钌(Ⅱ)催化1⁃苯基⁃5⁃吡唑啉酮和碳酸亚乙烯酯的偶联反应

Ruthenium (Ⅱ)⁃Catalyzed Coupling Reaction of 1⁃Phenyl⁃2⁃Pyrazolin⁃5⁃One with Ethylene Carbonate

王华 王欣 王贺 周明东 李蕾

Hua WANG Xin WANG He WANG Mingdong ZHOU Lei LI

辽宁石油化工大学 石油化工学院，辽宁 抚顺 113001

School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China

设计了一个新颖的钌(Ⅱ)催化1?苯基?5?吡唑啉酮与碳酸亚乙烯基的C-C/C-N环化反应。 在该转化过程中，碳酸亚乙烯酯作为乙炔醇或乙炔的替代物，不需要额外添加任何氧化剂和碱。该反应具有广阔的底物范围和良好的官能团相容性，能够以42%~87%的收率得到一系列的1H?吡唑并[1,2?a]噌啉酮。提出了一种可能涉及到串联的C-H活化/分子内C-N形成/消除CO2或CO 32-等历程的机制。此外，在执行克级反应时得到了一个令人满意的产率。

A novel ruthenium(Ⅱ)?catalyzed C-H/C-N annulation of 1?phenyl?2?pyrazolin?5?one with ethylene carbonate was designed. In this transformation, the vinylene carbonate acts as an ethynol or alkyne surrogate without any external oxidant as well as bases involved. The reaction exhibits a broad substrate scope with excellent functional group compatibility, affording a series of 1H?pyrazolo[1,2?a]cinnolin?1?ones in 42%~87% yields. A possible mechanism involving a sequential C-H activation/intramolecular C-N bond formation/ CO2 or CO 32- elimination is proposed. In addition, the reaction can also be carried out on a gram scale with satisfactory yield.

国家自然科学基金项目(21702087);辽宁省教育厅项目(L2020033)

10.12422/j.issn.1672-6952.2023.06.002