4-oxo-5-hexanolide | 134936-64-4

• 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: 4-oxo-5-hexanolide
• 英文别名: 6-Methyloxane-2,5-dione
• CAS: 134936-64-4
• 化学式: C₆H₈O₃
• 分子量: 128.128
• InChiKey: VUJGEIYAMCCQJV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-oxo-5-hexanolide 在 platinum(IV) oxide 吡啶 、 4-二甲氨基吡啶 、 盐酸羟胺 、 氢气 、 sodium acetate 作用下， 以 甲醇 、 二氯甲烷 、 水 、 溶剂黄146 为溶剂， 25.0~55.0 ℃ 、249.99 kPa 条件下， 反应 8.5h， 生成 5(S)-(1-hydroxyethyl)-2-pyrrolidinone
  参考文献：
  名称：

  A Convenient Synthesis of 5-Substituted 2-Pyrrolidinones via 2H-Pyran-3(6H)-ones

  摘要：

  6- 羟基-2H-吡喃-3(6H)-酮的琼斯氧化、随后的氢化、肟的形成和催化氢化，构成了一条从醛或酮开始合成各种 5-取代的 2-吡咯烷酮衍生物的有效途径。

  DOI：

  10.1055/s-1991-26470
• 作为产物：
  描述：

  6-hydroxy-2-methyl-2H-pyran-3(6H)-one 在 jones reagent 、 溶剂黄146 、 锌 作用下， 以 氯仿 、 丙酮 为溶剂， 反应 2.25h， 生成 4-oxo-5-hexanolide
  参考文献：
  名称：

  A Convenient Synthesis of 5-Substituted 2-Pyrrolidinones via 2H-Pyran-3(6H)-ones

  摘要：

  6- 羟基-2H-吡喃-3(6H)-酮的琼斯氧化、随后的氢化、肟的形成和催化氢化，构成了一条从醛或酮开始合成各种 5-取代的 2-吡咯烷酮衍生物的有效途径。

  DOI：

  10.1055/s-1991-26470

文献信息

• Allene epoxidation: synthesis of functionalized lactones by the DMDO oxidation of allenic acids
  作者：Jack K Crandall、Elisa Rambo

  DOI：10.1016/s0040-4020(02)00698-1

  日期：2002.8

  products are formed directly from allene oxides, keto lactones are formed. The corresponding spirodioxide intermediates give lactones with appropriately situated α-hydroxyketone moieties. An understanding of the regiochemistry of the epoxidations and the subsequent cyclizations of the reactive intermediates is developed, as are methods for the manipulation of the experimental conditions to favor the

  通过二甲基二环氧乙烷促进的氧化环化反应，一系列烯丙基羧酸已转化为官能化的内酯。这些转化通过未分离的氧化烯和螺二氧化物中间体的参与而合理化。起始烯丙酸的结构和反应条件决定了这两个中间物种中的哪个充当分离产物的来源。所制备的氧化剂溶液的使用通常通过螺二氧化物进行。而原位反应通常会产生衍生自氧化烯的产物。当直接由氧化烯形成产物时，会形成酮内酯。相应的螺二氧化物中间体产生具有适当定位的α-羟基酮部分的内酯。
• Rationalizing the Origin of Solerone (5-Oxo-4-hexanolide):  Biomimetic Synthesis and Identification of Key Metabolites in Sherry Wine
  作者：Dietmar Häring、Peter Schreier、Markus Herderich

  DOI：10.1021/jf960316j

  日期：1997.2.1

  A biomimetic synthesis of solerone (5-oxo-4-hexanolide, 1) using both enzymatic and acid-catalyzed reactions was performed. Starting from L-glutamic acid 5-ethyl ester (2) enzymatic oxidative deamination followed by subsequent decarboxylation of the corresponding 2-oxoglutaric acid Ei-ethyl ester (3) led to ethyl 4-oxobutanoate (4). In the presence of pyruvate, 4 served as key substrate for a novel acyloin condensation catalyzed by pyruvate decarboxylase (EC 4.1.1.1) from Saccharomyces cerevisiae. Finally, the resulting ethyl 4-hydroxy-5-oxo-hexanoate (5) was easily converted into solerone (1) in the presence of acid. The acyloin condensation of 3 with acetaldehyde to ethyl 5-hydroxy-4-oxohexanoate (6) revealed an alternative route to solerone (1). Acid-catalyzed lactonization of 6 produced 4-oxo-5-hexanolide (7) as well as 5 and 1 via keto-enol tautomerization. Confirming the relevance of the proposed biogenetic pathway, the solerone precursors 2-6 as well as delta-lactone 7 were identified in sherry by GC/MS analysis for the first time.
• A Convenient Synthesis of 5-Substituted 2-Pyrrolidinones via 2<i>H</i>-Pyran-3(6<i>H</i>)-ones
  作者：Minas P. Georgiadis、Serkos A. Haroutounian、Costas D. Apostolopoulos

  DOI：10.1055/s-1991-26470

  日期：——

  Jones oxidation of 6-hydroxy-2H-pyran-3(6H)-ones, subsequent hydrogenation, oxime formation and catalytic hydrogenation constitute an efficient route for the synthesis of various 5-substituted 2-pyrrolidinone derivatives starting from aldehydes or ketones.

  6- 羟基-2H-吡喃-3(6H)-酮的琼斯氧化、随后的氢化、肟的形成和催化氢化，构成了一条从醛或酮开始合成各种 5-取代的 2-吡咯烷酮衍生物的有效途径。
• Ru-Catalyzed Isomerization of Achmatowicz Derivatives: A Sustainable Route to Biorenewables and Bioactive Lactones
  作者：Miroslav Dangalov、Adolfo Fernández-Figueiras、Martin A. Ravutsov、Ekaterina Vakarelska、Maya K. Marinova、Nuno R. Candeias、Svilen P. Simeonov

  DOI：10.1021/acscatal.2c04867

  日期：2023.2.3

  A Ru-catalyzed isomerization of Achmatowicz derivatives that opens unexplored routes to diversify the biogenic furanic platform is reported. The mechanistic insights of this formally redox-neutral intramolecular process were studied computationally and by deuterium labeling. The transformation proved to be a robust synthetic tool to achieve the synthesis of bioderived-monomers and a series of 4-keto-δ-valerolactones

  报道了 Achmatowicz 衍生物的 Ru 催化异构化，该异构化开辟了使生物源呋喃平台多样化的未开发途径。通过计算和氘标记研究了这种正式的氧化还原中性分子内过程的机理见解。该转化被证明是一种强大的合成工具，可实现生物衍生单体和一系列 4-酮基-δ-戊内酯的合成，进一步促进了合成乙酰基合成的灵活策略的发展。还描述了两种天然产物（即 ( S , S )-muricatacin 和 ( S , S )-L-因子）的简洁且无保护基团的不对称全合成。