3-cyclohexene-1-methanol, 5-hydroxy-α,α,4-trimethyl-α-acetate

• 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: 3-cyclohexene-1-methanol, 5-hydroxy-α,α,4-trimethyl-α-acetate
• 英文别名: Hydroxy-alpha-terpenyl acetate；2-(5-hydroxy-4-methylcyclohex-3-en-1-yl)propan-2-yl acetate
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: ISKWEZUCHJMRLH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  乙酸松油酯	terpinyl acetate	80-26-2	C12H20O2	196.29

反应信息

• 作为反应物：
  描述：

  3-cyclohexene-1-methanol, 5-hydroxy-α,α,4-trimethyl-α-acetate 在 bis(acetylacetonate)oxovanadium 、 pinane hydroperoxide 作用下， 以 氯苯 为溶剂， 反应 5.0h， 以100%的产率得到Acetic acid 1-(5-hydroxy-6-methyl-7-oxa-bicyclo[4.1.0]hept-3-yl)-1-methyl-ethyl ester
  参考文献：
  名称：

  Metal-Catalyzed Oxidations with Pinane Hydroperoxide:  A Mechanistic Probe To Distinguish between Oxometal and Peroxometal Pathways

  摘要：

  The relative reactivities of tert-butyl hydroperoxide (TBHP) and pinane hydroperoxide (PHP) in metal (Cr, Mo, Ru, Se, V, and Zr)-catalyzed oxidations were compared. When these oxidations involve rate-limiting oxygen transfer from a peroxometal species to the substrate huge differences between TBHP and PHP were observed, e.g., molybdenum-catalyzed epoxidation of cyclohexene with TBHP gave a 98% yield while PHP gave 0%. When the reaction involves reaction of an oxometal species with the substrate as the rate-limiting step, little or no difference is observed, e.g., the selenium-catalyzed allylic oxidation of beta-pinene gave a 96% and 99% yield with TBHP and PHP, respectively. Small but significant differences are observed when reoxidation of the catalyst by the hydroperoxide to the active oxometal species is the rate-limiting step; e.g., the chromium-catalyzed oxidation of carveol gave carvone in 89% and 24% yield with TBHP and PHP, respectively. Hence, the effect of RO2H structure on rate is dependent on the rate-limiting step.

  DOI：

  10.1021/jo971270b
• 作为产物：
  描述：

  乙酸松油酯 在 ferredoxin reductase 、 [2Fe–2S] ferredoxin 、 cytochrome P₄₅₀ enzyme CYP₁₀₁C₁ 作用下， 以 aq. buffer 为溶剂， 以82%的产率得到3-cyclohexene-1-methanol, 5-hydroxy-α,α,4-trimethyl-α-acetate
  参考文献：
  名称：

  相同家族的两种细胞色素P450酶对烃衍生物的互补和选择性氧化

  摘要：

  细胞色素P450酶CYP101B1和CYP101C1，来自细菌新孢子虫DSM12444可高活性和选择性地羟基化类异戊二烯。为了扩展和建立其底物范围，以开发应用，研究了选择环烷烃，酮和醇的氧化。环烷被氧化，但两种酶均显示出中等的结合亲和力和较低的生产活性。我们通过将组氨酸残基切换为苯丙氨酸（H85F），使活性位点更具疏水性，从而改善了这些底物与CYP101B1的结合和活性。环烷烃骨架中酮部分的存在显着改善了两种酶的氧化活性。CYP101C1优选在C-2位置催化环烷酮的氧化，而CYP101B1在远离羰基的位置以较高的生产率氧化这些底物。这表明每种酶的活性位点中环酮的结合方向必须不同。线性酮也被两种酶氧化，但活性和选择性较低。CYP101B1比CYP101C1更有效地氧化具有酯导向基团的环状底物。两种酶都在远离酯导向基团的环系统上以高区域选择性催化这些酯的氧化。CYP101C1比CYP101B1

  DOI：

  10.1039/d0cy01040e

文献信息

• Complementary and selective oxidation of hydrocarbon derivatives by two cytochrome P450 enzymes of the same family
  作者：Md. Raihan Sarkar、Stephen G. Bell

  DOI：10.1039/d0cy01040e

  日期：——

  The cytochrome P450 enzymes CYP101B1 and CYP101C1, which are from the bacterium Novosphingobium aromaticivorans DSM12444, can hydroxylate norisoprenoids with high activity and selectivity. With the goal of expanding and establishing their substrate range with a view to developing applications, the oxidation of a selection of cyclic alkanes, ketones and alcohols was investigated. Cycloalkanes were oxidised

  细胞色素P450酶CYP101B1和CYP101C1，来自细菌新孢子虫DSM12444可高活性和选择性地羟基化类异戊二烯。为了扩展和建立其底物范围，以开发应用，研究了选择环烷烃，酮和醇的氧化。环烷被氧化，但两种酶均显示出中等的结合亲和力和较低的生产活性。我们通过将组氨酸残基切换为苯丙氨酸（H85F），使活性位点更具疏水性，从而改善了这些底物与CYP101B1的结合和活性。环烷烃骨架中酮部分的存在显着改善了两种酶的氧化活性。CYP101C1优选在C-2位置催化环烷酮的氧化，而CYP101B1在远离羰基的位置以较高的生产率氧化这些底物。这表明每种酶的活性位点中环酮的结合方向必须不同。线性酮也被两种酶氧化，但活性和选择性较低。CYP101B1比CYP101C1更有效地氧化具有酯导向基团的环状底物。两种酶都在远离酯导向基团的环系统上以高区域选择性催化这些酯的氧化。CYP101C1比CYP101B1
• Metal-Catalyzed Oxidations with Pinane Hydroperoxide:  A Mechanistic Probe To Distinguish between Oxometal and Peroxometal Pathways
  作者：H. E. B. Lempers、A. Ripollès i Garcia、R. A. Sheldon

  DOI：10.1021/jo971270b

  日期：1998.3.1

  The relative reactivities of tert-butyl hydroperoxide (TBHP) and pinane hydroperoxide (PHP) in metal (Cr, Mo, Ru, Se, V, and Zr)-catalyzed oxidations were compared. When these oxidations involve rate-limiting oxygen transfer from a peroxometal species to the substrate huge differences between TBHP and PHP were observed, e.g., molybdenum-catalyzed epoxidation of cyclohexene with TBHP gave a 98% yield while PHP gave 0%. When the reaction involves reaction of an oxometal species with the substrate as the rate-limiting step, little or no difference is observed, e.g., the selenium-catalyzed allylic oxidation of beta-pinene gave a 96% and 99% yield with TBHP and PHP, respectively. Small but significant differences are observed when reoxidation of the catalyst by the hydroperoxide to the active oxometal species is the rate-limiting step; e.g., the chromium-catalyzed oxidation of carveol gave carvone in 89% and 24% yield with TBHP and PHP, respectively. Hence, the effect of RO2H structure on rate is dependent on the rate-limiting step.