脱碳
化学
磷化氢
催化作用
反应性(心理学)
配体(生物化学)
位阻效应
镍
还原消去
氧化加成
反应机理
组合化学
光化学
药物化学
立体化学
有机化学
医学
生物化学
替代医学
受体
病理
作者
Xinghua Wang,Peng Jin,Shi-Qiang Li,Yanwei Wen,Fuke Wang,Huijuan Wei,Donghui Wei
摘要
Due to the ubiquity of carbonyl compounds and the abundance of nickel on the earth, nickel-catalyzed decarbonylation has garnered increasing attention in recent years. This type of reaction has seen significant developments in various aspects; however, certain challenges concerning reactivity, selectivity, and transformation efficiency remain pressing and demand urgent resolution. In this study, we employed DFT calculations to investigate the mechanism of nickel-catalyzed decarbonylation reactions involving lactones, as well as the effects of phosphine ligands. Mechanically, Ni(0) first activates the C(acyl)-O bond of the lactone, followed by a decarbonylation step, and ultimately results in reductive elimination under carbonyl coordination to yield the product. Through a comprehensive examination of the electronic and steric effects of the phosphine ligands, we deduced that the electronic effect of the ligand plays a dominant role in the decarbonylation reaction. By enhancing the electron-withdrawing ability of the ligand, the energy barrier of the entire reaction can be significantly reduced. The obtained insights should be valuable for understanding the detailed mechanism and the role of phosphine ligands in nickel catalysis. Moreover, they offer crucial clues for the rational design of more efficient catalytic reactions.
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