(2S,3R,4aS,5R,8aR)-2-methyl-3-(tert-butyldimethylsilyloxy)-5-[(ethoxycarbonyl)methyl]decahydroquinoline | 782498-24-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2S,3R,4aS,5R,8aR)-2-methyl-3-(tert-butyldimethylsilyloxy)-5-[(ethoxycarbonyl)methyl]decahydroquinoline
• 英文别名: ethyl 2-[(2S,3R,4aS,5R,8aR)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-1,2,3,4,4a,5,6,7,8,8a-decahydroquinolin-5-yl]acetate
• CAS: 782498-24-2
• 化学式: C₂₀H₃₉NO₃Si
• 分子量: 369.62
• InChiKey: KNVAITXWIJGYCJ-IGKNDFSCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3R,4aS,5R,8aR)-2-methyl-3-(tert-butyldimethylsilyloxy)-5-[(ethoxycarbonyl)methyl]decahydroquinoline 在 palladium on activated charcoal 草酰氯 、 氢气 、 sodium hexamethyldisilazane 、 二异丁基氢化铝 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 78.5h， 生成 (2S,3R,4aS,5S,8aR)-1-(tert-butoxycarbonyl)-2-methyl-3-(tert-butyldimethylsilyloxy)-5-[(5R)-5-(methoxymethoxy)octan-1-yl]decahydroquinoline
  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
• 作为产物：
  描述：

  [(2S,3R,4aS,8aR)-3-(tert-Butyl-dimethyl-silanyloxy)-2-methyl-octahydro-quinolin-(5E)-ylidene]-acetic acid ethyl ester 在 platinum on activated charcoal 氢气 作用下， 20.0 ℃ 、101.32 kPa 条件下， 反应 6.0h， 以351 mg的产率得到(2S,3R,4aS,5R,8aR)-2-methyl-3-(tert-butyldimethylsilyloxy)-5-[(ethoxycarbonyl)methyl]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

• 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.