4,4-Dimethyl-5-methylidene-3,3-diphenyloxolan-2-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,4-Dimethyl-5-methylidene-3,3-diphenyloxolan-2-one
• 化学式: C₁₉H₁₈O₂
• 分子量: 278.351
• InChiKey: GYIYIWJVDPEIKI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4,4-二甲基-5-亚甲基-1,3-二氧戊环-2-酮 、 二苯乙烯酮 在 四(三苯基膦)钯 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以17%的产率得到4,4-Dimethyl-5-methylidene-3,3-diphenyloxolan-2-one
  参考文献：
  名称：

  Palladium-catalyzed reaction of 5-methylene-1,3-dioxolan-2-ones. A new access to and reactivity of oxatrimethylenemethane-palladium

  摘要：

  The oxidative addition of 5-methylene-1,3-dioxolan-2-ones (1) to a low-valent palladium complex and the subsequent decarboxylation has been studied as an access to oxatrimethylenemethane-palladium (OTMM-Pd) intermediates in a catalytic process. The reaction of 5,6-dimethyl-4-methylene-1,3-dioxolan-2-one (1a) with norbornene in the presence of Pd(PPh3)4 gave 3-(2-methylpropanoyl)tricyclo[3.2.1.0(2,4)]octane (3a) via addition and isomerization. In the catalytic reaction of 1a with several isonitriles, insertion of two molecules of the isonitrile into OTMM intermediate 2a took place to give 2-iminofurans 11. Similarly, the carbonate 1a reacted with aromatic isocyanates to give the corresponding oxazolidinones 12 as a result of [3 + 2] cycloaddition. The reaction of la with trimethylsilyl cyanide gave cyanated silyl enol ether 17. The zwitterionic character of OTMM-Pd seems to explain this reactivity.

  DOI：

  10.1021/jo00057a033

文献信息

• Palladium-catalyzed reaction of 5-methylene-1,3-dioxolan-2-ones. A new access to and reactivity of oxatrimethylenemethane-palladium
  作者：Kouichi Ohe、Hideki Matsuda、Toshihisa Ishihara、Sensuke Ogoshi、Naoto Chatani、Shinji Murai

  DOI：10.1021/jo00057a033

  日期：1993.2

  The oxidative addition of 5-methylene-1,3-dioxolan-2-ones (1) to a low-valent palladium complex and the subsequent decarboxylation has been studied as an access to oxatrimethylenemethane-palladium (OTMM-Pd) intermediates in a catalytic process. The reaction of 5,6-dimethyl-4-methylene-1,3-dioxolan-2-one (1a) with norbornene in the presence of Pd(PPh3)4 gave 3-(2-methylpropanoyl)tricyclo[3.2.1.0(2,4)]octane (3a) via addition and isomerization. In the catalytic reaction of 1a with several isonitriles, insertion of two molecules of the isonitrile into OTMM intermediate 2a took place to give 2-iminofurans 11. Similarly, the carbonate 1a reacted with aromatic isocyanates to give the corresponding oxazolidinones 12 as a result of [3 + 2] cycloaddition. The reaction of la with trimethylsilyl cyanide gave cyanated silyl enol ether 17. The zwitterionic character of OTMM-Pd seems to explain this reactivity.