(S)-5-isopropyloxepan-2-one

• 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: (S)-5-isopropyloxepan-2-one
• 英文别名: (5S)-5-propan-2-yloxepan-2-one
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: DDGNHMWGQKMERH-QMMMGPOBSA-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 E_. coli expressing Brevibacterium sp. ChnB₁ monooxygenase 作用下， 以 various solvent(s) 为溶剂， 反应 12.0h， 生成 (S)-5-isopropyloxepan-2-one
  参考文献：
  名称：

  评估八种新型Baeyer-Villiger单加氧酶对烷基取代的环己酮的底物选择性和对映选择性

  摘要：

  最近，从居住在污水处理厂的细菌中克隆了编码八种拜尔-维利格单加氧酶的基因。我们进行了系统的研究，其中每个新克隆的酶以及不动杆菌属的环己酮单加氧酶。NCIB 9871用于氧化15种不同的烷基取代的环己酮。底物组包括相等数量的2-，3-和4-烷基取代的化合物，以探测每种酶对一系列同源的重要合成化合物的立体选择性。对于所有测试的4-烷基取代的环己酮，发现了能够提供相应的相应酶（See≥98％ee的内酯。对于所检查的2-烷基取代的环己酮也是如此。对于3-烷基取代的环己酮而言，情况更为复杂。在少数情况下，单一的Baeyer-Villiger单加氧酶对这些化合物具有很高的区域选择性和对映选择性。但是，更常见的是，它们仅显示出一种类型的选择性。尽管如此，具有这种性质的酶仍可以用作两步生物过程的一部分，在该过程中，最初的动力学拆分随后是对分离的光学纯酮的区域选择性氧化。

  DOI：

  10.1021/jo030253l

文献信息

• Recombinant Baker's Yeast as a Whole-Cell Catalyst for Asymmetric Baeyer−Villiger Oxidations
  作者：Jon D. Stewart、Kieth W. Reed、Carlos A. Martinez、Jun Zhu、Gang Chen、Margaret M. Kayser

  DOI：10.1021/ja972942i

  日期：1998.4.1

  4-substituted cyclohexanones (R = Me, Et, n-Pr, i-Pr, allyl, n-Bu), almost all of which were oxidized to the corresponding e-caprolactones in good yields and high enantioselectivities (typically ≥ 95%). Mesomeric 4-substituted cyclohexanones were oxidized to e-caprolactones in ≥ 92% ee. The engineered yeast strain also effected kinetic resolutions of 2-substituted cyclohexanones with enantioselectivity values

  来自不动杆菌属的环己酮单加氧酶 (EC 1.14.13.22)。NCIB 9871 已在面包酵母 (Saccharomyces cerevisiae) 中表达，以创建用于不对称 Baeyer-Villiger 氧化的通用试剂。这种“设计酵母”方法结合了使用纯化酶的优点（单一催化种类，无过度代谢等）和全细胞反应的优点（实验简单，无需辅因子再生等）。酵母试剂用于系统检测一系列2-、3-和4-取代的环己酮（R = Me、Et、n-Pr、i-Pr、烯丙基、n-Bu），几乎全部被氧化以良好的收率和高对映选择性（通常≥ 95%）转化为相应的ε-己内酯。内消旋 4-取代的环己酮在 ≥ 92% ee 中被氧化成ε-己内酯。工程酵母菌株还影响了 2-取代环己酮的动力学分辨率，对大于甲基的取代基的对映选择性值 ≥ 200。3-取代环的行为...
• The enzymatic baeyer-villiger oxidation: A study of 4-substituted cyclohexanones
  作者：Michael J. Taschner、Donald J. Black、Quin-Zene Chen

  DOI：10.1016/s0957-4166(00)80248-7

  日期：1993.6

  A study of the enzymatic Baeyer-Villiger oxidation of a number of 4-substituted cyclohexanones utilizing the enzyme cyclohexanone oxygenase (E.C. 1.14.13.-), isolated from the bacteria Acinetobacter NCIB 9871, is described.
• ‘Designer yeast’: a new reagent for enantioselective Baeyer–Villiger oxidations
  作者：Jon D. Stewart、Kieth W. Reed、Margaret M. Kayser

  DOI：10.1039/p19960000755

  日期：——

  The catalytic repertoire of baker's yeast has been expanded to include enantioselective Baeyer-Villiger oxidations. To create this catalyst, the Acinetobacter sp. cyclohexanone monooxygenase gene was inserted into a yeast expression vector and this was used to create a 'designer yeast' that performed oxidation reactions. Whole cell-mediated Baeyer-Villiger reactions were carried out on a 1.0 mmol scale and several cyclic ketones were converted in 20-30 h into the corresponding lactones in isolated yields of 60-83%. Under the reaction conditions, ketone reduction constituted only a minor side-reaction. Oxidation of prochiral 4-substituted cyclohexanones produced lactones with very high enantioselectivities.
• 10.1002/cbic.202400328
  作者：Li, Xu、Li, Congcong、Qu, Ge、Yuan, Bo、Sun, Zhoutong

  DOI：10.1002/cbic.202400328

  日期：——

  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.
• Assessing the Substrate Selectivities and Enantioselectivities of Eight Novel Baeyer−Villiger Monooxygenases toward Alkyl-Substituted Cyclohexanones
  作者：Brian G. Kyte、Pierre Rouvière、Qiong Cheng、Jon D. Stewart

  DOI：10.1021/jo030253l

  日期：2004.1.1

  4-alkyl-substituted cyclohexanones tested, enzymes were discovered that afforded each of the corresponding (S)-lactones in ≥98% ee. This was also true for the 2-alkyl-substituted cyclohexanones examined. The situation was more complex for 3-akyl-substituted cyclohexanones. In a few cases, single Baeyer−Villiger monooxygenases possessed both high regio- and enantioselectivities toward these compounds

  最近，从居住在污水处理厂的细菌中克隆了编码八种拜尔-维利格单加氧酶的基因。我们进行了系统的研究，其中每个新克隆的酶以及不动杆菌属的环己酮单加氧酶。NCIB 9871用于氧化15种不同的烷基取代的环己酮。底物组包括相等数量的2-，3-和4-烷基取代的化合物，以探测每种酶对一系列同源的重要合成化合物的立体选择性。对于所有测试的4-烷基取代的环己酮，发现了能够提供相应的相应酶（See≥98％ee的内酯。对于所检查的2-烷基取代的环己酮也是如此。对于3-烷基取代的环己酮而言，情况更为复杂。在少数情况下，单一的Baeyer-Villiger单加氧酶对这些化合物具有很高的区域选择性和对映选择性。但是，更常见的是，它们仅显示出一种类型的选择性。尽管如此，具有这种性质的酶仍可以用作两步生物过程的一部分，在该过程中，最初的动力学拆分随后是对分离的光学纯酮的区域选择性氧化。