5-Hydroxy-6-((2R,3S)-3-hydroxy-2-methyl-butyryl)-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: 5-Hydroxy-6-((2R,3S)-3-hydroxy-2-methyl-butyryl)-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one
• 英文别名: 5-hydroxy-6-[(2R,3S)-3-hydroxy-2-methyl-butanoyl]-2,2-dimethyl-10-propyl-pyrano[2,3-f]chromen-8-one；5-hydroxy-6-[(2R,3S)-3-hydroxy-2-methylbutanoyl]-2,2-dimethyl-10-propylpyrano[2,3-f]chromen-8-one
• 化学式: C₂₂H₂₆O₆
• 分子量: 386.445
• InChiKey: FCGLJCISYSOAJQ-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  93.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-Hydroxy-6-((2R,3S)-3-hydroxy-2-methyl-butyryl)-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one 在 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 (10R,11R)-10,11-dihydro-4-propyl-6,6,10,11-tetramethyl-2H,6H,12H-benzo[1,2-b;3,4-b';5,6-b'']tripyran-2,12-dione
  参考文献：
  名称：

  Synthesis of (+)-calanolide A, an anti-HIV agent, Via enzyme-catalyzed resolution of the aldol products

  摘要：

  The synthesis of (+)-calanolide A (1), an anti-HIV-1 agent, is described. A TiCl4-mediated aldol reaction of compound 2 stereoselectively produced the desired syn diastereomer (+/-)-5, which was resolved by a lipase-catalyzed acylation reaction. Under Mitsunobu conditions (Ph(3)P/DEAD), the syn aldol product (+)-5 led to the formation of trans-2,3-dimethyl chroman-4-one [(+)-3] with 94% ee, while the anti aldol product (+)-6 yielded both trans and cis derivatives (+)-3 and (+)-4 with 60% and 68% ee, respectively. Luche reduction on (+)-3 led to (+)-1 and (+)-calanolide B in a ratio of 9 : 1. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00433-8
• 作为产物：
  描述：

  5-hydroxy-2,2-dimethyl-10-propyl-6-propionyl-2H,8H-pyrano[2,3-f]chromen-8-one 在 四氯化钛 、 lithium diisopropyl amide 作用下， 生成 5-Hydroxy-6-((2R,3S)-3-hydroxy-2-methyl-butyryl)-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one
  参考文献：
  名称：

  Synthesis of (+)-calanolide A, an anti-HIV agent, Via enzyme-catalyzed resolution of the aldol products

  摘要：

  The synthesis of (+)-calanolide A (1), an anti-HIV-1 agent, is described. A TiCl4-mediated aldol reaction of compound 2 stereoselectively produced the desired syn diastereomer (+/-)-5, which was resolved by a lipase-catalyzed acylation reaction. Under Mitsunobu conditions (Ph(3)P/DEAD), the syn aldol product (+)-5 led to the formation of trans-2,3-dimethyl chroman-4-one [(+)-3] with 94% ee, while the anti aldol product (+)-6 yielded both trans and cis derivatives (+)-3 and (+)-4 with 60% and 68% ee, respectively. Luche reduction on (+)-3 led to (+)-1 and (+)-calanolide B in a ratio of 9 : 1. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00433-8

文献信息

• A Versatile Approach for Synthesis of 2,3-Dimethyl Chroman-4-ones, Intermediate for Calanolide Anti-HIV Agents,<i>VIA</i>Aldol/Mitsunobu Reactions
  作者：Albert Khilevich、John D. Rizzo、Michael T. Flavin、Abram K. Sheinkman、Aye Mar、Alla Kucherenko、Changren Yan、Sergey Dzekhtser、Darko Brankovic、Lin Lin、Jinjun Liu、Thomas M. Rizzo、Ze-Qi Xu

  DOI：10.1080/00397919608003792

  日期：1996.10

  Combined aldol/Mitsunobu reactions have been employed for the first time for synthesis of 2,3-dimethyl chroman-4-ones, intermediates for calanolide anti-HIV agents. Thus, the lithium enolate of chromene 1 reacted with acetaldehyde at -78 degrees C to afford the aldol products 4 and 5. Under Mitsunobu conditions (Ph(3)P/DEAD), the syn aldol product 4 led to the formation of trans-2,3-dimethyl chroman-4-one 2 while the anti aldol product 5 yielded both trans and cis derivatives (2 and 3). The use of other phosphorous and azo compounds in this reaction has also been investigated.