(+)-(R)-5-isopropyloxepan-2-one | 655233-10-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (+)-(R)-5-isopropyloxepan-2-one
• 英文别名: (5R)-5-propan-2-yloxepan-2-one
• CAS: 655233-10-6
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: DDGNHMWGQKMERH-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4-异丙基环己酮 在 C₄₉H₇₆N₄O₄ 、 scandium tris(trifluoromethanesulfonate) 、 间氯过氧苯甲酸 作用下， 以 乙酸乙酯 为溶剂， 反应 18.5h， 以75%的产率得到(+)-(R)-5-isopropyloxepan-2-one
  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

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
• Engineering of a Baeyer‐Villiger monooxygenase to Improve Substrate Scope, Stereoselectivity and Regioselectivity
  作者：Xu Li、Congcong Li、Ge Qu、Bo Yuan、Zhoutong Sun

  DOI：10.1002/cbic.202400328

  日期：2024.7.2

  Baeyer‐Villiger monooxygenases belong to a family of flavin‐binding proteins that catalyze the Baeyer‐Villiger (BV) oxidation of ketones to produce lactones or esters, which are important intermediates in pharmaceuticals or sustainable materials. Phenylacetone monooxygenase (PAMO) from Thermobifida fusca with moderate thermostability catalyzes the oxidation of aryl ketone substrates, but is limited by high specificity and narrow substrate scope. In the present study, we applied loop optimization by loop swapping followed by focused saturation mutagenesis in order to evolve PAMO mutants capable of catalyzing the regioselective BV oxidation of cyclohexanone and cyclobutanone derivatives with formation of either normal or abnormal esters or lactones. We further modulated PAMO to increase enantioselectivity. Crystal structure studies indicate that rotation occurs in the NADP‐binding domain and that the high B‐factor region is predominantly distributed in the catalytic pocket residues. Computational analyses further revealed dynamic character in the catalytic pocket and reshaped hydrogen bond interaction networks, which is more favorable for substrate binding. Our study provides useful insights for studying enzyme‐substrate adaptations.