4-Phenyl-3-(phenylmethyl)-2-butenoic acid methyl ester | 157731-51-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 4-Phenyl-3-(phenylmethyl)-2-butenoic acid methyl ester
• 英文别名: methyl 4-phenyl-3-(phenylmethyl)but-2-enoate；Methyl 3-benzyl-4-phenylbut-2-enoate；methyl 3-benzyl-4-phenylbut-2-enoate
• CAS: 157731-51-6
• 化学式: C₁₈H₁₈O₂
• 分子量: 266.34
• InChiKey: HKOKRJAKUWRTTN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Phenyl-3-(phenylmethyl)-2-butenoic acid methyl ester 在 正丁基锂 、 三苯基甲烷 、 三甲基铝 作用下， 反应 4.25h， 生成 6-Phenyl-5-(phenylmethyl)-4-hexen-1-yn-3-one
  参考文献：
  名称：

  Enynones in Organic Synthesis. 6. Synthesis of Spirocyclic Methylenecyclopentenones and Analogs of the Methylenomycin Class of Antibiotics. Mechanism of Phenol Catalysis

  摘要：

  Spirocyclic methylenecyclopentenones of general structure 18 were prepared in a single step from bis-acetylenic alcohols 29 by a process involving initial oxy-Cope rearrangement to afford (Z)-enynones 30-Z followed by electrocyclic ring closure. Mechanistic studies indicate that the initial step leading from 30-Z to 18 is a thermal 1,5-prototropic shift to afford dienols which can cyclize by a symmetry-allowed (pi(4)s + sigma(2)s + pi(2)a) process. This last step is catalyzed by certain phenols having low oxidation potentials, most likely by a mechanism involving single electron transfer. Dramatic rate enhancements were also observed for the cyclization of simple enynones 37 to methylenecyclopentenones 39 upon catalysis with either a-tocopherol (vitamin E, 40) or tert-butylcatechol(41). Further enhancements in both rate and yield were obtained under conditions of photoassisted single electron transfer (PET), which afforded 39 in yields of 80-98%.

  DOI：

  10.1021/jo00097a035
• 作为产物：
  描述：

  溴乙酸甲酯 、 二苄基甲酮 在 potassium carbonate 作用下， 以 乙醇 、 氯仿 为溶剂， 100.0 ℃ 、10.0 MPa 条件下， 反应 0.07h， 以84%的产率得到4-Phenyl-3-(phenylmethyl)-2-butenoic acid methyl ester
  参考文献：
  名称：

  一种用于原位 Wittig 型烯烃偶联的固相辅助流动方法

  摘要：

  的发展和一个随后的应用在 原位和固相的三苯基膦（PS-PPH 3）辅助的连续流协议，以促进描述与醛和酮系基板倒数初级和次级卤化物的耦合。

  DOI：

  10.1002/ejoc.202100761

文献信息

• A Solid‐Phase Assisted Flow Approach to <i>In Situ</i> Wittig‐Type Olefination Coupling
  作者：Joseph Tadros、Christian Dankers、Janice R. Aldrich‐Wright、Anastasios Polyzos、Christopher P. Gordon

  DOI：10.1002/ejoc.202100761

  日期：2021.8.6

  The development and subsequent application of an in situ and solid-phase triphenylphosphine (PS-PPh3) assisted continuous flow protocol to facilitate the coupling of reciprocal primary and secondary halides with aldehyde and ketone-based substrates is described.

  的发展和一个随后的应用在 原位和固相的三苯基膦（PS-PPH 3）辅助的连续流协议，以促进描述与醛和酮系基板倒数初级和次级卤化物的耦合。
• Enynones in Organic Synthesis. 6. Synthesis of Spirocyclic Methylenecyclopentenones and Analogs of the Methylenomycin Class of Antibiotics. Mechanism of Phenol Catalysis
  作者：Peter A. Jacobi、Lisa M. Armacost、Harry L. Brielmann、Reginald O. Cann、Joseph I. Kravitz、Michael J. Martinelli

  DOI：10.1021/jo00097a035

  日期：1994.9

  Spirocyclic methylenecyclopentenones of general structure 18 were prepared in a single step from bis-acetylenic alcohols 29 by a process involving initial oxy-Cope rearrangement to afford (Z)-enynones 30-Z followed by electrocyclic ring closure. Mechanistic studies indicate that the initial step leading from 30-Z to 18 is a thermal 1,5-prototropic shift to afford dienols which can cyclize by a symmetry-allowed (pi(4)s + sigma(2)s + pi(2)a) process. This last step is catalyzed by certain phenols having low oxidation potentials, most likely by a mechanism involving single electron transfer. Dramatic rate enhancements were also observed for the cyclization of simple enynones 37 to methylenecyclopentenones 39 upon catalysis with either a-tocopherol (vitamin E, 40) or tert-butylcatechol(41). Further enhancements in both rate and yield were obtained under conditions of photoassisted single electron transfer (PET), which afforded 39 in yields of 80-98%.