9-Methyl-6-(1-methylvinyl)-1,4-dioxaspiro<4,5>decane | 4643-59-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 9-Methyl-6-(1-methylvinyl)-1,4-dioxaspiro<4,5>decane
• 英文别名: (6S,9R)-9-methyl-6-prop-1-en-2-yl-1,4-dioxaspiro[4.5]decane
• CAS: 4643-59-8
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: UAOWUGRHCRDMAZ-MNOVXSKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  9-Methyl-6-(1-methylvinyl)-1,4-dioxaspiro<4,5>decane 在 二甲基硫 、 甲基锂 、 4-甲基苯磺酸吡啶 、 臭氧 作用下， 以 水 、 丙酮 为溶剂， 反应 9.75h， 生成 threo-2-<1-Hydroxy-1-(trimethylsilyl)ethyl>-5-methylcyclohexane-1-one
  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：

  长叶薄荷酮 、 乙二醇 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 24.0h， 以66%的产率得到9-Methyl-6-(1-methylvinyl)-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

• Miller, David; Bilodeau, Francois; Burnell, Robert H., Canadian Journal of Chemistry, 1991, vol. 69, # 7, p. 1100 - 1106
  作者：Miller, David、Bilodeau, Francois、Burnell, Robert H.

  DOI：——

  日期：——
• Total Synthesis and Absolute Configuration of Laurenditerpenol: A Hypoxia Inducible Factor-1 Activation Inhibitor
  作者：Amar G. Chittiboyina、Gundluru Mahesh Kumar、Paulo B. Carvalho、Yang Liu、Yu-Dong Zhou、Dale G. Nagle、Mitchell A. Avery

  DOI：10.1021/jm7011062

  日期：2007.12.13

  The absolute stereo structure of the natural product laurenditerpenol (IS, 6R, 7S, 10R, 11R, 14S, 15R) has been accomplished from eight plausible stereoisomers by its first asymmetric total synthesis in a highly convergent and flexible synthetic pathway. Six stereoisomers of laurenditerpenol were synthesized and evaluated for their biological activity.
• BULLIARD, M.;BALME, G.;MONTEIRO, N.;GORE, J., BULL. SOC. CHIM. FR.,(1991) N, C. 222-231
  作者：BULLIARD, M.、BALME, G.、MONTEIRO, N.、GORE, J.

  DOI：——

  日期：——
• 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.