2-isopropenyl-5,5-dimethyl-cyclohexanone | 848122-34-9

• 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: 2-isopropenyl-5,5-dimethyl-cyclohexanone
• 英文别名: (2S)-5,5-dimethyl-2-prop-1-en-2-ylcyclohexan-1-one
• CAS: 848122-34-9
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: WGFDFRQLKHHKTI-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-isopropenyl-5,5-dimethyl-cyclohexanone 在 叔丁基锂 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 1.17h， 生成 4-[2-(t-butyl-diphenyl-silanyloxy)-ethyl]-6,6-dimethyl-1-methylene-octahydro-naphthalen-4a-ol
  参考文献：
  名称：

  Conservation of the Planar Chiral Information in the Tandem Oxy-Cope/Ene Reaction

  摘要：

  We report the stereoselective synthesis of a Decalin unit using a tandem oxy-Cope/ene reaction. [3,3]-Shift of 1,2-divinyleyclohexenol 18 generates (1E, 3Z, 7E) cyclodecatrien-2-ol 23 which tautomerizes to ketone 21 (Figure 3). The chiral information embedded in 23 is transferred into the newly formed stereogenic carbon C6 in 21. The efficiency of the chirality transfer is a reflection of the difference in the rates of ring inversion versus tautomerization of 23. Ketone 21 undergoes a carbonyl-ene reaction to give Decalin 20. Assuming a rapid equilibrium between macrocyclic diastereomers, the diastereomeric ratio of the transannular ene reaction is governed by the Curtin-Hammett principle. Analysis of the conservation of the planar chiral information in the tandem oxy-Cope/ene reaction is presented.

  DOI：

  10.1021/jo047916z
• 作为产物：
  描述：

  3-甲基-6-(1-甲基乙烯基)-2-环己烯-1-酮 、 甲基锂 在 copper(l) iodide 作用下， 以 乙醚 为溶剂， 以83%的产率得到2-isopropenyl-5,5-dimethyl-cyclohexanone
  参考文献：
  名称：

  Conservation of the Planar Chiral Information in the Tandem Oxy-Cope/Ene Reaction

  摘要：

  We report the stereoselective synthesis of a Decalin unit using a tandem oxy-Cope/ene reaction. [3,3]-Shift of 1,2-divinyleyclohexenol 18 generates (1E, 3Z, 7E) cyclodecatrien-2-ol 23 which tautomerizes to ketone 21 (Figure 3). The chiral information embedded in 23 is transferred into the newly formed stereogenic carbon C6 in 21. The efficiency of the chirality transfer is a reflection of the difference in the rates of ring inversion versus tautomerization of 23. Ketone 21 undergoes a carbonyl-ene reaction to give Decalin 20. Assuming a rapid equilibrium between macrocyclic diastereomers, the diastereomeric ratio of the transannular ene reaction is governed by the Curtin-Hammett principle. Analysis of the conservation of the planar chiral information in the tandem oxy-Cope/ene reaction is presented.

  DOI：

  10.1021/jo047916z

文献信息

• Origin of Diastereoselectivity in the Tandem Oxy-Cope/Claisen/Ene Reaction:  Experimental and Theoretical Studies of the Ring Inversion Mechanism
  作者：Effiette L. O. Sauer、James Hooper、Tom Woo、Louis Barriault

  DOI：10.1021/ja066830f

  日期：2007.2.1

  the potential energy surface for the reaction and evaluate the relative energies of the ring inversions relative to those of the Claisen and ene reactions. Transition state energies thus obtained were found to support the presence of a high-energy transition state for the ring inversion of B to D provided R(1) not equal H. In addition, the calculations lent further support to the hypothesis that the

  我们在此报告了对 oxy-Cope/Claisen/ene 反应的反应机理的详细研究。制备了一系列手性底物，进行串联序列，并评估最终产物的对映体过量。观察到的对映体过量守恒被视为中间烯醇醚的环反转没有发生的证据。DFT 计算用于绘制反应的势能面，并评估环反转相对于 Claisen 和 ene 反应的相对能量。发现由此获得的过渡态能量支持 B 到 D 的环反转的高能过渡态的存在，前提是 R(1) 不等于 H。此外，