(+)-pseudosemiglabrinol | 163254-74-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: (+)-pseudosemiglabrinol
• 英文别名: (12R,15R,16S)-15-hydroxy-14,14-dimethyl-4-phenyl-3,11,13-trioxatetracyclo[8.6.0.02,7.012,16]hexadeca-1(10),2(7),4,8-tetraen-6-one
• CAS: 163254-74-8
• 化学式: C₂₁H₁₈O₅
• 分子量: 350.371
• InChiKey: XBKLVCYSINXGAW-DFQSSKMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  26
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (+)-pseudosemiglabrinol 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以93%的产率得到8-中氮茚甲胺,八氢-1,6,7-三(苯基甲氧基)-,1S-(1.α.,6.β.,7.α.,8.β.,8a.β.)-
  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：

  (3R,3aS,8aS)-2,2-dimethyl-3-(triisopropylsiloxy)-5-(methoxycarbonyl)-2,3,3a,8a-tetrahydro-1,8-dioxacyclopentinden-4-ol 在 哌啶 、 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 6.0h， 生成 (+)-pseudosemiglabrinol
  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.