phenylmethyl 4-(4-methoxyphenyl)-4-oxobutanoate | 119924-83-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenylmethyl 4-(4-methoxyphenyl)-4-oxobutanoate
• 英文别名: benzyl 4-(4-methoxyphenyl)-4-oxobutanoate；4-(4-methoxy-phenyl)-4-oxo-butyric acid benzyl ester；4-(4-Methoxy-phenyl)-4-oxo-buttersaeure-benzylester
• CAS: 119924-83-3
• 化学式: C₁₈H₁₈O₄
• 分子量: 298.339
• InChiKey: ICYPPRUNAIZZHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  phenylmethyl 4-(4-methoxyphenyl)-4-oxobutanoate 在 对甲苯磺酸 、 2-碘酰基苯甲酸 作用下， 以 二甲基亚砜 为溶剂， 反应 54.0h， 以80%的产率得到Benzyl 4-(4-methoxyphenyl)-4-oxobut-2-enoate
  参考文献：
  名称：

  使用IBX / p-TsOH通过3-苄基丙酸酯/丙酰胺的脱氢合成3-苄基丙烯酸酯/丙烯酰胺

  摘要：

  IBX / p- TsOH进行的脱氢用于将3-苯甲酰基丙酸酯/丙酰胺以中等至极好的收率转化为3-苯甲酰基丙烯酸酯/丙烯酰胺。3-苯甲酰基丙酰胺脱氢的反应时间明显短于酯脱氢的反应时间。

  DOI：

  10.1002/cjoc.201090225
• 作为产物：
  描述：

  丙烯酸苄酯 、 (4-methoxyphenyl)(phenylseleno)methanone 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 0.5h， 以60%的产率得到phenylmethyl 4-(4-methoxyphenyl)-4-oxobutanoate
  参考文献：
  名称：

  Acyl radicals: intermolecular and intramolecular alkene addition reactions

  摘要：

  A full study of the use of phenyl selenoesters as precursors to acyl radicals and their subsequent participation in intermolecular and intramolecular alkene addition reactions is detailed. Primary alkyl-, vinyl-, and aryl-substituted acyl radicals generated by Bu3SnH treatment of the corresponding phenyl selenoesters participate cleanly in intermolecular addition reactions with alkenes bearing electron-withdrawing or radical-stabilizing substituents at rates that exceed those of the potentially competitive decarbonylation or reduction. Similarly, their intramolecular addition to activated or unactivated alkenes proceeds without significant competitive reduction or decarbonylation and at rates generally greater-than-or-equal-to 1 x 10(6) s-1 with some occurring at rates greater-than-or-equal-to 3 x 10(7) s-1. Consistent with their behavior in intermolecular addition reactions, the 5-exo-trig cyclizations of secondary and tertiary alkyl-substituted acyl radicals to an unactivated olefin acceptor may be accompanied by varying degrees of decarbonylation, even under low-temperature free-radical reaction conditions. Studies are presented which suggest that the intramolecular additions of acyl radicals to alkenes under the conditions detailed herein may be regarded as irreversible, kinetically controlled processes which exhibit regioselectivity that is predictable based on well-established empirical rules set forth for the analogous free-radical cyclization reactions of alkyl radicals.

  DOI：

  10.1021/jo00031a021

文献信息

• Photochemical generation of acyl and carbamoyl radicals using a nucleophilic organic catalyst: applications and mechanism thereof
  作者：Eduardo de Pedro Beato、Daniele Mazzarella、Matteo Balletti、Paolo Melchiorre

  DOI：10.1039/d0sc02313b

  日期：——

  detail a strategy that uses a commercially available nucleophilic organic catalyst to generate acyl and carbamoyl radicals upon activation of the corresponding chlorides and anhydrides via a nucleophilic acyl substitution path. The resulting nucleophilic radicals are then intercepted by a variety of electron-poor olefins in a Giese-type addition process. The chemistry requires low-energy photons (blue

  我们详细介绍了一种策略，该策略使用相应的氯化物和酸酐通过激活后，使用市售的亲核有机催化剂来生成酰基和氨基甲酰基基团。亲核酰基取代路径。然后，在Giese型加成过程中，所得的亲核基团被各种贫电子烯烃截获。化学过程需要低能光子（蓝色LED）来激活酰基和氨基甲酰基自由基前体，由于它们的高还原电位，因此不容易基于氧化还原的激活机制。为了阐明这种催化光化学自由基产生策略的关键机理，我们结合了瞬态吸收光谱研究，电化学研究，量子产率测量和关键中间体的表征。我们确定了各种非循环中间体，它们与反应性自由基进行光调节平衡。
• Phenyl selenoesters as effective precursors of acyl radicals for use in intermolecular alkene addition reactions
  作者：Dale L. Boger、R. J. Mathvink

  DOI：10.1021/jo00269a001

  日期：1989.4
• Photoredox-Catalyzed α-C(sp³)–H Activation of Unprotected Secondary Amines: Facile Access to 1,4-Dicarbonyl Compounds
  作者：Qian Zhang、Yan Huang、Le-Wu Zhan、Wan-Ying Tang、Jing Hou、Bin-Dong Li

  DOI：10.1021/acs.orglett.0c02571

  日期：2020.10.2

  A photoredox-catalyzed alpha-C(sp(3))-H activation approach of unprotected secondary amines is reported. Such transformations provide facile access to various 1,4-dicarbonyl compounds using readily available amines and alpha,beta-unsaturated compounds as feedstocks under air conditions. The substrate scope of this method is broad, and a wide array of functional groups are tolerated.
• BOGER, D. L.;MATHVINK, R. J., J. ORG. CHEM., 54,(1989) N, C. 1777-1779
  作者：BOGER, D. L.、MATHVINK, R. J.

  DOI：——

  日期：——
• Acyl radicals: intermolecular and intramolecular alkene addition reactions
  作者：Dale L. Boger、Robert J. Mathvink

  DOI：10.1021/jo00031a021

  日期：1992.2

  A full study of the use of phenyl selenoesters as precursors to acyl radicals and their subsequent participation in intermolecular and intramolecular alkene addition reactions is detailed. Primary alkyl-, vinyl-, and aryl-substituted acyl radicals generated by Bu3SnH treatment of the corresponding phenyl selenoesters participate cleanly in intermolecular addition reactions with alkenes bearing electron-withdrawing or radical-stabilizing substituents at rates that exceed those of the potentially competitive decarbonylation or reduction. Similarly, their intramolecular addition to activated or unactivated alkenes proceeds without significant competitive reduction or decarbonylation and at rates generally greater-than-or-equal-to 1 x 10(6) s-1 with some occurring at rates greater-than-or-equal-to 3 x 10(7) s-1. Consistent with their behavior in intermolecular addition reactions, the 5-exo-trig cyclizations of secondary and tertiary alkyl-substituted acyl radicals to an unactivated olefin acceptor may be accompanied by varying degrees of decarbonylation, even under low-temperature free-radical reaction conditions. Studies are presented which suggest that the intramolecular additions of acyl radicals to alkenes under the conditions detailed herein may be regarded as irreversible, kinetically controlled processes which exhibit regioselectivity that is predictable based on well-established empirical rules set forth for the analogous free-radical cyclization reactions of alkyl radicals.