(E)-4-methylenehex-2-enal | 76251-90-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-4-methylenehex-2-enal
• 英文别名: 4-ethyl-2,4-pentadienal；(E)-4-methylidenehex-2-enal
• CAS: 76251-90-6
• 化学式: C₇H₁₀O
• 分子量: 110.156
• InChiKey: WSWNANHLCNHTIC-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  (E)-4-methylenehex-2-enal 在 palladium on activated charcoal 四氧化锇 、 钾硼氢 、 四丁基氟化铵 、 氨 、 氢气 、 ammonium formate 、 potassium carbonate 、 三乙胺 、 对苯二酚 、 苯甲酸 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 乙醇 、 二氯甲烷 、 乙酸乙酯 、 苯 为溶剂， 反应 56.67h， 生成 20-epi-lochneridine
  参考文献：
  名称：

  Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 11. Total Syntheses of (−)-Lochneridine and (−)- and Racemic 20-epi-Lochneridine

  摘要：

  Enantioselective syntheses of (-)-lochneridine (1) and (-)-epi-lochneridine (2) were obtained by two alternative C-20 diastereoselective syntheses of the respective pentacyclic (3aS,5S,11bR)-methyl 12-oxo-3,5-ethano-2,3,3a,4,5,7-hexahydro-3H-pyrrolo[2,3-d]carbazole-6-carboxylate ((-)-8) and tetracyclic methyl (2S,3aS,5R,11bR))-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(2-(1-butenyl))-1H-pyrrolo[2,3d]carbazole-6-carboxylate ((-)-12b) precursors from tryptophan derived 2-[(methoxycarbonyl)methyl]3-[2(S)-(methoxy or benzyloxycarbonyl)-2-(N-b-benzyl)aminoethyl]indole (15 or 16). While a modified Grignard reaction of the ketone (-)-8 provided (-)-lochneridine (1), dihydroxylation and cyclization of the olefin (-)-12b gave its C-20 epimer (2).

  DOI：

  10.1021/jo981401o
• 作为产物：
  描述：

  4-ethyl-2,4-pentadienol 在 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到(E)-4-methylenehex-2-enal
  参考文献：
  名称：

  Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 11. Total Syntheses of (−)-Lochneridine and (−)- and Racemic 20-epi-Lochneridine

  摘要：

  Enantioselective syntheses of (-)-lochneridine (1) and (-)-epi-lochneridine (2) were obtained by two alternative C-20 diastereoselective syntheses of the respective pentacyclic (3aS,5S,11bR)-methyl 12-oxo-3,5-ethano-2,3,3a,4,5,7-hexahydro-3H-pyrrolo[2,3-d]carbazole-6-carboxylate ((-)-8) and tetracyclic methyl (2S,3aS,5R,11bR))-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(2-(1-butenyl))-1H-pyrrolo[2,3d]carbazole-6-carboxylate ((-)-12b) precursors from tryptophan derived 2-[(methoxycarbonyl)methyl]3-[2(S)-(methoxy or benzyloxycarbonyl)-2-(N-b-benzyl)aminoethyl]indole (15 or 16). While a modified Grignard reaction of the ketone (-)-8 provided (-)-lochneridine (1), dihydroxylation and cyclization of the olefin (-)-12b gave its C-20 epimer (2).

  DOI：

  10.1021/jo981401o

文献信息

• Catalytic Regioselective γ-Methylenation of α,β-Unsaturated Aldehydes Using Formaldehyde via Vinylogous Aldol Condensation
  作者：Mahesh S. Kutwal、Sachin Dev、Chandrakumar Appayee

  DOI：10.1021/acs.orglett.8b04110

  日期：2019.4.19

  first vinylogous aldol condensation of α,β-unsaturated aldehydes using aqueous formaldehyde is developed under mild reaction conditions to form the γ-methylenated products with excellent regioselectivity. Using this methodology, a short synthesis of α-triticene, an antifungal compound, is achieved in two steps. The practicality of this methodology is demonstrated by the gram-scale synthesis. Formation of

  在温和的反应条件下，使用甲醛水溶液进行的α，β-不饱和醛的首个乙烯基醇醛缩合反应，形成了具有良好区域选择性的γ-甲基化产物。使用这种方法，可以在两个步骤中完成抗真菌化合物α-三苯甲基的短合成。这种方法的实用性由克级综合证明。还描述了由巴豆醛形成的不寻常的双γ-官能化产物和由苯乙二醛形成的直接不对称乙烯基醇醛醇产物。
• Palladium-catalyzed three carbon chain extension reactions with acrolein acetals. A convenient synthesis of conjugated dienals
  作者：Babu A. Patel、Jin-Il I. Kim、Diana D. Bender、Lien-Chung Kao、Richard F. Heck

  DOI：10.1021/jo00319a004

  日期：1981.3
• Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 11. Total Syntheses of (−)-Lochneridine and (−)- and Racemic 20-<i>epi</i>-Lochneridine
  作者：Martin E. Kuehne、Feng Xu

  DOI：10.1021/jo981401o

  日期：1998.12.1

  Enantioselective syntheses of (-)-lochneridine (1) and (-)-epi-lochneridine (2) were obtained by two alternative C-20 diastereoselective syntheses of the respective pentacyclic (3aS,5S,11bR)-methyl 12-oxo-3,5-ethano-2,3,3a,4,5,7-hexahydro-3H-pyrrolo[2,3-d]carbazole-6-carboxylate ((-)-8) and tetracyclic methyl (2S,3aS,5R,11bR))-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(2-(1-butenyl))-1H-pyrrolo[2,3d]carbazole-6-carboxylate ((-)-12b) precursors from tryptophan derived 2-[(methoxycarbonyl)methyl]3-[2(S)-(methoxy or benzyloxycarbonyl)-2-(N-b-benzyl)aminoethyl]indole (15 or 16). While a modified Grignard reaction of the ketone (-)-8 provided (-)-lochneridine (1), dihydroxylation and cyclization of the olefin (-)-12b gave its C-20 epimer (2).