5-(tert-butyl)oxepan-2-one | 34680-83-6

• 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: 5-(tert-butyl)oxepan-2-one
• 英文别名: 4-tert-butyl-ε-caprolactone；5-tert-Butyl-2-oxepanone；5-tert-butyloxepan-2-one
• CAS: 34680-83-6
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: XFKCBMHHCWKGMQ-UHFFFAOYSA-N

物化性质

• 熔点：
  57.5-58.5 °C(Solv: heptane (142-82-5))
• 沸点：
  130-135 °C(Press: 2 Torr)
• 密度：
  0.956±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-(tert-butyl)oxepan-2-one 在 jones reagent 、 对甲苯磺酸 作用下， 以 丙酮 为溶剂， 反应 1.0h， 生成 3-Tert-butyl-6-methoxy-6-oxohexanoic acid
  参考文献：
  名称：

  Stereochemistry of the reversible cyclization of .omega.-formylalkyl radicals

  摘要：

  The reactions of 6-bromo-4-(1',1'-dimethylethyl)hexanal (4), 5-bromo-3-(1',1'-dimethylethyl)pentanal (11), and 5-bromo-4-(1',1'-dimethylethyl)pentanal (17) with tributylstannane have been investigated in detail. The major products are the debrominated aldehydes and cycloalkanols which arise from the cyclization of the intermediate omega-formylalkyl radicals. The stersochemical outcome of the cyclization of these radicals is dependent on the stannane concentration. At high concentrations of stannane the cyclization is essentially irreversible with the cycloalkoxy radicals being trapped before beta-scission can occur. Under these conditions the relative amount of cis and trans cycloalkanols formed are equal to the ratio of the rate constants for the two modes of cyclization; both 4 and 17 show a small preference for trans cyclization, but 11 gives equal amounts of the two diastereomers. When the stannane concentration is lowered, the lifetime of the cycloalkoxy radicals increases allowing beta-scission to occur. Thus, the cis and trans cycloalkoxy radicals approach a thermodynamic equilibrium which is reflected in the relative yields of the cis and trans cycloalkanols.

  DOI：

  10.1021/jo00044a034
• 作为产物：
  描述：

  4-叔丁基环己酮 在 acyltransferase from Mycobacterium smegmatis 、 双氧水 、 乙酸乙酯 作用下， 以 水 为溶剂， 反应 90.0h， 以99%的产率得到5-(tert-butyl)oxepan-2-one
  参考文献：
  名称：

  使用耻垢分枝杆菌的酰基转移酶稳定地合成化学酶内酯

  摘要：

  证明了从耻垢分枝杆菌分离的酰基转移酶在环酮化学酶Baeyer-Villiger氧化为内酯的新应用。酰基转移酶在苛刻的反应条件下表现出高活性和高稳定性，例如在60％aq。在45°C下为H 2 O 2。这为新型高产内酯合成的鲁棒化学酶法铺平了道路。

  DOI：

  10.1016/j.catcom.2016.03.021

文献信息

• ε-Caprolactone manufacture via efficient coupling Baeyer-Villiger oxidation with aerobic oxidation of alcohols
  作者：Renfeng Du、Haoran Yuan、Chenxuan Zhao、Yongtao Wang、Jia Yao、Haoran Li

  DOI：10.1016/j.mcat.2020.110947

  日期：2020.7

  sacrificed alcohols were transformed into corresponding ketones which were also valuable chemicals. Furthermore, the efficiency of the alcohols was achieved to unprecedented 52 %. The Baeyer-Villiger oxidation of various other cycloalkanones was also examined. The substituent group effect on the efficiency of sacrificed alcohols was investigated in which weak electron-donating substituent induced nearly

  为了避免使用过酸氧化剂或高浓度过氧化氢，这些氧化剂或高浓度过氧化氢具有潜在的危险性和爆炸性，在本文中，开发了一种新的制备ε-己内酯的方法，其中使用分子氧作为末端氧化剂。商用N-羟基邻苯二甲酰亚胺和硝酸铈铵用作增加ε-己内酯收率的关键催化剂。例如，ε-己内酯的选择性为92％，环己酮的转化率为85％，这与使用高浓度过氧化氢的策略相当。牺牲的醇被转化成相应的酮，它们也是有价值的化学物质。此外，醇的效率达到了前所未有的52％。还检查了各种其他环烷酮的Baeyer-Villiger氧化。研究了取代基基团对牺牲醇效率的影响，其中弱的供电子性取代基几乎诱导了ε​​-己内酯的定量产率。
• Three-component reductive alkylation of 2-hydroxy-1,4-naphthoquinones with lactols
  作者：Eliana E. Kim、Evans O. Onyango、Jennifer R. Pace、Timothy M. Abbot、Liangfeng Fu、Gordon W. Gribble

  DOI：10.1016/j.tetlet.2016.01.036

  日期：2016.2

  Lactols II, obtained by DIBAL reduction of their corresponding lactones I, in equilibrium with their hydroxyaldehyde tautomers III were used in a three-component reductive alkylation with 2-hydroxy-1,4-naphthoquinone to give a series of 3-alkylated 2-hydroxy-1,4-naphthoquinone derivatives IV.

  通过DIBAL还原相应的内酯I并与羟醛互变异构体III平衡获得的Lactols II与2-羟基-1,4-萘醌进行三组分还原烷基化反应，得到一系列3-烷基化的2-羟基-1，4-萘醌衍生物IV。
• 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。
• Selective and Shape-Selective Baeyer–Villiger Oxidations of Aromatic Aldehydes and Cyclic Ketones with Sn-Beta Zeolites and H2O2
  作者：Michael Renz、Teresa Blasco、Avelino Corma、Vicente Fornés、Robert Jensen、Laszlo Nemeth

  DOI：10.1002/1521-3765(20021018)8:20<4708::aid-chem4708>3.0.co;2-u

  日期：2002.10.18

  oxidized to the corresponding unsaturated lactones with very high chemoselectivity. The catalyst is also selective for the oxidation of aromatic aldehydes with H2O2, producing the formate ester or the corresponding hydrolyzed product, that is the alcohol. Shape-selective oxidations are observed for isomeric reactants with different molecular shapes. The catalytic Sn sites have been characterized by 119Sn

  Sn-Beta用作Baeyer-Villiger与过氧化氢反应的非均相催化剂。环状酮被转化成相应的内酯，而不饱和酮则以非常高的化学选择性被氧化成相应的不饱和内酯。该催化剂对于用H 2 O 2氧化芳族醛也是选择性的，产生甲酸酯或相应的水解产物，即醇。对于具有不同分子形状的异构体反应物，观察到形状选择氧化。已经通过119Sn MAS-NMR光谱表征了催化的Sn位点，并且已经证明了四面体结合到沸石骨架中。原位红外光谱和18 O标记实验表明，氧化机理涉及Criegee型中间体。
• Cerium-free Luche reduction directed by rehydrated alumina
  作者：Ebenezer Jones-Mensah、Leslie A. Nickerson、Jackson L. Deobald、Hailey J. Knox、Alyssa B. Ertel、Jakob Magolan

  DOI：10.1016/j.tet.2016.03.017

  日期：2016.6

  A 1,2-regioselective reduction of α,β-unsaturated ketones to their corresponding allylic alcohols is accomplished with NaBH4 in the presence of acidic activated alumina rehydrated to the Brockmann II grade by adding 3 % w/w water. The substrate scope includes eight ketones reduced in high regio- and diastereoselectivity to their corresponding allylic alcohols. This is the first example of the strategy

  在添加3％w / w水的情况下，用NaBH 4将酸化的氧化铝复水至Brockmann II级，可以用NaBH 4将α，β-不饱和酮的1,2-区域选择性还原为相应的烯丙基醇。底物范围包括八个酮，其相对于其相应的烯丙醇具有较高的区域和非对映选择性。这是通过部分再水化系统调节氧化铝表面化学以调节反应选择性的策略的第一个例子。从成本和程序简单性的角度来看，氧化铝是常见的Luche还原添加剂CeCl 3的有吸引力的替代品。