tert-Butyl 4-oxo-6-phenyl-4H-pyran-3-carboxylate | 134653-74-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: tert-Butyl 4-oxo-6-phenyl-4H-pyran-3-carboxylate
• 英文别名: 3-(tert-butoxycarbonyl)-6-phenyl-4-pyrone；Tert-butyl 4-oxo-6-phenylpyran-3-carboxylate
• CAS: 134653-74-0
• 化学式: C₁₆H₁₆O₄
• 分子量: 272.301
• InChiKey: PHYSJIHIEDQQQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  tert-Butyl 4-oxo-6-phenyl-4H-pyran-3-carboxylate 在 sodium tetrahydroborate 、 silica gel 、 三氟乙酸酐 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 30.5h， 生成 tert-butyl 7-hydroxy-4-oxo-2-phenyl-8,8a-dihydro-7H-chromene-4a-carboxylate
  参考文献：
  名称：

  还原性黄酮的合成与反应

  摘要：

  描述了一系列4H-吡喃-4-酮（3c-e）与富电子二烯（11a,b）进行环加成反应，生成还原型黄酮（12）的过程。随后，这些还原型黄酮与盐酸、三氟乙酸酐、乙基邻氨基苯甲酸酯（19a）和邻氨基苯腈（19b）的反应也被描述。

  DOI：

  10.1039/a602245f
• 作为产物：
  描述：

  苯甲酰氯 、 tert-butyl (Z)-2-((dimethylamino)methylene)-3-oxobutanoate 在 盐酸 、 正丁基锂 、 六甲基二硅氮烷 作用下， 生成 tert-Butyl 4-oxo-6-phenyl-4H-pyran-3-carboxylate
  参考文献：
  名称：

  Generation and in situ acylation of enaminone anions: a convenient synthesis of 3-carbethoxy-4(1H)-pyridinones and -4-pyrones and related compounds

  摘要：

  Treatment of 2-[(dimethylamino)methylene]-3-oxobutanoates 9 or 10 with LiN(SiMe3)2 in the presence of RCOCl results in C-acylation. The resulting intermediate, without isolation, may be converted to 6-R 3-Carbethoxy-4-pyrones (e.g., 12) by H3O+ or to the corresponding pyridinones (e.g., 13) by NH4OAc. Typically, yields are 55-75% for R groups lacking acidic alpha or gamma protons and ca. 30% for R = Me2CH or MeCH = CH. Replacing 9 with MeCOC(= CHNMe2)SCH2Ph (from MeCOCH2SCH2Ph and Me2NCH(OMe)2 similarly affords 3(PhCH2S)-substituted products such as 29. Alkylation of the pyridinone anions produces mixtures of N- and O-substituted compounds, with the latter predominating; aminolysis of the isolated pyrones (R'NH2-HOAc, where R' = alkyl, Ar, HO, etc.) is the preferred route to the 1-R'-substituted pyridinones.

  DOI：

  10.1021/jo00016a028

文献信息

• Systematic Diversity-Oriented Synthesis of Reduced Flavones from γ-Pyrones to Probe Biological Performance Diversity
  作者：Erica M. Gerlach、Melissa A. Korkmaz、Ivan Pavlinov、Qiwen Gao、Leslie N. Aldrich

  DOI：10.1021/acschembio.9b00294

  日期：2019.7.19

  chemical diversity with the hypothesis that chemical diversity will lead to diverse biological activities. We took a systematic approach to DOS to develop a focused library of reduced flavones from γ-pyrones with diversity of appendage, stereochemistry, and chemical properties to determine which features of small molecules are most predictive of biological performance diversity. The effects of these systematic

  面向多样性的合成（DOS）历史上一直专注于具有相当大的化学多样性的小分子集合的开发，其假设是化学多样性将导致多种生物活性。我们对DOS采取了系统化的方法，从γ-吡喃酮中开发了具有还原性的黄酮类化合物的重点文库，该文库具有附肢，立体化学和化学性质的多样性，以确定小分子的哪些特征最能预测生物性能的多样性。这些变化对生物多样性的影响是通过细胞涂漆和细胞毒性试验确定的，以比较多种评估方法的结果。我们观察到更大比例的sp3杂化原子（fsp3）并不总能增强生物多样性，立体化学和附属物多样性都有助于生物多样性，并且吡喃酮类化合物的亲脂性与生物多样性相关。这些结果将有助于开发一种通用算法，以预测在合成DOS文库时应考虑哪些化学特征，以创建生物学性能多样的小分子集合，以进行探针和药物发现。
• Substituent effects on the 4π + 2π cycloadditions of 4H-pyran-4-one derivatives
  作者：Mónika Rudas、Imre Fejes、Miklós Nyerges、Áron Szöllõsy、László Tõke、Paul W. Groundwater

  DOI：10.1039/a900827f

  日期：——

  The simple γ-pyranones 4, 5, and 6 undergo 4π + 2π cycloaddition reactions with Danishefsky’s diene 8 and azomethine ylides 12, 16, and 25 to give a range of cycloadducts. The position of the electron-withdrawing group is the decisive factor in these reactions, with the 2-substituted derivatives 5 and 6 being less reactive than the 3-substituted γ-pyranone 4. The esters, 4 and 5, react via addition across the 2,3-CC bond of the pyranone ring, whilst the aldehyde 6 reacts via addition across the CO of the carbaldehyde group.

  简单的δ-吡喃酮 4、5 和 6 与丹尼舍夫斯基二烯 8 和偶氮甲基酰化物 12、16 和 25 发生 4ÏÂ +Â 2Ï 环加成反应，生成一系列环加成物。在这些反应中，取电子基团的位置是决定性因素，2-取代的衍生物 5 和 6 的反应活性低于 3-取代的δ-吡喃酮 4。酯类 4 和 5 通过吡喃酮环的 2,3-CC 键发生加成反应，而醛类 6 则通过甲醛基团的 CO 发生加成反应。
• An Efficient Synthesis of Reduced Flavones via Diels-Alder Addition to 4H-Pyran-4-ones
  作者：Paul W. Groundwater、David E. Hibbs、Michael B. Hursthouse、Miklós Nyerges

  DOI：10.3987/com-95-7341

  日期：——
• Synthesis and reactions of reduced flavones
  作者：W. Groundwater、E. Hibbs、B. Hursthouse、Miklós Nyerges

  DOI：10.1039/a602245f

  日期：——

  The cycloadditions of a series of 4H-pyran-4-ones 3c–e with electron-rich dienes 11a,b to give reduced flavones 12 is described. The subsequent reactions of these reduced flavones with HCl, trifluoroacetic anhydride, ethyl anthranilate 19a and anthranilonitrile 19b is also described.

  描述了一系列4H-吡喃-4-酮（3c-e）与富电子二烯（11a,b）进行环加成反应，生成还原型黄酮（12）的过程。随后，这些还原型黄酮与盐酸、三氟乙酸酐、乙基邻氨基苯甲酸酯（19a）和邻氨基苯腈（19b）的反应也被描述。
• Generation and in situ acylation of enaminone anions: a convenient synthesis of 3-carbethoxy-4(1H)-pyridinones and -4-pyrones and related compounds
  作者：Stuart W. McCombie、William A. Metz、Dennis Nazareno、Bandarpalle B. Shankar、Jayaram Tagat

  DOI：10.1021/jo00016a028

  日期：1991.8

  Treatment of 2-[(dimethylamino)methylene]-3-oxobutanoates 9 or 10 with LiN(SiMe3)2 in the presence of RCOCl results in C-acylation. The resulting intermediate, without isolation, may be converted to 6-R 3-Carbethoxy-4-pyrones (e.g., 12) by H3O+ or to the corresponding pyridinones (e.g., 13) by NH4OAc. Typically, yields are 55-75% for R groups lacking acidic alpha or gamma protons and ca. 30% for R = Me2CH or MeCH = CH. Replacing 9 with MeCOC(= CHNMe2)SCH2Ph (from MeCOCH2SCH2Ph and Me2NCH(OMe)2 similarly affords 3(PhCH2S)-substituted products such as 29. Alkylation of the pyridinone anions produces mixtures of N- and O-substituted compounds, with the latter predominating; aminolysis of the isolated pyrones (R'NH2-HOAc, where R' = alkyl, Ar, HO, etc.) is the preferred route to the 1-R'-substituted pyridinones.