methyl 4-oxo-2-phenyl-4H-chromene-3-carboxylate | 78589-68-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: methyl 4-oxo-2-phenyl-4H-chromene-3-carboxylate
• 英文别名: methyl 4-oxo-2-phenylchromene-3-carboxylate
• CAS: 78589-68-1
• 化学式: C₁₇H₁₂O₄
• 分子量: 280.28
• InChiKey: AFOOLBMWQXUWHW-UHFFFAOYSA-N

物化性质

• 熔点：
  102 °C
• 沸点：
  426.2±45.0 °C(Predicted)
• 密度：
  1.304±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  methyl 4-oxo-2-phenyl-4H-chromene-3-carboxylate 以70%的产率得到3-benzoyl-4-hydroxycoumarin
  参考文献：
  名称：

  十六烷基环化新方法。应用'一种合成的原始酰基-3羟基-4-香豆素等羟基11-苯并（b）12 [h] one吨酮-12

  摘要：

  间苯和对乙酰氧基苯甲酰氯与Ph3P = CH-COOMe的反应导致的酮基的热分解分别在皂化为间苯丙酸和对苯丙酸后导致。酰基的邻位取代通常会改变反应的方向。苯甲酰氧基-或苯乙酰氧基苯甲酰氯分别提供：和令人满意的产率。第一种和第二种的皂化得到：这构成了一条新的，方便的途径，可制得3-酰基4-羟基香豆素和11-羟基12 H-苯并（b）氧杂蒽12-。这些最后产物的形成涉及该酰氧基取代基的羰基，而不是如先前在这些系列中观察到的酰氯的羰基。

  DOI：

  10.1016/s0040-4020(01)92042-3
• 作为产物：
  描述：

  1-(2-hydroxyphenyl)-3-phenylprop-2-yn-1-one 在 三丁基膦 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 2.08h， 生成 methyl 4-oxo-2-phenyl-4H-chromene-3-carboxylate
  参考文献：
  名称：

  A concise total synthesis of biologically active frutinones via tributylphosphine-catalyzed tandem acyl transfer-cyclization

  摘要：

  A concise and step-economical total synthesis of biologically active frutinones has been achieved. Tributylphosphine (PBu3) efficiently induced the tandem acyl transfer-cyclization of carbonates 5 to afford 3-methoxycarbonylflavone derivatives 4 in excellent yields. Finally, concomitant deprotection and lactonization under acidic conditions furnished the desired frutinones A (1a), B (1b), and the proposed structure of frutinone C (1c). (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.03.073

文献信息

• Flavone carboxylic acid derivatives
  申请人：Shionogi & Co., Ltd.

  公开号：US04831052A1

  公开（公告）日：1989-05-16

  Novel flavone carboxylic acid derivatives, intermediates therefor, and method for the preparation thereof, and their use in the differentiation of certain types of malignant cells, are all disclosed, certain of the novel compounds disclosed to be superior to retinoic acid in their activity.

  小说黄酮羧酸衍生物，其中间体及其制备方法，以及它们在区分某些类型的恶性细胞中的应用，均已披露，其中某些新化合物在活性上被证实优于视黄酸。
• Alcohol Mediated Synthesis of 4-Oxo-2-aryl-4<i>H</i>-chromene-3-carboxylate Derivatives from 4-Hydroxycoumarins
  作者：Manoj R. Zanwar、Mustafa J. Raihan、Sachin D. Gawande、Veerababurao Kavala、Donala Janreddy、Chun-Wei Kuo、Ram Ambre、Ching-Fa Yao

  DOI：10.1021/jo301044y

  日期：2012.8.3

  The unusual alcohol mediated formation of 4-oxo-2-aryl-4H-chromene-3-carboxylate (flavone-3-carboxylate) derivatives from 4-hydroxycoumarins and β-nitroalkenes in an alcoholic medium is described. The transformation occurs via the in situ formation of a Michael adduct, followed by the alkoxide ion mediated rearrangement of the intermediate. The effect of the different alcohol and nonalcohol media on

  这种不寻常的醇介导的4-氧代-2-芳基-4-的形成ħ色烯-3-羧酸甲酯（黄酮-3-羧酸）衍生物由4-羟基香豆素和β-硝基烯烃在醇介质进行说明。该转化通过原位形成迈克尔加合物而发生，随后是醇盐离子介导的中间体重排。研究了不同醇和非醇介质对反应的影响。
• Design and synthesis of chiral and regenerable [2.2]paracyclophane-based NAD(P)H models and application in biomimetic reduction of flavonoids
  作者：Zhou-Hao Zhu、Yi-Xuan Ding、Bo Wu、Yong-Gui Zhou

  DOI：10.1039/d0sc04188b

  日期：——

  With the rapid development of biomimetic asymmetric reduction, the demand for efficient chiral and regenerable NAD(P)H models is growing rapidly. Herein, a new class of [2.2]paracyclophane-based chiral and regenerable NAD(P)H models (CYNAMs) was designed and synthesized. The first enantioselective biomimetic reduction of tetrasubstituted alkene flavonoids has been successfully realized through enzyme-like

  随着仿生不对称还原的快速发展，对有效手性和可再生NAD（P）H模型的需求正在迅速增长。本文中，设计并合成了一类新的基于[2.2]对环环烷的手性和可再生NAD（P）H模型（CYNAM）。四取代烯烃类黄酮的首次对映选择性仿生还原已通过类似酶的双功能协同活化成功实现，手性黄烷酮的收率高达99％，ee高达99％。
• One-pot synthesis of 2-aryl-3-alkoxycarbonyl chromones through a cascade Lewis acid-catalyzed aldehyde olefination/oxa-Michael addition/oxidation
  作者：Ningning Wang、Shuying Cai、Chao Zhou、Ping Lu、Yanguang Wang

  DOI：10.1016/j.tet.2012.11.008

  日期：2013.1

  were effectively constructed from aryl aldehydes and 3-(2-(methoxymethoxy)phenyl)propiolates via a cascade Lewis acid catalyzed phenol ether deprotection/aldehyde olefination/intramolecular oxa-Michael addition reaction, and a sequential oxidation. This four-step reaction could be conducted in one-pot with high atom efficiency.

  通过级联路易斯酸催化的酚醚脱保护/醛烯化/分子内氧杂-迈克尔加成反应和顺序氧化反应，由芳基醛和3-（2-（甲氧基甲氧基）苯基）丙酸酯有效地构建了2-芳基-3-烷氧基羰基色酮。该四步反应可以在一个锅中以高原子效率进行。
• Asymmetric Transfer Hydrogenation of 2,3-Disubstituted Flavanones through Dynamic Kinetic Resolution Enabled by Retro-Oxa-Michael Addition: Construction of Three Contiguous Stereogenic Centers
  作者：Qing-Xian Xie、Li-Xia Liu、Zhou-Hao Zhu、Chang-Bin Yu、Yong-Gui Zhou

  DOI：10.1021/acs.joc.2c00418

  日期：2022.6.3

  A ruthenium-catalyzed asymmetric transfer hydrogenation of 2,3-disubstituted flavanones was developed for the construction of three contiguous stereocenters under basic conditions through a combination of dynamic kinetic resolution and retro-oxa-Michael addition, giving chiral flavanols with excellent enantioselectivities and diastereoselectivities. The reaction proceeded via a base-catalyzed retro-oxa-Michael

  通过动态动力学拆分和逆氧-迈克尔加成的结合，开发了一种钌催化的 2,3-二取代黄烷酮的不对称转移氢化，用于在碱性条件下构建三个连续的立体中心，从而使手性黄烷醇具有优异的对映选择性和非对映选择性。该反应通过碱催化的逆氧-迈克尔加成同时消旋两个立体中心与高度对映选择性的酮转移氢化步骤进行。在不损失活性和对映选择性的情况下，可以在克级实现不对称转移氢化。