(3R,3aS,8aS)-2,2-dimethyl-3-(triisopropylsiloxy)-5-(methoxycarbonyl)-2,3,3a,6,7,8a-hexahydro-5H-1,8-dioxacyclopentinden-4-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃类
• 英文名称: (3R,3aS,8aS)-2,2-dimethyl-3-(triisopropylsiloxy)-5-(methoxycarbonyl)-2,3,3a,6,7,8a-hexahydro-5H-1,8-dioxacyclopentinden-4-one
• 化学式: C₂₃H₃₈O₆Si
• 分子量: 438.637
• InChiKey: VFYMCLSBBNUOID-FOOMGETCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  30.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

上下游信息

反应信息

• 作为反应物：
  描述：

  (3R,3aS,8aS)-2,2-dimethyl-3-(triisopropylsiloxy)-5-(methoxycarbonyl)-2,3,3a,6,7,8a-hexahydro-5H-1,8-dioxacyclopentinden-4-one 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 1,4-二氧六环 为溶剂， 反应 5.0h， 以74%的产率得到(3R,3aS,8aS)-2,2-dimethyl-3-(triisopropylsiloxy)-5-(methoxycarbonyl)-2,3,3a,8a-tetrahydro-1,8-dioxacyclopentinden-4-ol
  参考文献：
  名称：

  Total Synthesis and Absolute Configuration of Pseudosemiglabrin, a Platelet Aggregation Antagonist, and Its Diastereomer Semiglabrin

  摘要：

  A general approach to the synthesis of the flavone-furo[2,3-b]furan ring system present in numerous biologically-active secondary metabolites of Tephrosia sp. has been developed and applied in one racemic synthesis and two asymmetric syntheses of four members of the family. It uses 2-diazo-1,3-cyclohexanedione as the keystone of the ring system, uniting it with a dihydrofuran through a rhodium-mediated dipolar cycloaddition. The enolate of this tricyclic intermediate is then utilized to elaborate a salicylate that is subjected to a concise annulation protocol with benzaldehyde to produce the tetracycle. Stereochemical control is accomplished by the use of three strategies. Reduction of a ketone from the more accessible face of a folded bicyclooctane ring system produces the endo stereochemistry. Steric hindrance by a bulky allylic siloxy group directs the cycloaddition to the opposite face of the prochiral alkene to generate the exo stereochemistry. Finally, a novel hydroxyl-directed cycloaddition simultaneously produces the endo stereochemistry and accesses the opposite enantiomeric series.

  DOI：

  10.1021/ja00122a011
• 作为产物：
  描述：

  2-diazocyclohexane-1,3-dione 在 rhodium(II) acetate dimer 、 咪唑 、 4-二甲氨基吡啶 、 potassium hydride 、 sodium hydride 作用下， 以 氟苯 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 (3R,3aS,8aS)-2,2-dimethyl-3-(triisopropylsiloxy)-5-(methoxycarbonyl)-2,3,3a,6,7,8a-hexahydro-5H-1,8-dioxacyclopentinden-4-one
  参考文献：
  名称：

  Total Synthesis and Absolute Configuration of Pseudosemiglabrin, a Platelet Aggregation Antagonist, and Its Diastereomer Semiglabrin

  摘要：

  A general approach to the synthesis of the flavone-furo[2,3-b]furan ring system present in numerous biologically-active secondary metabolites of Tephrosia sp. has been developed and applied in one racemic synthesis and two asymmetric syntheses of four members of the family. It uses 2-diazo-1,3-cyclohexanedione as the keystone of the ring system, uniting it with a dihydrofuran through a rhodium-mediated dipolar cycloaddition. The enolate of this tricyclic intermediate is then utilized to elaborate a salicylate that is subjected to a concise annulation protocol with benzaldehyde to produce the tetracycle. Stereochemical control is accomplished by the use of three strategies. Reduction of a ketone from the more accessible face of a folded bicyclooctane ring system produces the endo stereochemistry. Steric hindrance by a bulky allylic siloxy group directs the cycloaddition to the opposite face of the prochiral alkene to generate the exo stereochemistry. Finally, a novel hydroxyl-directed cycloaddition simultaneously produces the endo stereochemistry and accesses the opposite enantiomeric series.

  DOI：

  10.1021/ja00122a011

文献信息

• Total Synthesis and Absolute Configuration of Pseudosemiglabrin, a Platelet Aggregation Antagonist, and Its Diastereomer Semiglabrin
  作者：Michael C. Pirrung、Yong Rok Lee

  DOI：10.1021/ja00122a011

  日期：1995.5

  A general approach to the synthesis of the flavone-furo[2,3-b]furan ring system present in numerous biologically-active secondary metabolites of Tephrosia sp. has been developed and applied in one racemic synthesis and two asymmetric syntheses of four members of the family. It uses 2-diazo-1,3-cyclohexanedione as the keystone of the ring system, uniting it with a dihydrofuran through a rhodium-mediated dipolar cycloaddition. The enolate of this tricyclic intermediate is then utilized to elaborate a salicylate that is subjected to a concise annulation protocol with benzaldehyde to produce the tetracycle. Stereochemical control is accomplished by the use of three strategies. Reduction of a ketone from the more accessible face of a folded bicyclooctane ring system produces the endo stereochemistry. Steric hindrance by a bulky allylic siloxy group directs the cycloaddition to the opposite face of the prochiral alkene to generate the exo stereochemistry. Finally, a novel hydroxyl-directed cycloaddition simultaneously produces the endo stereochemistry and accesses the opposite enantiomeric series.