(5-氧代四氢呋喃-2-基)乙酸甲酯 | 5904-80-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 中文名称: (5-氧代四氢呋喃-2-基)乙酸甲酯
• 英文名称: (5-oxotetrahydrofuran-2-yl)methyl acetate
• 英文别名: ω-acetoxy-γ-pentanolactone；5-(acetoxymethyl)dihydro-2(3H)-furanone；dihydro-5-acetoxymethyl-2(3H)-furanone；5-acetoxymethyl-2-tetrahydrofuranone；5-acetoxymethyl-dihydro-furan-2-one；5-Acetoxymethyl-dihydro-furan-2-on；(5-Oxooxolan-2-yl)methyl acetate
• CAS: 5904-80-3；79580-69-1；112607-21-3；112709-12-3
• 化学式: C₇H₁₀O₄
• 分子量: 158.154
• InChiKey: BXLQWTUDERRWIA-UHFFFAOYSA-N

物化性质

• 沸点：
  100-103 °C(Press: 0.1 Torr)
• 密度：
  1.181±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (5-氧代四氢呋喃-2-基)乙酸甲酯 在 Burkholderia cepacia lipase 、 水 、 sodium hydroxide 作用下， 以 aq. phosphate buffer 、 丙酮 为溶剂， 生成 (5S)-5-(hydroxymethyl)-2-oxo-tetrahydrofuran 、 (R)-γ-羟甲基-γ-丁内酯 (R)-4,5-二氢-5-羟甲基-2(3H)-呋喃酮 (R)-5-羟甲基-2-氧代四氢呋喃
  参考文献：
  名称：

  洋葱伯克霍尔德氏菌脂肪酶对γ-丁内酯伯醇的对映和非对映选择性的分子基础

  摘要：

  AbstractBurkholderia cepacia lipase (BCL) shows high enantioselectivity toward chiral primary alcohols, but this enantioselectivity is often unpredictable, especially for substrates that contain an oxygen at the stereocenter. For example, BCL resolves β‐substituted‐γ‐acetyloxymethyl‐γ‐butyrolactones (acetates of a chiral primary alcohol) by hydrolysis of the acetate, but the enantioselectivity varies with the nature and orientation of the β‐alkyl substituent. BCL favors the (R)‐primary alcohol when the β‐alkyl substituent is hydrogen (E=30) or trans methyl (E=38), but the (S)‐primary alcohol when it is cis methyl (E=145). To rationalize this unusual selectivity, we used a combination of experiments to show the importance of polar interactions and modeling to reveal differences in orientations of the enantiomers. Removal of either the lactone carbonyl in the substrate or the polar side chains in the enzyme by using a related enzyme without these side chains decreased the enantioselectivity at least four‐fold. Modeling revealed that the slow enantiomers do not bind by exchanging the location of two substituents relative to the fast enantiomer. Instead, three substituents remain in the same region, but the fourth substituent, hydrogen, inverts to a new location, like an umbrella in a strong wind. In this orientation the favored stereoisomers have similar shapes, thus accounting for the unusual stereoselectivity. The ratio of catalytically productive orientations for the fast vs. slow enantiomers in a molecular dynamic simulation correlated (R2=0.82) with the degree of enantioselectivity including the case where the enantioselectivity reversed. Weighting this ratio by the ratio of H‐bonds in the polar interaction to account for different binding strengths improved the correlation with the measured enantioselectivity to R2=0.97. The modeling identifies key interactions responsible for high enantioselectivity in this class of substrates.magnified image

  DOI：

  10.1002/adsc.201400510
• 作为产物：
  描述：

  四氢糠醇乙酸酯 在 碘苯二乙酸 、 叔丁基过氧化氢 作用下， 以 硝基甲烷 、 癸烷 为溶剂， 反应 12.0h， 以65%的产率得到(5-氧代四氢呋喃-2-基)乙酸甲酯
  参考文献：
  名称：

  Oxidative transformation of cyclic ethers/amines to lactones/lactams using a DIB/TBHP protocol

  摘要：

  使用DIB/TBHP方案，开发了一种对环醚和胺进行新颖的C-H氧化反应，生成相应的内酯和内酰胺。该反应温和且不涉及金属试剂。此外，研究表明取代基的电子性质会影响氧化反应的选择性。

  DOI：

  10.1039/c3ra44184a

文献信息

• Triflic Acid Catalyzed Oxidative Lactonization and Diacetoxylation of Alkenes Using Peroxyacids as Oxidants
  作者：Yan-Biao Kang、Lutz H. Gade

  DOI：10.1021/jo202491y

  日期：2012.2.3

  A clean and efficient diacetoxylation reaction of alkenes catalyzed by triflic acid using commercially available peroxyacids as the oxidants has been developed. This method was also applied in oxidative lactonizations of unsaturated carboxylic acids in good to high yields.

  已经开发了使用可商购的过氧酸作为氧化剂的三氟甲磺酸催化的烯烃的清洁且有效的二乙酰氧基化反应。该方法还以高产率到高产率用于不饱和羧酸的氧化内酯化。
• Aerobic Acetoxyhydroxylation of Alkenes Co-catalyzed by Organic Nitrite and Palladium
  作者：Xian-Min Chen、Xiao-Shan Ning、Yan-Biao Kang

  DOI：10.1021/acs.orglett.6b02743

  日期：2016.10.21

  An aerobic acetoxyhydroxylation of alkenes cooperatively catalyzed by organic nitrite and palladium at room temperature using clean and cheap air as the sole oxidant has been developed. Various vicinal diols, diacetoxyalkanes, and dihalogenoalkanes have been synthesized. The gram-scale synthesis has also been approached. Vicinal difluorination and dichlorolation products have also been achieved via

  已经开发了有机亚硝酸盐和钯在室温下使用清洁廉价的空气作为唯一氧化剂协同催化的烯烃的好氧乙酰氧基羟化反应。已经合成了各种邻二醇，二乙酰氧基烷烃和二卤代烷烃。也已经进行了克级合成。通过该反应也已经获得了邻二氟和二氯化产物。
• Analytic and preparative resolution of recemic ?- and ?-lactones by chromatography on cellulose triacetate. Relationship between elution order and absolute configuration
  作者：Eric Francotte、Dieter Lohmann

  DOI：10.1002/hlca.19870700615

  日期：1987.9.23

  biologically active substances) have been separated chromatographically on the chiral phase cellulose triacetate, crystallographic form I (CTAI). For different series of five-membered-ring lactones, relationships have been found between the elution order of the enantiomers and their absolute configuration. Preparative resolutions of γ-Phenyl-γ-butyrolactone (1) and of the Pheromone component 5b have been carried

  在手性相三醋酸纤维素上色谱分离了各种手性五元和六元环内酯的对映异构体（重要的一类化合物（香料和信息素成分，生物活性物质合成中的关键中间体）） （CTAI）。对于不同系列的五元环内酯，已经发现对映异构体的洗脱顺序与其绝对构型之间的关系。进行了γ-苯基-γ-丁内酯（1）和信息素成分5b的制备拆分，以证明该方法可用于克级分离。
• Efficient Oxidative Cleavage of Tetrahydrofuran-2-methanols to γ-Lactones by a 2-Iodobenzamide Catalyst in Combination with Oxone^®
  作者：Takayuki Yakura、Yuto Horiuchi、Yushi Nishimura、Akihiro Yamada、Hisanori Nambu、Tomoya Fujiwara

  DOI：10.1002/adsc.201500795

  日期：2016.3.17

  An environmentally friendly oxidative cleavage of tetrahydrofuran‐2‐methanols to the corresponding γ‐lactones using a catalytic amount of 2‐iodo‐N‐isopropylbenzamide has been developed. The reaction of various tetrahydrofuran‐2‐methanols with the catalyst in the presence of Oxone® (2 KHSO5⋅KHSO4⋅K2SO4) as a co‐oxidant in DMF at room temperature successfully affords the corresponding lactones in good

  已开发出使用催化量的2-碘-N-异丙基苯甲酰胺对四氢呋喃-2-甲醇进行环境友好的氧化裂解为相应的γ-内酯。各种四氢呋喃-2-基甲醇与催化剂在存在反应的Oxone ®（2 KHSO 5 ⋅KHSO 4 ⋅K 2 SO 4），其在室温下共氧化剂在DMF成功得到良好的相应的内酯，以高收率，并通过还原后处理即可轻松实现催化剂的回收。该方法之所以显着，是因为它可以在温和的条件下将四氢呋喃-2-甲醇转化为γ-内酯，而无需使用任何有毒的重金属。
• [4-Iodo-3-(isopropylcarbamoyl)phenoxy]acetic Acid as a Highly Reactive and Easily Separable Catalyst for the Oxidative Cleavage of Tetrahydrofuran-2-methanols to γ-Lactones
  作者：Takayuki Yakura、Tomoya Fujiwara、Hideyuki Nishi、Yushi Nishimura、Hisanori Nambu

  DOI：10.1055/s-0037-1610657

  日期：2018.10

  product were easily separated by only liquid–liquid separation without chromatography. In addition, using a mixture of nitromethane and N,N-dimethylformamide as the solvent and heating enabled a low catalyst loading, a short reaction time, and high product yield. Oxidative cleavage using the new catalyst can be used as a practical and efficient method for synthesizing γ-lactones.

  [4-Iodo-3-(异丙基氨基甲酰基)苯氧基]乙酸被开发为一种高活性且易于分离的催化剂，用于在 Oxone® (2KHSO5·KHSO4·K2SO4) 存在下将四氢呋喃-2-甲醇氧化裂解为 γ-内酯) 作为助氧化剂。这种新催化剂的反应性大大高于我们之前报道的催化剂 2-碘-N-异丙基苯甲酰胺。新催化剂和产物很容易通过仅液-液分离而无需色谱法分离。此外，使用硝基甲烷和N,N-二甲基甲酰胺的混合物作为溶剂和加热能够实现低催化剂负载、短反应时间和高产物收率。使用新催化剂进行氧化裂解可作为一种实用且有效的合成γ-内酯的方法。