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Citation: Zhiqian Huang, Yiying Yang, Yuchen Ma, Dongju Zhang. 乙基溴化镁与二异丙基酮反应的计算化学研究[J]. University Chemistry, ;2022, 37(7): 210800. doi: 10.3866/PKU.DXHX202108001 shu

乙基溴化镁与二异丙基酮反应的计算化学研究

School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China

Received Date: 1 August 2021

格氏试剂与羰基化合物的亲核加成反应是构建C―C键的经典反应，该反应通常伴生的副反应主要包括羰基化合物的还原反应、烯醇化反应等。以乙基溴化镁(EtMgBr)与二异丙基酮(CO(iPr)₂)的反应为例，通过量子化学计算研究了格氏试剂与羰基化合物的亲核加成反应、还原反应和烯醇化反应。结果表明，通过Schlenk平衡形成的二乙基镁(MgEt₂)比EtMgBr更容易与CO(iPr)₂反应，与教科书中定性描述的反应机理明显不同；乙醚溶剂对反应性能有重要影响，特别是更有利于亲核加成反应；计算的三个反应的能垒差可以合理解释实验所观察的主产物与副产物的产率比。
- Grignard reagents,
- Carbonyl compounds,
- Nucleophilic addition,
- Reduction,
- Enolization
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