(5aR,6aS,7aS,11aR,11bR)-hexahydro-5,5,7a,11b-tetramethyl-5H,6aH-oxepino<4,3-f>oxireno<1>benzopyran-3,9(2H,10H)-dione

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (5aR,6aS,7aS,11aR,11bR)-hexahydro-5,5,7a,11b-tetramethyl-5H,6aH-oxepino<4,3-f>oxireno<1>benzopyran-3,9(2H,10H)-dione
• 英文别名: (1R,3S,5S,10R,11R)-5,11,16,16-tetramethyl-2,6,15-trioxatetracyclo[9.5.0.01,3.05,10]hexadecane-7,14-dione
• 化学式: C₁₇H₂₄O₅
• 分子量: 308.375
• InChiKey: HTSGPHPZSYMWBH-XNMUYTFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (3aS,9aR,9bR)-4,6,8,9,9a,9b-hexahydro-3a,6,6,9a-tetramethyl-1H-benzindene-3,7(1H,3aH)-dione 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以51%的产率得到(5aR,6aS,7aS,11aR,11bR)-hexahydro-5,5,7a,11b-tetramethyl-5H,6aH-oxepino<4,3-f>oxireno<1>benzopyran-3,9(2H,10H)-dione
  参考文献：
  名称：

  Total Synthesis of (-)-Austalide B. A Generic Solution to Elaboration of the Pyran/p-Cresol/Butenolide Triad

  摘要：

  The toxic meroterpenoid (-)-austalide B has been prepared in its natural form by chemical modification of the readily available optically active enedione 11. Following stereocontrolled Robinson annulation to give 13 and fully regiocontrolled gem-dimethylation of this intermediate, the highly functionalized tetracyclic ortho ester 22 was produced in four additional steps. At this point, it proved an easy matter to obtain 23 by Baeyer-Villiger oxidation. For the purpose of annealing rings E and F, carbomethoxy trinate 41 was prepared and coupled to 42 through the agency of Pd-2(dba)(3) and (furyl)(3)P. With arrival at 39, it proved possible by sequential intramolecular Claisen condensation, O-methylation, and modest warming to produce 50. Deprotection of the secondary hydroxyl and inversion of its configuration delivered synthetic austalide B, which exhibited melting point, specific rotation, infrared, and NMR properties (H-1 and C-13) identical to the natural material obtained from South Africa.

  DOI：

  10.1021/ja00104a012

文献信息

• Total Synthesis of (-)-Austalide B. A Generic Solution to Elaboration of the Pyran/p-Cresol/Butenolide Triad
  作者：Leo A. Paquette、Ting-Zhong Wang、Matthew R. Sivik

  DOI：10.1021/ja00104a012

  日期：1994.12

  The toxic meroterpenoid (-)-austalide B has been prepared in its natural form by chemical modification of the readily available optically active enedione 11. Following stereocontrolled Robinson annulation to give 13 and fully regiocontrolled gem-dimethylation of this intermediate, the highly functionalized tetracyclic ortho ester 22 was produced in four additional steps. At this point, it proved an easy matter to obtain 23 by Baeyer-Villiger oxidation. For the purpose of annealing rings E and F, carbomethoxy trinate 41 was prepared and coupled to 42 through the agency of Pd-2(dba)(3) and (furyl)(3)P. With arrival at 39, it proved possible by sequential intramolecular Claisen condensation, O-methylation, and modest warming to produce 50. Deprotection of the secondary hydroxyl and inversion of its configuration delivered synthetic austalide B, which exhibited melting point, specific rotation, infrared, and NMR properties (H-1 and C-13) identical to the natural material obtained from South Africa.