phenyl 3-benzyl-5-methylene-2-oxotetrahydro-2H-pyran-3-carboxylate | 1181692-70-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: phenyl 3-benzyl-5-methylene-2-oxotetrahydro-2H-pyran-3-carboxylate
• CAS: 1181692-70-5
• 化学式: C₂₀H₁₈O₄
• 分子量: 322.361
• InChiKey: MFLVSVUOFMPKKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.32
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1-甲基靛红 、 phenyl 3-benzyl-5-methylene-2-oxotetrahydro-2H-pyran-3-carboxylate 在 allyl(cyclopentadiene)palladium(II) 、 N,N-dibenzhydrylbenzo[d][1,3,2]benzodioxaphosphepin-6-amine 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以76%的产率得到phenyl 3'-benzyl-1-methyl-5'-methylene-2-oxo-3',4',5',6'-tetrahydrospiro[indoline-3,2'-pyran]-3'-carboxylate
  参考文献：
  名称：

  Stereoselective Synthesis of Spirooxindoles by Palladium-Catalyzed Decarboxylative Cyclization of γ-Methylidene-δ-valerolactones with Isatins

  摘要：

  A new synthetic method of spirooxindole derivatives has been developed by way of a palladium-catalyzed decarboxylative cyclization of gamma-methylidene-delta-valerolactones with isatins. By employing a newly prepared phosphoramidite ligand, the reaction proceeds smoothly with excellent diastereoselectivity. Preliminary results of its application to asymmetric catalysis using a chiral phosphoramidite ligand are also described.

  DOI：

  10.1021/ol901348f
• 作为产物：
  描述：

  diphenyl (2-(tert-butyldimethylsiloxy)methyl-2-propen-1-yl)(benzyl)malonate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以50%的产率得到phenyl 3-benzyl-5-methylene-2-oxotetrahydro-2H-pyran-3-carboxylate
  参考文献：
  名称：

  Stereoselective Synthesis of Spirooxindoles by Palladium-Catalyzed Decarboxylative Cyclization of γ-Methylidene-δ-valerolactones with Isatins

  摘要：

  A new synthetic method of spirooxindole derivatives has been developed by way of a palladium-catalyzed decarboxylative cyclization of gamma-methylidene-delta-valerolactones with isatins. By employing a newly prepared phosphoramidite ligand, the reaction proceeds smoothly with excellent diastereoselectivity. Preliminary results of its application to asymmetric catalysis using a chiral phosphoramidite ligand are also described.

  DOI：

  10.1021/ol901348f

文献信息

• Mechanistic Investigation of the Palladium-Catalyzed Decarboxylative Cyclization of γ-Methylidene-δ-valerolactones with Isocyanates: Kinetic Studies and Origin of the Site Selectivity in the Nucleophilic Attack at a (π-Allyl)palladium
  作者：Ryo Shintani、Takaoki Tsuji、Soyoung Park、Tamio Hayashi

  DOI：10.1021/ja1023223

  日期：2010.6.2

  of this selectivity is provided. The selectivity between 3 and 4 is also influenced by the nature of the nitrogen substituent on isocyanates 2, and more electron-rich substituents tend to give higher selectivity toward azaspiro[2.4]heptanones 4. These studies represent the first systematic investigation into the selectivity between terminal attack and central attack at (pi-allyl)palladium species by

  描述了钯催化的 γ-亚甲基-δ-戊内酯 1 与异氰酸酯 2 的脱羧环化反应的机理研究。该反应可以被钯三芳基膦配合物有效催化，得到哌啶酮 3 和/或氮杂螺[2.4]庚酮 4。通过使用 NMR 光谱的动力学研究，已经确定内酯 1 氧化加成到钯 (0) 是转换-催化循环的限制步骤。通过改变三芳基膦配体的电子特性，可以轻松控制 3 和 4 之间的产物分布，并解释了这种选择性的起源。3 和 4 之间的选择性还受异氰酸酯 2 上氮取代基的性质影响，