dihydro-2H-pyran-2,5(3H)-dione

• 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: dihydro-2H-pyran-2,5(3H)-dione
• 英文别名: ternatolide；4-oxo-valerolactone；4-oxo-δ-valerolactone；Tetrahydropyran-2,5-dione；oxane-2,5-dione
• 化学式: C₅H₆O₃
• 分子量: 114.101
• InChiKey: GYHJUGYOSOGTKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  dihydro-2H-pyran-2,5(3H)-dione 在 sodium tetrahydroborate 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 以98 %的产率得到5-(羟基甲基)二氢呋喃-2(3H)-酮
  参考文献：
  名称：

  Achmatowicz 衍生物的 Ru 催化异构化：生物可再生能源和生物活性内酯的可持续途径

  摘要：

  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。

  DOI：

  10.1021/acscatal.2c04867
• 作为产物：
  描述：

  2,6-二氢-6-羟基-3(3H)-吡喃酮 在 cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate 作用下， 以 乙腈 为溶剂， 以99 %的产率得到dihydro-2H-pyran-2,5(3H)-dione
  参考文献：
  名称：

  Achmatowicz 衍生物的 Ru 催化异构化：生物可再生能源和生物活性内酯的可持续途径

  摘要：

  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。

  DOI：

  10.1021/acscatal.2c04867

文献信息

• Cu‐Catalyzed Tandem Oxidation‐Intramolecular Cannizzaro Reaction of Biorenewables and Bioactive Molecules
  作者：Hristo Petkov、Martin A. Ravutsov、Manuel J. Verganista、Yavor N. Mitrev、Nuno R. Candeias、Svilen P. Simeonov

  DOI：10.1002/cssc.202400013

  日期：——

  A Cu-catalyzed tandem oxidation-intramolecular Cannizzaro reaction that converts α-hydroxyketones into valuable α-hydroxyesters under mild conditions is reported. The substrate scope encompasses biorenewable synthons and complex structures, such as steroids. We provided mechanistic insights using isotope labeling and rationalization by computational means.

  据报道，铜催化的串联氧化-分子内坎尼扎罗反应可在温和条件下将 α-羟基酮转化为有价值的 α-羟基酯。底物范围包括生物可再生合成子和复杂结构，例如类固醇。我们使用同位素标记和计算手段合理化提供了机制见解。
• A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process
  作者：Albert Padwa、Alan T. Price、Lin Zhi

  DOI：10.1021/jo952078h

  日期：1996.1.1

  alpha-Diazo ketones containing an amido group in the gamma-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a gamma-keto delta-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated st-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can be attributed to the competitive hydrolysis of the zwitterionic intermediate. The Rh(II)-catalyzed reaction of the diazo ketoamide derived from N-benzylpiperidone with DMAD afforded two different types of cycloadducts. In addition to the spiro cyclopentyl epoxide, a product derived from trapping of the carbonyl ylide dipole was also obtained, thereby providing additional support for the proposed mechanism.
• 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。