[(4aS,6S,8aS)-2-[2-(1H-indol-3-yl)ethyl]-3-oxo-1,4,4a,5,6,8a-hexahydroisoquinolin-6-yl] 2,2-dimethylpropanoate | 158146-60-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: [(4aS,6S,8aS)-2-[2-(1H-indol-3-yl)ethyl]-3-oxo-1,4,4a,5,6,8a-hexahydroisoquinolin-6-yl] 2,2-dimethylpropanoate
• CAS: 158146-60-2
• 化学式: C₂₄H₃₀N₂O₃
• 分子量: 394.514
• InChiKey: GBBOSHIBHXTWBG-GBESFXJTSA-N

物化性质

• 沸点：
  587.1±50.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  62.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [(4aS,6S,8aS)-2-[2-(1H-indol-3-yl)ethyl]-3-oxo-1,4,4a,5,6,8a-hexahydroisoquinolin-6-yl] 2,2-dimethylpropanoate 在 palladium on activated charcoal 甲醇 、 六甲基磷酰三胺 、 sodium hydroxide 、 sodium tetrahydroborate 、 四丙基高钌酸铵 、 乙醇 、 4 A molecular sieve 、 氢气 、 L-Selectride 、 potassium carbonate 、 N-甲基吗啉氧化物 、 lithium diisopropyl amide 、 三氯氧磷 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 37.75h， 生成 育亨宾
  参考文献：
  名称：

  Symmetry-Driven Synthesis of Indole Alkaloids: Asymmetric Total Syntheses of (+)-Yohimbine, (-)-Yohimbone, (-)-Yohimbane, and (+)-Alloyohimbane

  摘要：

  Total asymmetric syntheses of the target alkaloids are reported. The syntheses involve the preparation of enantiomerically pure (S,S)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one 7 and its meso isomer 5. Each ketone is then converted into a ring-expanded lactam using an oxaziridine synthesis/rearrangement protocol. The applications of Bischler-Napieralski ring constructions along with appropriate functional group transformations afford enantiomerically enriched alloyohimbane or yohimbane from the meso- or C-2-symmetric ketones, respectively. A cis-5,6-diacetoxy compound (18) derived from the (S,S)-ketone served as the starting material for the total syntheses of the more highly functionalized alkaloids. Accordingly, a site-specific insertion of the indole-containing side chain was accomplished via stereoselective formation of an oxaziridine followed by its stereospecific rearrangement. The selectivity of this sequence allowed for the differentiation of alcohols at C-17 and C-18 (yohimbine numbering) and the synthesis of Delta 18,19-yohimbone. This alpha,beta-unsaturated ketone was converted into either (-)-yohimbone or (+)-yohimbine using standard chemistry.

  DOI：

  10.1021/ja00099a019
• 作为产物：
  描述：

  [(4aS,6S,7R,8aR)-7-hydroxy-2-[2-(1H-indol-3-yl)ethyl]-3-oxo-1,4,4a,5,6,7,8,8a-octahydroisoquinolin-6-yl] 2,2-dimethylpropanoate 在 SPh2 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以63%的产率得到[(4aS,6S,8aS)-2-[2-(1H-indol-3-yl)ethyl]-3-oxo-1,4,4a,5,6,8a-hexahydroisoquinolin-6-yl] 2,2-dimethylpropanoate
  参考文献：
  名称：

  Symmetry-Driven Synthesis of Indole Alkaloids: Asymmetric Total Syntheses of (+)-Yohimbine, (-)-Yohimbone, (-)-Yohimbane, and (+)-Alloyohimbane

  摘要：

  Total asymmetric syntheses of the target alkaloids are reported. The syntheses involve the preparation of enantiomerically pure (S,S)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one 7 and its meso isomer 5. Each ketone is then converted into a ring-expanded lactam using an oxaziridine synthesis/rearrangement protocol. The applications of Bischler-Napieralski ring constructions along with appropriate functional group transformations afford enantiomerically enriched alloyohimbane or yohimbane from the meso- or C-2-symmetric ketones, respectively. A cis-5,6-diacetoxy compound (18) derived from the (S,S)-ketone served as the starting material for the total syntheses of the more highly functionalized alkaloids. Accordingly, a site-specific insertion of the indole-containing side chain was accomplished via stereoselective formation of an oxaziridine followed by its stereospecific rearrangement. The selectivity of this sequence allowed for the differentiation of alcohols at C-17 and C-18 (yohimbine numbering) and the synthesis of Delta 18,19-yohimbone. This alpha,beta-unsaturated ketone was converted into either (-)-yohimbone or (+)-yohimbine using standard chemistry.

  DOI：

  10.1021/ja00099a019

文献信息

• Symmetry-Driven Synthesis of Indole Alkaloids: Asymmetric Total Syntheses of (+)-Yohimbine, (-)-Yohimbone, (-)-Yohimbane, and (+)-Alloyohimbane
  作者：Jeffrey Aube、Shomir Ghosh、Mehmet Tanol

  DOI：10.1021/ja00099a019

  日期：1994.10

  Total asymmetric syntheses of the target alkaloids are reported. The syntheses involve the preparation of enantiomerically pure (S,S)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one 7 and its meso isomer 5. Each ketone is then converted into a ring-expanded lactam using an oxaziridine synthesis/rearrangement protocol. The applications of Bischler-Napieralski ring constructions along with appropriate functional group transformations afford enantiomerically enriched alloyohimbane or yohimbane from the meso- or C-2-symmetric ketones, respectively. A cis-5,6-diacetoxy compound (18) derived from the (S,S)-ketone served as the starting material for the total syntheses of the more highly functionalized alkaloids. Accordingly, a site-specific insertion of the indole-containing side chain was accomplished via stereoselective formation of an oxaziridine followed by its stereospecific rearrangement. The selectivity of this sequence allowed for the differentiation of alcohols at C-17 and C-18 (yohimbine numbering) and the synthesis of Delta 18,19-yohimbone. This alpha,beta-unsaturated ketone was converted into either (-)-yohimbone or (+)-yohimbine using standard chemistry.