(3aS,6S,6aS)-3a-methyl-6-propan-2-yl-4,5,6,6a-tetrahydropentalen-1-one | 131934-85-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aS,6S,6aS)-3a-methyl-6-propan-2-yl-4,5,6,6a-tetrahydropentalen-1-one
• CAS: 131934-85-5
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: VROVLGDPAJTDOE-WCQGTBRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (3aS,6S,6aS)-3a-methyl-6-propan-2-yl-4,5,6,6a-tetrahydropentalen-1-one 在 platinum(IV) oxide 氢气 作用下， 以 乙醇 为溶剂， 反应 0.67h， 以98%的产率得到(3aS,6S,6aS)-2,3,4,5,6,6a-hexahydro-6-isopropyl-3a-methyl-1-(3aH)-pentalenone
  参考文献：
  名称：

  Synthetic studies on basmane diterpenes. Enantiospecific total synthesis of (+)-7,8-epoxy-2-basmen-6-one by Claisen ring expansion

  摘要：

  The first synthesis of an epoxybasmenone is described. The enantiospecific pathway begins by transforming optically pure aldehyde 10 into bicyclic lactone 39. Methylenation of 39 by means of the Tebbe reaction allows for operation of a Claisen rearrangement that proceeds almost completely by way of chair transition state 44 to give the cyclooctadienone 42. Regiospecific cyclopentannulation with installation of four additional stereogenic centers rested upon successful introduction of a functionalized four-carbon chain as in 48, facially controlled hydrogenation of the conjugated double bond, cyclization, and hydroxyl-directed epoxidation. Finally, Swern oxidation led to the target molecule 3, whose three-dimensional structural features were confirmed by X-ray crystallography.

  DOI：

  10.1021/ja00007a039
• 作为产物：
  描述：

  (5S)-isopropyl-2-methylcyclopent-1-enecarboxaldehyde 在 barium manganate 、 三氟化硼乙醚 、 magnesium 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 47.0h， 生成 (3aS,6S,6aS)-3a-methyl-6-propan-2-yl-4,5,6,6a-tetrahydropentalen-1-one
  参考文献：
  名称：

  Synthetic studies on basmane diterpenes. Enantiospecific total synthesis of (+)-7,8-epoxy-2-basmen-6-one by Claisen ring expansion

  摘要：

  The first synthesis of an epoxybasmenone is described. The enantiospecific pathway begins by transforming optically pure aldehyde 10 into bicyclic lactone 39. Methylenation of 39 by means of the Tebbe reaction allows for operation of a Claisen rearrangement that proceeds almost completely by way of chair transition state 44 to give the cyclooctadienone 42. Regiospecific cyclopentannulation with installation of four additional stereogenic centers rested upon successful introduction of a functionalized four-carbon chain as in 48, facially controlled hydrogenation of the conjugated double bond, cyclization, and hydroxyl-directed epoxidation. Finally, Swern oxidation led to the target molecule 3, whose three-dimensional structural features were confirmed by X-ray crystallography.

  DOI：

  10.1021/ja00007a039

文献信息

• Synthetic studies on basmane diterpenes. Enantiospecific total synthesis of (+)-7,8-epoxy-2-basmen-6-one by Claisen ring expansion
  作者：Leo A. Paquette、Ho Jung Kang

  DOI：10.1021/ja00007a039

  日期：1991.3

  The first synthesis of an epoxybasmenone is described. The enantiospecific pathway begins by transforming optically pure aldehyde 10 into bicyclic lactone 39. Methylenation of 39 by means of the Tebbe reaction allows for operation of a Claisen rearrangement that proceeds almost completely by way of chair transition state 44 to give the cyclooctadienone 42. Regiospecific cyclopentannulation with installation of four additional stereogenic centers rested upon successful introduction of a functionalized four-carbon chain as in 48, facially controlled hydrogenation of the conjugated double bond, cyclization, and hydroxyl-directed epoxidation. Finally, Swern oxidation led to the target molecule 3, whose three-dimensional structural features were confirmed by X-ray crystallography.