6-[(acetoxy)methyl]-6-hydroxy-2H-pyran-3(6H)-one | 120040-08-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 6-[(acetoxy)methyl]-6-hydroxy-2H-pyran-3(6H)-one
• 英文别名: 2H-Pyran-3(6H)-one, 6-[(acetyloxy)methyl]-6-hydroxy-；(2-hydroxy-5-oxopyran-2-yl)methyl acetate
• CAS: 120040-08-6
• 化学式: C₈H₁₀O₅
• 分子量: 186.164
• InChiKey: ZKMNECGBCBPSRD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6-[(acetoxy)methyl]-6-hydroxy-2H-pyran-3(6H)-one 在 吡啶 、 4-二甲氨基吡啶 、 2,6-二叔丁基吡啶 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 14.5h， 生成 (1RS,5RS,6SR,7RS)-5-[(acetyloxy)methyl]-7-methyl-6-phenyl-8-oxabicyclo[3.2.1]oct-3-en-2-one
  参考文献：
  名称：

  Synthesis of the 5-hydroxymethyl-6-aryl-8-oxabicyclo[3.2.1]oct-3-en-2-one natural products descurainin and cartorimine

  摘要：

  Reaction of pyranulose 6 with styrenes 12c or 13 and Et3N in CH2O2 at 25 degrees C afforded the [5+2] cycloadducts 14c and 15, which were hydrolyzed to give the natural products I and descurainin (2) in 24 and 27% overall yield, respectively. Heating pyranulose 6 with cinnamate ester 21 in the presence of 2,6-di-t-butylpyridine in CH3CN at 175 degrees C afforded the [5+2] cycloadduct, which was hydrolyzed to give cartorimine (3) in 13% yield. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.10.083
• 作为产物：
  描述：

  5-乙酰氧基甲基-2-呋喃醛 在 sodium tetrahydroborate 、 溴 作用下， 以 乙醇 、 甲醇 、 水 为溶剂， 反应 0.17h， 以80%的产率得到6-[(acetoxy)methyl]-6-hydroxy-2H-pyran-3(6H)-one
  参考文献：
  名称：

  Synthesis of (±)-cartorimine

  摘要：

  Heating pyranulose 4 and cinnamate 2 in the presence of 2,6-di-t-butylpyridine in CH3CN afforded the [5 divided by 2] cycloadduct, which was hydrolyzed to give 13% of cartorimine (1). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.12.007

文献信息

• Efficient generation of an oxidopyrylium ylide using a Pd catalyst and its [5+2] cycloadditions with several dipolarophiles
  作者：Hiroyuki Suga、Taichi Iwai、Masahiro Shimizu、Kie Takahashi、Yasunori Toda

  DOI：10.1039/c7cc09552j

  日期：——

  6-acetoxy-6-acetoxymethyl-2H-pyran-3(6H)-one using a Pd catalyst and [5+2] cycloadditions of the resulting ylide are described. Among substituted styrene derivatives as dipolarophiles, electron-rich styrenes showed higher yield (up to 80%). The [5+2] cycloaddition reactions can also be applied to exo-methylene cyclic compounds, and an improved method for the synthesis of polygalolide intermediate has been

  描述了使用Pd催化剂从6-乙酰氧基-6-乙酰氧基甲基-2 H-吡喃-3（6 H）-1生成氧化吡啶鎓叶立德的有效方法，以及所得的叶立德的[5 + 2]环加成。在取代的苯乙烯衍生物（如双极性亲和剂）中，富电子苯乙烯显示出更高的收率（高达80％）。[5 + 2]环加成反应也可以用于外亚甲基环状化合物，并且已经证明了一种改进的合成聚没食子酸酯中间体的方法。
• Triethylamine Enables Catalytic Generation of Oxidopyrylium Ylides for [5+2] Cycloadditions with Alkenes: An Efficient Entry to 8-Oxabicyclo[3.2.1]octane Frameworks
  作者：Yasunori Toda、Masahiro Shimizu、Taichi Iwai、Hiroyuki Suga

  DOI：10.1002/adsc.201800290

  日期：2018.6.15

  of 8‐oxabicyclo[3.2.1]octane derivatives including synthetic intermediates of natural products is described, in which triethylamine effectively catalyzes [5+2] cycloaddition reactions between oxidopyrylium ylides and alkenes. This method can be applied not only to intermolecular cycloadditions with various alkenes but also to intramolecular cycloadditions. The key finding is that the combined use of

  描述了一种制备包括天然产物合成中间体在内的一系列8-氧杂双环[3.2.1]辛烷衍生物的有效方法，其中三乙胺有效地催化了氧化吡啶鎓内酯与烯烃之间的[5 + 2]环加成反应。该方法不仅可以应用于具有各种烯烃的分子间环加成，而且可以应用于分子内环加成。关键发现是将具有适当碱性的有机碱与带有合适离去基团的氧化吡啶鎓前体组合使用可促进碱式氧化吡啶鎓的催化生成。
• A novel, environment-friendly method to prepare pyranones from furfural alcohols <i>via</i> photocatalytic O₂ oxidation in an aqueous phase
  作者：Bei Zhou、Yun-Feng Tao、Yu-Juan He、Lan-Xiang Liu、Zu-Hui Chang、Xiang-Hong Li、Tong Lin、Guan-Ben Du

  DOI：10.1039/d2gc03344e

  日期：——

  This study developed a novel photocatalytic method to synthesize pyranones from furfural alcohols. By using 0.2 mol% equivalent of tris-Ir(ppy)3 as a photocatalyst under visible light and O2 as the reaction atmosphere, furfural alcohols were rapidly oxidized and hydrolyzed in the aqueous reaction solution to produce diol intermediates, which further underwent hydrolysis, furan ring-opening and rearrangement

  本研究开发了一种新的光催化方法从糠醛醇合成吡喃酮。在可见光下，以0.2 mol%当量的tris-Ir(ppy) 3作为光催化剂，O 2作为反应气氛，糠醇在反应水溶液中快速氧化水解生成二醇中间体，二醇中间体进一步水解，呋喃开环重排形成最终产物吡喃酮。整个反应在室温下进行，收率高达86%，转化效率高达90%。该方法具有通用性，适用于 5- 和 α-OH 位点上具有不同取代基的糠醛醇。我们原地使用IR 和实时 NMR 检查反应动力学，GC-MS 和同位素标记实验跟踪反应中原子转移的来源，EPR 识别单线态氧。结果表明，该反应遵循一级速率方程，O 2氧化是决速步骤。转移的H 原子来自H 2 O 溶剂，O 原子来自O 2气氛，单线态氧来自O 2光催化。紫外-可见和循环伏安法结果表明，该光催化反应涉及单电子转换过程。我们还使用 DFT 计算来模拟反应路线，并表明 tris-Ir(ppy) 3光催化 O
• Synthesis of (±)-cartorimine
  作者：Barry B. Snider、James F. Grabowski

  DOI：10.1016/j.tetlet.2004.12.007

  日期：2005.1

  Heating pyranulose 4 and cinnamate 2 in the presence of 2,6-di-t-butylpyridine in CH3CN afforded the [5 divided by 2] cycloadduct, which was hydrolyzed to give 13% of cartorimine (1). (C) 2004 Elsevier Ltd. All rights reserved.
• Preparation of 6-Hydroxy-2H-pyran-3(6H)-one from 2-Furylcarbinol by Photooxidation. Synthesis of a Pheromone of Vespa orientalis
  作者：Yueh-Hsiung Kuo、Yueh-Hsiung Kuo、Kae-Shyang Shih

  DOI：10.3987/com-90-5433

  日期：——

  Photooxidation of 2-furylcarbinols followed by reduction with triphenylphosphine afforded 6-hydroxy-2H-pyran-3(6H)-ones in excellent yield. The method was applied to synthesis of 6-undecyltetrahydro-2-pyrone, a pheromone of Vespa orientalis.