trans-1,5-Dimethylcyclohex-2-en-1-ol | 157750-04-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-1,5-Dimethylcyclohex-2-en-1-ol
• 英文别名: (1R,5R)-1,5-Dimethyl-2-cyclohexen-1-ol；(1R,5R)-1,5-dimethylcyclohex-2-en-1-ol
• CAS: 157750-04-4
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: QYEGQMZZOCXIAZ-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (R)-5-methyl-cyclohex-2-enone 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 三甲基铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.25h， 以87%的产率得到trans-1,5-Dimethylcyclohex-2-en-1-ol
  参考文献：
  名称：

  Kinetic Resolution of Chiral Cyclohex-2-enones by Rhodium(I)/binap-Catalyzed 1,2- and 1,4-Additions

  摘要：

  The feasibility of kinetic resolutions of racemic monosubstituted cyclohex-2-enones by Rh/binap-catalyzed reactions was investigated. 1,2-Addition of AlMe3 to the 5-substituted derivatives furnished allylic alcohols in the matched case, while the less reactive enantiomers were either left over or transformed into trans-3,5-disubstituted cyclohexanones in parallel or sequential 1,4-additions. Altogether, these represent regiodivergent reactions on racemic mixtures. In contrast, 1,4-addition of aryl groups led to inferior results since either catalyst or substrate control dominated.

  DOI：

  10.1021/ol300387f

文献信息

• Improved Synthesis of Cyclic Tertiary Allylic Alcohols by Asymmetric 1,2-Addition of AlMe₃to Enones
  作者：Andreas Kolb、Wei Zuo、Jürgen Siewert、Klaus Harms、Paultheo von Zezschwitz

  DOI：10.1002/chem.201303061

  日期：2013.11.25

  be transformed into tertiary allylic alcohols with excellent levels of enantioselectivity and high yields. The obtained products are versatile synthetic building blocks, shown by a highly enantioselective formal total synthesis of the pheromone (−)‐frontalin as well as formation of a bicyclic lactone that has the core structure of the natural flavour component “wine lactone”.

  据报道，开发了一种改进的方案，用于将对映体选择性Rh I / binap催化的AlMe 3 1,2 1,2加成到环状烯酮上。反应的31 P NMR分析表明，处于静止状态的催化剂是氯桥联的二聚体。这种见解导致了AgBF 4的使用作为原位活化二聚体预催化剂的添加剂。因此，现在相对于铑，催化剂负载量可以降低到仅1mol％。各种5-7元环状烯酮可以转化为叔烯丙醇，具有出色的对映选择性和高收率。所获得的产品是多功能的合成构件，以信息素（-）-额叶蛋白的高度对映选择性正式全合成以及具有天然风味成分“酒内酯”核心结构的双环内酯的形成为代表。
• Kinetic Resolution of Chiral Cyclohex-2-enones by Rhodium(I)/binap-Catalyzed 1,2- and 1,4-Additions
  作者：Andreas Kolb、Sebastian Hirner、Klaus Harms、Paultheo von Zezschwitz

  DOI：10.1021/ol300387f

  日期：2012.4.20

  The feasibility of kinetic resolutions of racemic monosubstituted cyclohex-2-enones by Rh/binap-catalyzed reactions was investigated. 1,2-Addition of AlMe3 to the 5-substituted derivatives furnished allylic alcohols in the matched case, while the less reactive enantiomers were either left over or transformed into trans-3,5-disubstituted cyclohexanones in parallel or sequential 1,4-additions. Altogether, these represent regiodivergent reactions on racemic mixtures. In contrast, 1,4-addition of aryl groups led to inferior results since either catalyst or substrate control dominated.