(tert-butyldimethylsilyloxy)-5-oxodecahydroquinoline 在 水 、 sodium hexamethyldisilazane 、 三氯乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 (2S,3R,4aS,8aR)-3-(tert-Butyl-dimethyl-silanyloxy)-5-formyl-2-methyl-octahydro-quinoline-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Lepadins B，d，e和h的全合成；确定后三种生物碱的构型。

  摘要：

  DOI：

  10.1002/anie.200460128

文献信息

• Total Synthesis of Lepadins B, D, E, and H; Determination of the Configuration of the Latter Three Alkaloids
  作者：Xiaotao Pu、Dawei Ma

  DOI：10.1002/anie.200460128

  日期：2004.8.13
• 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.