6-(1-tert-Butyl-1-hydroxyethyl)-1,4-dioxaspiro<4.5>decane

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-(1-tert-Butyl-1-hydroxyethyl)-1,4-dioxaspiro<4.5>decane
• 英文别名: 2-(1,4-dioxaspiro[4.5]decan-6-yl)-3,3-dimethylbutan-2-ol
• 化学式: C₁₄H₂₆O₃
• 分子量: 242.359
• InChiKey: LIEHYNGFNSCYCB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  6-(1-tert-Butyl-1-hydroxyethyl)-1,4-dioxaspiro<4.5>decane 在 4-甲基苯磺酸吡啶 作用下， 以 水 、 丙酮 为溶剂， 以82%的产率得到2-(1-tert-Butyl-1-hydroxyethyl)cyclohexanone
  参考文献：
  名称：

  Syntheses and Theoretical Studies of Exocyclic .gamma.-Oxoalkenyltrimethylsilanes. An Approach to the Stereodefined Exocyclic Tetrasubstituted Alkenes

  摘要：

  The Z-selectivity in the dehydration of alpha-hydroxy-gamma-oxoalkyltrimethylsilanes under acidic conditions was studied from experimental and theoretical points of view. Experimental results showed that (Z)-gamma-oxoalkenyltrimethylsilanes were thermodynamic products under these conditions. The dehydration studies of the compound involving the tert-butyl group instead of the TMS group pointed out that not only steric but also electronic effects of Si could contribute to the distribution of the products as well as their stereochemistries. Theoretical studies using ab initio calculation at the 6-31G* level indicated that the (Z)-isomer was thermodynamically more stable than the corresponding (E)-isomer. Detail examinations of the optimized structures showed that the configuration of Si in the (Z)-isomer was slightly distorted from tetrahedral. Interpretation of the geometrical change of Si to rationalization of the thermodynamic preference was discussed fi om the viewpoint of possible coordination of the carbonyl oxygen to Si. Those (Z)-gamma-oxoalkenyltrimethylsilanes would have potential to be the novel type of alkenylmetal compounds in organic synthesis as we demonstrated in the construction of stereodefined exocyclic tetrasubstituted alkene.

  DOI：

  10.1021/jo00099a027
• 作为产物：
  描述：

  2-乙酰基环己酮 、 alkaline earth salt of/the/ methylsulfuric acid 在 对甲苯磺酸 作用下， 以 乙醚 、 正戊烷 、 苯 为溶剂， 反应 3.0h， 生成 6-(1-tert-Butyl-1-hydroxyethyl)-1,4-dioxaspiro<4.5>decane
  参考文献：
  名称：

  Syntheses and Theoretical Studies of Exocyclic .gamma.-Oxoalkenyltrimethylsilanes. An Approach to the Stereodefined Exocyclic Tetrasubstituted Alkenes

  摘要：

  The Z-selectivity in the dehydration of alpha-hydroxy-gamma-oxoalkyltrimethylsilanes under acidic conditions was studied from experimental and theoretical points of view. Experimental results showed that (Z)-gamma-oxoalkenyltrimethylsilanes were thermodynamic products under these conditions. The dehydration studies of the compound involving the tert-butyl group instead of the TMS group pointed out that not only steric but also electronic effects of Si could contribute to the distribution of the products as well as their stereochemistries. Theoretical studies using ab initio calculation at the 6-31G* level indicated that the (Z)-isomer was thermodynamically more stable than the corresponding (E)-isomer. Detail examinations of the optimized structures showed that the configuration of Si in the (Z)-isomer was slightly distorted from tetrahedral. Interpretation of the geometrical change of Si to rationalization of the thermodynamic preference was discussed fi om the viewpoint of possible coordination of the carbonyl oxygen to Si. Those (Z)-gamma-oxoalkenyltrimethylsilanes would have potential to be the novel type of alkenylmetal compounds in organic synthesis as we demonstrated in the construction of stereodefined exocyclic tetrasubstituted alkene.

  DOI：

  10.1021/jo00099a027

文献信息

• Syntheses and Theoretical Studies of Exocyclic .gamma.-Oxoalkenyltrimethylsilanes. An Approach to the Stereodefined Exocyclic Tetrasubstituted Alkenes
  作者：Kazuhiko Nakatani、Tomoko Izawa、Sachihiko Isoe

  DOI：10.1021/jo00099a027

  日期：1994.10

  The Z-selectivity in the dehydration of alpha-hydroxy-gamma-oxoalkyltrimethylsilanes under acidic conditions was studied from experimental and theoretical points of view. Experimental results showed that (Z)-gamma-oxoalkenyltrimethylsilanes were thermodynamic products under these conditions. The dehydration studies of the compound involving the tert-butyl group instead of the TMS group pointed out that not only steric but also electronic effects of Si could contribute to the distribution of the products as well as their stereochemistries. Theoretical studies using ab initio calculation at the 6-31G* level indicated that the (Z)-isomer was thermodynamically more stable than the corresponding (E)-isomer. Detail examinations of the optimized structures showed that the configuration of Si in the (Z)-isomer was slightly distorted from tetrahedral. Interpretation of the geometrical change of Si to rationalization of the thermodynamic preference was discussed fi om the viewpoint of possible coordination of the carbonyl oxygen to Si. Those (Z)-gamma-oxoalkenyltrimethylsilanes would have potential to be the novel type of alkenylmetal compounds in organic synthesis as we demonstrated in the construction of stereodefined exocyclic tetrasubstituted alkene.