(R)-(+)-6-Hydroxy-4-methyl-hexansaeure

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: (R)-(+)-6-Hydroxy-4-methyl-hexansaeure
• 英文别名: (4R)-6-hydroxy-4-methylhexanoic acid
• 化学式: C₇H₁₄O₃
• 分子量: 146.186
• InChiKey: MSWBISKOQFARTB-ZCFIWIBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-(+)-6-Hydroxy-4-methyl-hexansaeure 在 Jones reagent 作用下， 以 丙酮 为溶剂， 反应 24.0h， 生成 (R)-(+)-3-甲基己二酸
  参考文献：
  名称：

  对映选择性 Baeyer-Villiger 氧化：内消旋环酮的去对称化和外消旋 2-芳基环己酮的动力学拆分

  摘要：

  在手性 N,N'-二氧化物-Sc(III) 配合物催化剂存在下，实现了外消旋和内消旋环酮的催化对映选择性 Baeyer-Villiger (BV) 氧化。前手性环己酮和环丁酮的 BV 氧化分别提供了一系列具有光学活性的 ε- 和 γ-内酯，产率高达 99%，ee 高达 95%。同时，外消旋 2-芳基环己酮的动力学拆分也是通过异常 BV 氧化实现的。Enantioenriched 3-aryloxepan-2-ones，其形成与迁移能力相反，被优先获得。内酯和未反应的酮均具有高 ee 值。

  DOI：

  10.1021/ja309262f
• 作为产物：
  描述：

  (R)-(+)-β-香茅醇 在 potassium permanganate 、 sodium periodate 作用下， 生成 (R)-(+)-6-Hydroxy-4-methyl-hexansaeure
  参考文献：
  名称：

  Syntheses of some optically active .epsilon.-caprolactones

  摘要：

  DOI：

  10.1021/ja00998a024

文献信息

• Correction to Enantioselective Baeyer–Villiger Oxidation: Desymmetrization of Meso Cyclic Ketones and Kinetic Resolution of Racemic 2-Arylcyclohexanones
  作者：Lin Zhou、Xiaohua Liu、Jie Ji、Yuheng Zhang、Xiaolei Hu、Lili Lin、Xiaoming Feng

  DOI：10.1021/ja3112719

  日期：2012.12.12
• Lipase-Catalyzed Ring-Opening Polymerizations of 4-Substituted ε-Caprolactones:  Mechanistic Considerations
  作者：Joris W. Peeters、Oscar van Leeuwen、Anja R. A. Palmans、E. W. Meijer

  DOI：10.1021/ma050510j

  日期：2005.6.1

  Lipase-catalyzed ring-opening polymerizations of 4-substituted epsilon-caprolactones employing Novozym 435 as the biocatalyst demonstrate dramatic differences in polymerization rates and selectivity depending on the size of the substituent. Quantification of the reaction rates shows that the polymerization rate decreases by a factor of 2 upon the introduction of a Me substituent at the 4-position. Moreover, 4-EtCL polymerizes 5 times slower than 4-MeCl and 4-PrCL is even 70 times slower. The decrease in polymerization rate is accompanied by a strong decrease in enantioselectivity: while the E-ratio of 4-MeCL polymerization is 16.9, the E-ratios of 4-EtCL and 4-PrCL are 7.1 and 2.0, respectively. Interestingly, Novozym 435 displays S-selectivity for 4-MeCL and 4-EtCL in the polymerization reaction, but the enantioselectivity is changed to the (R)-enantiomer in the case of the 4-PrCL. The nature of these differences was investigated by hydrolyzing all monomers in water/diisopropyl ether mixtures employing Novozym 435 as the catalyst. In the hydrolysis reactions, the rates are only moderately affected upon increasing the substituent size, and the enantioselectivity is S in all cases, also for 4-PrCL. Again, a steady decrease of the E-ratio was observed upon increasing the substituent size, but this was less pronounced than in the polymerization reactions: the E-ratios were 17.6, 12.4, and 4.6, going from 4-MeCL to 4-PrCL. For 4-substituted epsilon-caprolactones, the results obtained are a clear indication that the chirality of the propagating alcohol chain end is important in the catalytic cycle and that-in contrast to unsubstituted lactones-the rate-determining step is not necessarily the formation of the acyl-enzyme intermediate but more likely the deacylation of the acyl-enzyme intermediate by the propagating alcohol chain end.
• Enantioselective Baeyer–Villiger Oxidation: Desymmetrization of Meso Cyclic Ketones and Kinetic Resolution of Racemic 2-Arylcyclohexanones
  作者：Lin Zhou、Xiaohua Liu、Jie Ji、Yuheng Zhang、Xiaolei Hu、Lili Lin、Xiaoming Feng

  DOI：10.1021/ja309262f

  日期：2012.10.17

  N'-dioxide-Sc(III) complex catalysts. The BV oxidations of prochiral cyclohexanones and cyclobutanones afforded series of optically active ε- and γ-lactones, respectively, in up to 99% yield and 95% ee. Meanwhile, the kinetic resolution of racemic 2-arylcyclohexanones was also realized via an abnormal BV oxidation. Enantioenriched 3-aryloxepan-2-ones, whose formation is counter to the migratory aptitude, were

  在手性 N,N'-二氧化物-Sc(III) 配合物催化剂存在下，实现了外消旋和内消旋环酮的催化对映选择性 Baeyer-Villiger (BV) 氧化。前手性环己酮和环丁酮的 BV 氧化分别提供了一系列具有光学活性的 ε- 和 γ-内酯，产率高达 99%，ee 高达 95%。同时，外消旋 2-芳基环己酮的动力学拆分也是通过异常 BV 氧化实现的。Enantioenriched 3-aryloxepan-2-ones，其形成与迁移能力相反，被优先获得。内酯和未反应的酮均具有高 ee 值。
• Syntheses of some optically active .epsilon.-caprolactones
  作者：Charles G. Overberger、Howard. Kaye

  DOI：10.1021/ja00998a024

  日期：1967.10