(4aS,5R,8aR)-5-Methyl-2-propyl-3-(toluene-4-sulfonyl)-4a,5,6,7,8,8a-hexahydro-1H-quinolin-4-one | 213838-20-1

• 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: (4aS,5R,8aR)-5-Methyl-2-propyl-3-(toluene-4-sulfonyl)-4a,5,6,7,8,8a-hexahydro-1H-quinolin-4-one
• 英文别名: (4aS,5R,8aR)-5-methyl-3-(4-methylphenyl)sulfonyl-2-propyl-4a,5,6,7,8,8a-hexahydro-1H-quinolin-4-one
• CAS: 213838-20-1
• 化学式: C₂₀H₂₇NO₃S
• 分子量: 361.505
• InChiKey: YNQDDUVNMIEQLI-KYJSFNMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  71.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4aS,5R,8aR)-5-Methyl-2-propyl-3-(toluene-4-sulfonyl)-4a,5,6,7,8,8a-hexahydro-1H-quinolin-4-one 在 platinum(IV) oxide 、 palladium on activated charcoal disodium hydrogenphosphate 、 sodium amalgam 、 氢气 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 氯仿 为溶剂， 25.0 ℃ 、10.13 MPa 条件下， 反应 174.5h， 生成 箭毒蛙毒素 C
  参考文献：
  名称：

  Enantioselective Synthesis of (−)-Pumiliotoxin C from a Chiral Amino Ester and an Acetylenic Sulfone that Acts as an Alkene Dipole Equivalent

  摘要：

  A new synthesis of the naturally occurring (-)-enantiomer of the dendrobatid alkaloid pumiliotoxin C (1) was achieved by the conjugate addition of methyl (-)-cis-2-amino-trans-6-methylcyclohexanecarboxylate (3) to 1-(p-toluenesulfonyl)-1-pentyne (4), followed by intramolecular acylation to afford (4aS,5R,8aR)-4a,5,6,7,8,8a-hexahydro-5-methyl-2-propyl-3-(p-toluenesulfonyl)-4-quinolinone (2). The acetylenic sulfone thus acts as the synthetic equivalent of an alkene dipole species. The required enantiopure amino ester 3 was obtained by an approach based on pig liver esterase (PLE)-mediated hydrolysis. Thus, the (-)- and (+)-enantiomers of racemic dimethyl trans-3-methylcyclohexane-cis,cis-1,2-dicarboxylate (6) afforded the corresponding half-esters 7 and 8, respectively, when treated with PLE. The desired half-ester 7 was recovered intact after selective conversion of the free carboxylic acid group of the byproduct 8 into its benzyl ester. Half-ester 7 was converted into enantiopure (-)-6 with diazomethane, followed by regioselective saponification and Curtius rearrangement to afford the required enantiopure key intermediate 3. Finally, hydrogenation of the enol triflate of enaminone 2, followed by reductive desulfonylation, afforded the product (-)-1.

  DOI：

  10.1021/jo980647q
• 作为产物：
  描述：

  (1S,2R,6R)-2-Methyl-6-{1-[1-(toluene-4-sulfonyl)-meth-(Z)-ylidene]-butylamino}-cyclohexanecarboxylic acid methyl ester 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以50%的产率得到(4aS,5R,8aR)-5-Methyl-2-propyl-3-(toluene-4-sulfonyl)-4a,5,6,7,8,8a-hexahydro-1H-quinolin-4-one
  参考文献：
  名称：

  Enantioselective Synthesis of (−)-Pumiliotoxin C from a Chiral Amino Ester and an Acetylenic Sulfone that Acts as an Alkene Dipole Equivalent

  摘要：

  A new synthesis of the naturally occurring (-)-enantiomer of the dendrobatid alkaloid pumiliotoxin C (1) was achieved by the conjugate addition of methyl (-)-cis-2-amino-trans-6-methylcyclohexanecarboxylate (3) to 1-(p-toluenesulfonyl)-1-pentyne (4), followed by intramolecular acylation to afford (4aS,5R,8aR)-4a,5,6,7,8,8a-hexahydro-5-methyl-2-propyl-3-(p-toluenesulfonyl)-4-quinolinone (2). The acetylenic sulfone thus acts as the synthetic equivalent of an alkene dipole species. The required enantiopure amino ester 3 was obtained by an approach based on pig liver esterase (PLE)-mediated hydrolysis. Thus, the (-)- and (+)-enantiomers of racemic dimethyl trans-3-methylcyclohexane-cis,cis-1,2-dicarboxylate (6) afforded the corresponding half-esters 7 and 8, respectively, when treated with PLE. The desired half-ester 7 was recovered intact after selective conversion of the free carboxylic acid group of the byproduct 8 into its benzyl ester. Half-ester 7 was converted into enantiopure (-)-6 with diazomethane, followed by regioselective saponification and Curtius rearrangement to afford the required enantiopure key intermediate 3. Finally, hydrogenation of the enol triflate of enaminone 2, followed by reductive desulfonylation, afforded the product (-)-1.

  DOI：

  10.1021/jo980647q