α-cyclohexyl-3-methyloxiranemethanol | 114180-68-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: α-cyclohexyl-3-methyloxiranemethanol
• 英文别名: cyclohexyl-(3-methyloxiran-2-yl)methanol
• CAS: 114180-68-6；120849-49-2
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: UHNSGEXOTHKKDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.71
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.76
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  α-cyclohexyl-3-methyloxiranemethanol 在 碲化氢 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以17%的产率得到1-环己基-2-丁烯醇
  参考文献：
  名称：

  A tellurium transposition route to allylic alcohols: overcoming some limitations of the Sharpless-Katsuki asymmetric epoxidation

  摘要：

  Good yields of enantiomeric allylic alcohols can be obtained in high enantiomeric excess (ee) by combining the Sharpless-Katsuki asymmetric epoxidation process (SAE) with tellurium chemistry. The advantages of the tellurium process are as follows: (1) the 50% yield limitation on the allylic alcohol in the Sharpless kinetic resolution (SKR) can be overcome; (2) allylic tertiary alcohols which are unsatisfactory substrates in the SKR can be obtained in high optical purity; (3) optically active secondary allylic alcohols with tertiary alkyl substituents (e.g. tert-butyl) at C-1 can be obtained in high ee; (4) optically active sterically congested cis secondary alcohols can be obtained in high ee; and (5) the nuisance of the slow SAE of some vinyl carbinols can be avoided. The key step in the reaction sequence is either a stereospecific 1,3-trans position of double bond and alcohol functionalities or an inversion of the alcohol configuration with concomitant deoxygenation of the epoxide function in epoxy alcohols. Trans secondary allylic alcohols can be converted to cis secondary allylic alcohols by way of erythro epoxy alcohols (glycidols); threo glycidyl derivatives are converted to trans secondary allylic alcohols. These transformations are accomplished by the action of telluride ion, generated in situ from the element, on a glycidyl sulfonate ester. Reduction of elemental Te is conveniently done with rongalite (HOCH2SO2Na) in an aqueous medium. This method is satisfactory when Te2- is required to attack a primary carbon site of a glycidyl sulfonate. In cases where Te2- is required to attack a secondary carbon site, reduction of the tellurium must be done with NaBH4 or LiEt3BH. Elemental tellurium is precipitated during the course of the reactions and can be recovered and reused.

  DOI：

  10.1021/jo00055a029

文献信息

• A tellurium transposition route to allylic alcohols: overcoming some limitations of the Sharpless-Katsuki asymmetric epoxidation
  作者：Donald C. Dittmer、Robert P. Discordia、Yanzhi Zhang、Christopher K. Murphy、Archana Kumar、Aurora S. Pepito、Yuesheng Wang

  DOI：10.1021/jo00055a029

  日期：1993.1

  Good yields of enantiomeric allylic alcohols can be obtained in high enantiomeric excess (ee) by combining the Sharpless-Katsuki asymmetric epoxidation process (SAE) with tellurium chemistry. The advantages of the tellurium process are as follows: (1) the 50% yield limitation on the allylic alcohol in the Sharpless kinetic resolution (SKR) can be overcome; (2) allylic tertiary alcohols which are unsatisfactory substrates in the SKR can be obtained in high optical purity; (3) optically active secondary allylic alcohols with tertiary alkyl substituents (e.g. tert-butyl) at C-1 can be obtained in high ee; (4) optically active sterically congested cis secondary alcohols can be obtained in high ee; and (5) the nuisance of the slow SAE of some vinyl carbinols can be avoided. The key step in the reaction sequence is either a stereospecific 1,3-trans position of double bond and alcohol functionalities or an inversion of the alcohol configuration with concomitant deoxygenation of the epoxide function in epoxy alcohols. Trans secondary allylic alcohols can be converted to cis secondary allylic alcohols by way of erythro epoxy alcohols (glycidols); threo glycidyl derivatives are converted to trans secondary allylic alcohols. These transformations are accomplished by the action of telluride ion, generated in situ from the element, on a glycidyl sulfonate ester. Reduction of elemental Te is conveniently done with rongalite (HOCH2SO2Na) in an aqueous medium. This method is satisfactory when Te2- is required to attack a primary carbon site of a glycidyl sulfonate. In cases where Te2- is required to attack a secondary carbon site, reduction of the tellurium must be done with NaBH4 or LiEt3BH. Elemental tellurium is precipitated during the course of the reactions and can be recovered and reused.