(6-甲基-5-氧代-2H-吡喃-2-基)乙酸酯 | 33647-89-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 中文名称: (6-甲基-5-氧代-2H-吡喃-2-基)乙酸酯
• 英文名称: 2-methyl-6-acetoxy-3-oxo-3,6-dihydro-2H-pyran
• 英文别名: 1-O-acetyl-2,3,6-trideoxy-α,β-DL-glycero-hex-2-enopyranos-4-ulose；6-acetoxy-2-methyl-2H-pyran-3(6H)-one；(6-methyl-5-oxo-2H-pyran-2-yl) acetate
• CAS: 33647-89-1；33647-90-4；86707-88-2；89824-88-4；120142-90-7；120142-96-3；120142-98-5；120143-00-2；62357-52-2
• 化学式: C₈H₁₀O₄
• 分子量: 170.165
• InChiKey: GMRFAZZMYGJAQO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  (6-甲基-5-氧代-2H-吡喃-2-基)乙酸酯 在 三乙胺 作用下， 以 氯仿 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Regioselective Synthesis of Novel 7-5-8-Fused Oxabridged Tricyclic Molecules via Consecutive Dipolar Cycloaddition of Pentafulvenes with 3-Oxidopyrylium Betaines

  摘要：

  五碳烯烃与各种取代的氧化吡啶鎓甜菜碱发生连续的二极环加成反应，形成了一类结构有趣的新型 7-5-8 熔合氧化三环分子。

  DOI：

  10.1055/s-2006-942366
• 作为产物：
  描述：

  DL-1-(2-呋喃基)乙醇 在 吡啶 、 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 作用下， 生成 (6-甲基-5-氧代-2H-吡喃-2-基)乙酸酯
  参考文献：
  名称：

  [6+3] Cycloaddition of pentafulvenes with 3-oxidopyrylium betaine: a novel methodology toward the synthesis of 5–8 fused oxabridged cyclooctanoids

  摘要：

  Pentafulvenes undergo a facile [6+3] cycloaddition with 3-oxidopyrylium betaine, generated from the corresponding pyranulose acetate, leading to the formation of 5-8 fused oxabridged cyclooctanoids. The product is formed by a [6+3] cycloaddition, followed by a 1,5-hydrogen shift of the initially formed [6+3] adduct. The reaction was found to be general and a number of fulvenes with a wide range of substituents at the exocyclic double bond, that is, at the C6 position followed a similar reactivity pattern. The [6+3] adduct, a 5-8 fused oxabridged cyclooctanoid, is potentially amenable to a number of synthetic transformations due to the presence of an alpha, beta-unsaturated ketone and cyclopentadiene part. By selecting appropriately substituted fulvene and pyranulose acetates, it is possible to use this methodology for the synthesis of a wide range of 5-8 fused cyclooctanoids. The experimental results have been rationalized on the basis of theoretical calculations. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.04.017

文献信息

• Asymmetric synthesis of trans-4,5-dioxygenated cyclopentenone derivatives by organocatalyzed rearrangement of pyranones and enzymatic dynamic kinetic resolution
  作者：João P.M. Nunes、Luís F. Veiros、Pedro D. Vaz、Carlos A.M. Afonso、Stephen Caddick

  DOI：10.1016/j.tet.2011.02.018

  日期：2011.4

  Dioxygenated cyclopentenones are versatile building blocks for the synthesis of several natural products. Herein we report a direct asymmetric synthesis of trans-4,5-dioxygenated cyclopentenone derivatives through base-catalyzed rearrangement of pyranones followed by dynamic kinetic resolution. Milder conditions than previously reported for this rearrangement have been found regarding amine base catalysis

  双氧合环戊烯酮是用于合成多种天然产物的通用构建基块。在本文中，我们报告了通过碱催化的吡喃酮重排，然后进行动态动力学拆分，直接反对称合成反式-4,5-二加氧环戊烯酮衍生物。在胺碱催化，溶剂和温度影响方面，已经发现比先前报道的用于这种重排的条件更温和的条件。所有数据都支持一种机制，该机制涉及由吡喃酮衍生的烯醇的电环开环形成的中间体的环化。我们已经开发了反式-4-叔丁基不对称合成的条件经由脂肪酶诱导的动力学动力学拆分，以81％的收率和95％的ee得到-丁氧基-5-羟基环戊-2-烯酮和类似的双加氧环戊烯酮。
• Design, Synthesis, and Phenotypic Profiling of Pyrano‐Furo‐Pyridone Pseudo Natural Products
  作者：Andreas Christoforow、Julian Wilke、Aylin Binici、Axel Pahl、Claude Ostermann、Sonja Sievers、Herbert Waldmann

  DOI：10.1002/anie.201907853

  日期：2019.10.7

  Natural products (NPs) inspire the design and synthesis of novel biologically relevant chemical matter, for instance through biology-oriented synthesis (BIOS). However, BIOS is limited by the partial coverage of NP-like chemical space by the guiding NPs. The design and synthesis of "pseudo NPs" overcomes these limitations by combining NP-inspired strategies with fragment-based compound design through

  天然产物 (NP) 激发了新型生物学相关化学物质的设计和合成，例如通过面向生物学的合成 (BIOS)。然而，BIOS 受到引导 NP 对类 NP 化学空间的部分覆盖的限制。“伪纳米粒子”的设计和合成克服了这些限制，通过将纳米粒子衍生的片段与生物合成无法获得的前所未有的化合物类别相结合，将纳米粒子启发的策略与基于片段的化合物设计相结合。我们描述了吡喃并呋喃吡啶酮（PFP）假纳米颗粒的开发和生物学评价，该纳米颗粒将吡啶酮和二氢吡喃纳米颗粒片段以三种异构体排列组合在一起。化学信息学分析表明，PFP 位于类似 NP 的化学空间区域，该区域未被现有 NP 覆盖，而是被药物和相关化合物覆盖。与目标无关的“细胞绘画”测定中的表型分析表明，PFP 诱导活性氧的形成，并且是结构新颖的线粒体复合物 I 抑制剂。
• Diastereoselective 1,3-dipolar cycloaddition of pyrylium ylides with chiral enamides
  作者：Kirill Tchabanenko、Colleen Sloan、Yves-Mael Bunetel、Philip Mullen

  DOI：10.1039/c2ob07007c

  日期：——

  Chiral enamides 5f–i were found to react with pyrylium ylides to give cycloadducts 6d–i in good yields with an excellent level of stereoselectivity. The chiral auxiliary was successfully removed on hydrogenolysis of compound 6f in continuous flow (H-Cube) resulting in the first asymmetric synthesis of complex amine 8.

  发现手性烯酰胺5f–i与吡啶阳离子反应，生成了立体选择性极高的环加成物6d–i，并且产率良好。在连续流动（H-Cube）条件下对化合物6f进行氢解，成功去除了手性辅助基，首次实现复杂胺8的非对称合成。
• Intermolecular Regio‐ and Stereoselective Hetero‐[5+2] Cycloaddition of Oxidopyrylium Ylides and Cyclic Imines
  作者：Changgui Zhao、Daniel A. Glazier、Daoshan Yang、Dan Yin、IIia A. Guzei、Michael M. Aristov、Peng Liu、Weiping Tang

  DOI：10.1002/anie.201811896

  日期：2019.1.14

  We have developed the first intermolecular hetero‐[5+2] cycloaddition reaction between oxidopyrylium ylides and cyclic imines with excellent control of regio‐ and stereoselectivity. Surprisingly, divergent stereochemistry was observed depending on the substitution pattern of the oxidopyrylium ylide. This new reaction provides quick access to highly substituted nitrogen‐containing seven‐membered rings—azepanes

  我们开发了第一个分子间异[5 + 2]环氧化吡啶鎓和环状亚胺之间的杂分子间[5 + 2]环加成反应，可很好地控制区域选择性和立体选择性。出乎意料的是，根据氧化吡啶鎓叶立德的取代模式观察到不同的立体化学。这种新的反应使人们可以快速进入高度取代的含氮七元环-氮杂环丁烷。值得注意的是，广泛的氧化吡啶鎓基团和环状亚胺参与了这种新型的异[5 + 2]环加成反应，并且环加合物可以轻松转化为生物活性天然产物的核心骨架。DFT计算表明，环加成反应通过逐步途径进行，亚胺氮原子充当亲核试剂以引发环加成反应。
• [6+3] Cycloaddition of fulvenes with 3-oxidopyrylium betaine: a novel methodology for the synthesis of fused cyclooctanoid natural products
  作者：K.V. Radhakrishnan、K. Syam Krishnan、Mohan M. Bhadbhade、Gaurav V. Bhosekar

  DOI：10.1016/j.tetlet.2005.05.042

  日期：2005.7

  Fulvenes undergo an easy [6+3] cycloaddition with 3-oxidopyrylium betaines leading to 5–8 fused oxabridged cyclooctanoids.

  富勒烯与3个氧化吡啶鎓甜菜碱容易进行[6 + 3]环加成反应，从而生成5–8个稠合的氧桥联环庚烷类化合物。