methyl 4-oxo-2-(2-oxo-2-phenylethyl)-4-phenylbutanoate | 172980-59-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-oxo-2-(2-oxo-2-phenylethyl)-4-phenylbutanoate
• 英文别名: methyl 4-oxo-2-(2-oxo-2-phenylethyl)-4-phenylbutyrate；Methyl 4-oxo-2-phenacyl-4-phenylbutanoate
• CAS: 172980-59-5
• 化学式: C₁₉H₁₈O₄
• 分子量: 310.35
• InChiKey: UZPNYAPYXULUSH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  60.4
• 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-(2-oxo-2-phenylethyl)-4-phenylbutanoate 在 氢氧化钾 作用下， 以 甲醇 、 水 为溶剂， 反应 1.0h， 生成 4-oxo-2-phenacyl-4-phenyl-butyric acid
  参考文献：
  名称：

  Ligand-Induced Selectivity in the Rhodium(II)-Catalyzed Reactions of α-Diazo Carbonyl Compounds

  摘要：

  3-Allyl-2,5-diazopentanedione and 3-butenyl-2,5-diazopentanedione were allowed to react with a trace amount of a rhodium(II) catalyst in methylene chloride at room temperature. The major products isolated correspond to the internal trapping of a carbonyl ylide as well as intramolecular cyclopropanation. Changing the catalyst from Rh-2(OAc)(4) to Rh-2(cap)(4) to Rh-2(tfa)(4) caused a significant alteration in product distribution. A rather unusual and unexpected regiochemical crossover in the cycloaddition occurred when Rh-2(tfa)(4) was used and is most likely due to complexation of the metal with the dipole. A computational approach to rationalize the observed product distribution was carried out. The thermodynamic stabilities of cycloaddition transition states were approximated from the computationally derived strain energies of ground state molecules using traditional force-field techniques. Globally minimized ground state energies were obtained for all possible cycloaddition products, and final strain energies were calculated. In all cases studied, the lower energy isomer corresponded to the cycloadduct actually isolated. A study of the regiochemical aspects of the Rh(II)-catalyzed reaction of 1-diazo-3-(2-oxo-2-phenylethyl)hexane-2, was also carried out. Cyclization of the initially formed rhodium carbenoid occurred exclusively across the acetyl rather than the benzoyl group. The structure of the internal cycloadduct was assigned on the basis of a proton-detected multiple-bond heteronuclear multiple-quantum coherence experiment.

  DOI：

  10.1021/jo951576n
• 作为产物：
  描述：

  3-苯基丙酸甲酯 在 二甲基硫 、 对甲苯磺酸 、 臭氧 、 lithium diisopropyl amide 作用下， 以 甲醇 为溶剂， 反应 45.0h， 生成 methyl 4-oxo-2-(2-oxo-2-phenylethyl)-4-phenylbutanoate
  参考文献：
  名称：

  Ligand-Induced Selectivity in the Rhodium(II)-Catalyzed Reactions of α-Diazo Carbonyl Compounds

  摘要：

  3-Allyl-2,5-diazopentanedione and 3-butenyl-2,5-diazopentanedione were allowed to react with a trace amount of a rhodium(II) catalyst in methylene chloride at room temperature. The major products isolated correspond to the internal trapping of a carbonyl ylide as well as intramolecular cyclopropanation. Changing the catalyst from Rh-2(OAc)(4) to Rh-2(cap)(4) to Rh-2(tfa)(4) caused a significant alteration in product distribution. A rather unusual and unexpected regiochemical crossover in the cycloaddition occurred when Rh-2(tfa)(4) was used and is most likely due to complexation of the metal with the dipole. A computational approach to rationalize the observed product distribution was carried out. The thermodynamic stabilities of cycloaddition transition states were approximated from the computationally derived strain energies of ground state molecules using traditional force-field techniques. Globally minimized ground state energies were obtained for all possible cycloaddition products, and final strain energies were calculated. In all cases studied, the lower energy isomer corresponded to the cycloadduct actually isolated. A study of the regiochemical aspects of the Rh(II)-catalyzed reaction of 1-diazo-3-(2-oxo-2-phenylethyl)hexane-2, was also carried out. Cyclization of the initially formed rhodium carbenoid occurred exclusively across the acetyl rather than the benzoyl group. The structure of the internal cycloadduct was assigned on the basis of a proton-detected multiple-bond heteronuclear multiple-quantum coherence experiment.

  DOI：

  10.1021/jo951576n

文献信息

• Redox-Neutral Dual Functionalization of Electron-Deficient Alkenes
  作者：Fredrik Pettersson、Giulia Bergonzini、Carlo Cassani、Carl-Johan Wallentin

  DOI：10.1002/chem.201701589

  日期：2017.6.1

  Visible-light photoredox catalysis has been utilized in a new multicomponent reaction forming β-functionalized δ-diketones under mild conditions in an operationally convenient manner. Single-electron reduction of in situ generated carboxylic acid derivatives forms acyl radicals that react further via 1,2-acylalkylation of olefins in an intermolecular, three-components cascade reaction, giving valuable

  可见光光氧化还原催化已用于一种新的多组分反应中，该反应在温和条件下以操作方便的方式形成β-官能化的δ-二酮。原位生成的羧酸衍生物的单电子还原形成了酰基基团，它们通过分子间的三组分级联反应通过烯烃的1,2-酰基烷基化进一步反应，从而从易于获得的起始原料中获得了有价值的合成实体。已经使用了各种各样的基板，展示了具有广泛基板范围的可靠方法。
• Four-component radical-dual-difunctionalization (RDD) and decarbonylative alkylative peroxidation of two different alkenes with aliphatic aldehydes and TBHP
  作者：Ren-Xiang Liu、Feng Zhang、Yong Peng、Luo Yang

  DOI：10.1039/c9cc05764a

  日期：——

  of a single alkene to radical-dual-difunctionalization of two different alkenes! Abundant aliphatic aldehydes were readily decarbonylated into alkyl radicals for the cascade construction of C(sp3)–C(sp3), C(sp3)–C(sp3) and C(sp3)–O bonds via double radical addition and radical–radical coupling, following the intrinsic nucleophilic/electrophilic reactivity of both the radicals and alkenes.

  从单个烯烃的双官能化到两个不同烯烃的自由基-双-双官能化！丰富的脂族醛很容易通过双自由基加成反应而脱羰基化为C（sp 3）–C（sp 3），C（sp 3）–C（sp 3）和C（sp 3）–O键的级联结构的烷基。自由基和烯烃之间固有的亲核/亲电反应性，然后进行自由基-自由基偶联。
• 1,5-DIARYL-3,3-DISUBSTITUTED-1,5-PENTANEDIONE - A SYNTHON FOR 2,4,6-TRISUBSTITUTED HETEROCYCLES
  作者：V. Padmavathi、A. Balaiah、B. Jagan Mohan Reddy、A. Padmaja

  DOI：10.1515/hc.2003.9.6.599

  日期：2003.1

  carbon framework constitutes the development of heterocycles. In our endeavor to prepare a new class of heterocycles, we have reported the reactivity of phenacyl bromide with active methylene compounds under different conditions'. During our studies in this area we have prepared 1,5-diaryl3,3-disubstituted-l,5-pentanedione from the above substrates. The 1,5-diketo and gemdiester / cyano ester groups have

  2,4,6-三取代的杂环是通过 1,5-二芳基-3,3-二甲氧基羰基,5-戊烷二酮 (1) 和 1 中的 ^e/n-二取代基和酮基官能团的官能化制备的,5-二芳基-3-cyano3-ethoxycarbonyl-1,5-pentanedione (4)。简介：碳-碳键形成反应对于设计所需的分子结构很重要。在碳框架内掺杂杂原子构成了杂环的发展。在我们努力制备一类新的杂环时，我们报道了苯甲酰溴在不同条件下与活性亚甲基化合物的反应性。在我们在该领域的研究期间，我们已经从上述底物制备了 1,5-二芳基 3,3-二取代-1,5-戊二酮。1、在 DMSO 中用 NaCl 处理 1 直接提供 1,5-二芳基-3-甲氧羰基-1,5-戊二酮 (3)。类似地，在DMSO中用NaCl处理1，5-二芳基-3-氰基-3-乙氧基羰基-1，5-戊二酮(4)得到1，5-二芳基-3-氰基-1，5-戊二酮(5)。化合物 4 在
• Four-Component Radical Dual Difunctionalization (RDD) of Two Different Alkenes with Aldehydes and <i>tert</i>-Butyl Hydroperoxide (TBHP): An Easy Access to β,δ-Functionalized Ketones
  作者：Chuan-Shuo Wu、Ren-Xiang Liu、Da-You Ma、Cui-Ping Luo、Luo Yang

  DOI：10.1021/acs.orglett.9b02264

  日期：2019.8.2

  A convenient Fe-catalyzed four-component radical dual difunctionalization and ordered assembly of two alkenes with aromatic/aliphatic aldehydes and TBHP to provide chain elongated β,δ-functionalized ketones via a one-pot procedure has been developed. Aldehydes were homolytically cleavaged to produce acyl radicals and subsequently allowed for the successive construction of C(sp2)–C(sp3), C(sp3)–C(sp3)

  已经开发了一种方便的铁催化的四组分自由基双双官能化方法，并通过一锅法将两个烯烃与芳族/脂肪族醛和TBHP进行有序组装，以提供链长的β，δ-官能化的酮。醛被同质裂解产生酰基自由基，随后允许通过以下方式连续构建C（sp 2）–C（sp 3），C（sp 3）–C（sp 3）和C（sp 3）–O键遵循自由基和烯烃固有的核/亲电反应性，实现双自由基插入和自由基-自由基偶联。
• 一种β，δ-位不同官能团取代的芳香酮类化合物的制备方法
  申请人：湘潭大学

  公开号：CN110256249B

  公开（公告）日：2023-06-27

  本发明公开一种β，δ‑位不同官能团取代的芳香酮类化合物的制备方法。本方法用芳香醛、缺电子烯烃、苯乙烯衍生物和叔丁基过氧化氢为反应底物，在过渡金属的催化下发生自由基串联反应生成过氧化物；然后向反应体系中加入碱，将过氧化物直接转化为β，δ‑位不同官能团取代的芳香酮类化合物。本方法用叔丁基过氧化氢作为自由基引发剂和氧化剂，将芳香醛转化为酰基自由基；然后酰基自由基对缺电子烯烃(如丙烯酸酯类、丙烯腈、丙烯酰胺类化合物)和苯乙烯类衍生物依次发生加成，最后和叔丁基过氧化氢发生偶联，得到相应的过氧化物；新生成的过氧化物在碱的作用下发生Kornblum‑DeLaMare重排，通过一锅反应，得到β，δ‑位不同官能团取代的芳香酮类化合物。反应温度为25‑150℃，反应时间为0.1‑72小时。它克服了传统方法合成β，δ‑位不同官能团取代的芳香酮类化合物合成步骤复杂，且选择性较差的缺点。它与已有方法相比：一次反应实现两个烯烃的双官能团化反应和交叉偶联，构筑3个新的化学键和引入两个新的功能团芳香酮产物中；原料廉价易得，操作简单，更安全、更经济有效、同时对空气、水分、光均不敏感，产率较高，产物易分离纯化，有很好的应用前景。