(3aS,7aS)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one | 158250-03-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aS,7aS)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one
• 英文别名: 8-Oxo-trans-bicyclo<4.3.0>nonen-3；(3aS,7aS)-1,3,3a,4,7,7a-hexahydroinden-2-one
• CAS: 158250-03-4
• 化学式: C₉H₁₂O
• 分子量: 136.194
• InChiKey: XTHWLHROZDWGOU-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3aS,7aS)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one 在 N-甲基吗啉 、 吡啶 、 4-二甲氨基吡啶 、 四氧化锇 作用下， 以 水 、 丙酮 、 甲苯 为溶剂， 反应 18.0h， 生成 (3aS,5R,6S,7aS)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one
  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：

  (+/-)-(trans-cyclohex-4-ene-1,2-diyl)-di-acetonitrile 在 氢氧化钾 、 sodium hydride 、 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 81.0h， 生成 (3aS,7aS)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one
  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.