2-(1'-hydroxy-1'-methyl-ethyl)-2-cyclohexen-1-ol | 220589-54-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(1'-hydroxy-1'-methyl-ethyl)-2-cyclohexen-1-ol
• 英文别名: 2-(2-Hydroxypropan-2-yl)cyclohex-2-en-1-ol
• CAS: 220589-54-8
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: SXZXHMBCFUCIBQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-(1,2-Epoxycyclohexyl)propan-2-ol 在 aluminum isopropoxide 作用下， 以 异丙醇 为溶剂， 反应 8.0h， 以36%的产率得到2-(1'-hydroxy-1'-methyl-ethyl)-2-cyclohexen-1-ol
  参考文献：
  名称：

  Stereoselective Reductive Rearrangement of α-Hydroxy Epoxides:  A New Method for Synthesis of 1,3-Diols¹

  摘要：

  A novel and short synthetic method for the stereoselective synthesis of 1,3-diols has been developed by an unusual reductive rearrangement of a series of cl-hydroxy epoxides with aluminum isopropoxide. The reaction process was also investigated with deuterium-labeled aluminum isopropoxide, which revealed a site-specific 1,2-carbon-to-carbon migration and successive stereoselective hydride shift. The main synthetically valuable feature is that up to three contiguous carbon centers, the C-1, C-2, and C-3, were stereoselectively controlled with C-2 being quaternary. This reaction is of particular importance to the synthesis of newly developed powerful asymmetric hydrogenation catalysts containing the chiral ligands of spirocyclic diols.

  DOI：

  10.1021/jo981097z

文献信息

• Identification of alkyl radicals derived from an allergenic cyclic tertiary allylic hydroperoxide by combined use of radical trapping and ESR studies
  作者：Elena Giménez Arnau、Laure Haberkorn、Loris Grossi、Jean-Pierre Lepoittevin

  DOI：10.1016/s0040-4020(02)00453-2

  日期：2002.7

  which generated the same allyloxyl radical by in situ photolysis of the corresponding nitrite formed in the presence of t-BuONO (which also played the role of spin-trap). The formation and trapping of carbon-centered radicals derived from the allyloxyl radical, as well as from the peroxyl radical, are described. The generation of these highly reactive radicals in the epidermis could lead to the formation

  结合自由基捕获和ESR研究，鉴定了源自1-（1-氢过氧-1-甲基乙基）环己烯（一种致敏性环状叔烯丙基氢过氧化物）的烷基。在含有稳定清除剂1,1,3,3-四甲基异吲哚啉-2-基氧基的乙腈水溶液中进行了自由基捕获实验，并用光，热和TPP-Fe 3+作为自由基诱导剂。对氢过氧化物的烯丙醇前体进行了ESR旋阱研究，该前体通过在存在t时形成的相应亚硝酸盐进行原位光解而生成相同的烯丙氧基。-BuONO（也起到了自旋陷阱的作用）。描述了衍生自烯丙氧基和过氧自由基的以碳为中心的自由基的形成和俘获。这些高反应性自由基在表皮中的产生可能导致抗原性结构的形成，这是过敏性接触性皮炎机制的第一步。
• Stereoselective Reductive Rearrangement of α-Hydroxy Epoxides:  A New Method for Synthesis of 1,3-Diols¹
  作者：Yong Qiang Tu、Liang Dong Sun、Ping Zhen Wang

  DOI：10.1021/jo981097z

  日期：1999.1.1

  A novel and short synthetic method for the stereoselective synthesis of 1,3-diols has been developed by an unusual reductive rearrangement of a series of cl-hydroxy epoxides with aluminum isopropoxide. The reaction process was also investigated with deuterium-labeled aluminum isopropoxide, which revealed a site-specific 1,2-carbon-to-carbon migration and successive stereoselective hydride shift. The main synthetically valuable feature is that up to three contiguous carbon centers, the C-1, C-2, and C-3, were stereoselectively controlled with C-2 being quaternary. This reaction is of particular importance to the synthesis of newly developed powerful asymmetric hydrogenation catalysts containing the chiral ligands of spirocyclic diols.