(+/-)-Spironon-8-ene-2,2'-<1,3>dioxolan>-6-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-Spironon-8-ene-2,2'-<1,3>dioxolan>-6-one
• 英文别名: (1'S,5'S)-spiro[1,3-dioxolane-2,2'-bicyclo[3.2.2]non-8-ene]-6'-one
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: CPIYJEKTJATYLT-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-Spironon-8-ene-2,2'-<1,3>dioxolan>-6-one 在 正丁基锂 、 叔丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 、 正戊烷 为溶剂， 反应 44.5h， 生成 (1S,5S,6R)-6-<(S)-3-Isopropyl-1-cyclopenten-1-yl>spironon-8-ene-2,2'-<1,3>dioxolan>-6-ol
  参考文献：
  名称：

  Exploratory Synthetic Studies Involving the Tricyclo[9.3.0.02,8]tetradecane Ring System Peculiar to the Cyathins

  摘要：

  Following an improved preparation of 2-methylene-1,3-dithiolane, this ketene acetal was shown to undergo inverse-electron-demand Diels-Alder cycloaddition to tropone. Regiocontrolled copper hydride reduction and resolution via sulfoximine adducts was readily achieved to give (-)-9. Addition to 9 of the chiral nonracemic vinyl bromides 21 and 22 proceeded with endo capture of the nucleophilic vinyllithium to give carbinols that underwent anionic oxy-Cope rearrangement at somewhat elevated temperatures. The [3,3] sigmatropic event delivered cis,syn,cis-tricyclo[9.3.0.0(2,8)]tetradecnones possessing structural frameworks related to the cyathins. Once 31 was in hand, it proved an easy matter to introduce added unsaturation and oxygen substituents. The tendency of certain derivatives for transannular cyclization was made quite apparent. Attempts to introduce a C(6)-alpha-methyl substituent was not achieved, chiefly as the result of the overall molecular concavity of this class of intermediates. A variety of reactions aimed at enhancing the level of functionality in rings B and C was explored and processes conducive to the attainment of these goals were developed.

  DOI：

  10.1021/jo00083a034
• 作为产物：
  描述：

  环庚三烯酮 在 正丁基锂 、 MoO5*pyridine*HMPA 、 methylcopper 、 二异丁基氢化铝 、 对甲苯磺酸 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 、 二氯甲烷 、 甲苯 、 苯 为溶剂， 反应 54.0h， 生成 (+/-)-Spironon-8-ene-2,2'-<1,3>dioxolan>-6-one
  参考文献：
  名称：

  Exploratory Synthetic Studies Involving the Tricyclo[9.3.0.02,8]tetradecane Ring System Peculiar to the Cyathins

  摘要：

  Following an improved preparation of 2-methylene-1,3-dithiolane, this ketene acetal was shown to undergo inverse-electron-demand Diels-Alder cycloaddition to tropone. Regiocontrolled copper hydride reduction and resolution via sulfoximine adducts was readily achieved to give (-)-9. Addition to 9 of the chiral nonracemic vinyl bromides 21 and 22 proceeded with endo capture of the nucleophilic vinyllithium to give carbinols that underwent anionic oxy-Cope rearrangement at somewhat elevated temperatures. The [3,3] sigmatropic event delivered cis,syn,cis-tricyclo[9.3.0.0(2,8)]tetradecnones possessing structural frameworks related to the cyathins. Once 31 was in hand, it proved an easy matter to introduce added unsaturation and oxygen substituents. The tendency of certain derivatives for transannular cyclization was made quite apparent. Attempts to introduce a C(6)-alpha-methyl substituent was not achieved, chiefly as the result of the overall molecular concavity of this class of intermediates. A variety of reactions aimed at enhancing the level of functionality in rings B and C was explored and processes conducive to the attainment of these goals were developed.

  DOI：

  10.1021/jo00083a034

文献信息

• Exploratory Synthetic Studies Involving the Tricyclo[9.3.0.02,8]tetradecane Ring System Peculiar to the Cyathins
  作者：Karl R. Dahnke、Leo A. Paquette

  DOI：10.1021/jo00083a034

  日期：1994.2

  Following an improved preparation of 2-methylene-1,3-dithiolane, this ketene acetal was shown to undergo inverse-electron-demand Diels-Alder cycloaddition to tropone. Regiocontrolled copper hydride reduction and resolution via sulfoximine adducts was readily achieved to give (-)-9. Addition to 9 of the chiral nonracemic vinyl bromides 21 and 22 proceeded with endo capture of the nucleophilic vinyllithium to give carbinols that underwent anionic oxy-Cope rearrangement at somewhat elevated temperatures. The [3,3] sigmatropic event delivered cis,syn,cis-tricyclo[9.3.0.0(2,8)]tetradecnones possessing structural frameworks related to the cyathins. Once 31 was in hand, it proved an easy matter to introduce added unsaturation and oxygen substituents. The tendency of certain derivatives for transannular cyclization was made quite apparent. Attempts to introduce a C(6)-alpha-methyl substituent was not achieved, chiefly as the result of the overall molecular concavity of this class of intermediates. A variety of reactions aimed at enhancing the level of functionality in rings B and C was explored and processes conducive to the attainment of these goals were developed.