(3R)-2,2-dimethyl-2,3-dihydro-2H-furan-3-ol | 163192-61-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (3R)-2,2-dimethyl-2,3-dihydro-2H-furan-3-ol
• 英文别名: (3R)-2,2-dimethyl-3H-furan-3-ol
• CAS: 163192-61-8
• 化学式: C₆H₁₀O₂
• 分子量: 114.144
• InChiKey: UWPVRPHJZMYVMV-RXMQYKEDSA-N

物化性质

• 沸点：
  174.9±39.0 °C(Predicted)
• 密度：
  1.052±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R)-2,2-dimethyl-2,3-dihydro-2H-furan-3-ol 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
• 作为产物：
  描述：

  (2RS,3S,4R)-5,5-dimethyl-2-hydroxy-3,4-(isopropylidenedioxy)tetrahydrofuran 在 四氯化碳 、 六甲基磷酰三胺 、 氨 、 lithium 作用下， 生成 (3R)-2,2-dimethyl-2,3-dihydro-2H-furan-3-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

文献信息

• Hydroxy direction of the rhodium-mediated dipolar cycloaddition of cyclic carbenoids with vinyl ethers
  作者：Michael C. Pirrung、Yong Rok Lee

  DOI：10.1039/c39950000673

  日期：——

  The dipolar cycloaddition of cyclic diazocarbonyl compounds with vinyl ethers is directed in a syn fashion by allylic hydroxy groups.

  环状重氮羰基化合物与乙烯基醚的偶极环加成以顺式方式由烯丙基羟基引导。
• 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.