Theoretical and Experimental Investigation of Palladium(II)-Catalyzed Decarboxylative Addition of Arenecarboxylic Acid to Nitrile

详细信息    查看全文

• 作者：Fredrik Svensson ; Rajendra S. Mane ; Jonas S盲vmarker ; Mats Larhed ; Christian Sk枚ld
• 刊名：Organometallics
• 出版年：2013
• 出版时间：January 28, 2013
• 年：2013
• 卷：32
• 期：2
• 页码：490-497
• 全文大小：419K
• 年卷期：v.32,no.2(January 28, 2013)
• ISSN：1520-6041

文摘

The reaction mechanism of palladium(II)-catalyzed decarboxylative addition of 2,6-dimethoxybenzoic acid to acetonitrile was investigated by means of density functional theory (DFT) calculations. Calculations of the free energy profile for decarboxylation and carbopalladation indicated carbopalladation as the rate-determining step of the reaction. Investigation of the free energy profile for a series of experimentally evaluated nitrogen-based bidentate palladium ligands revealed that higher energy is required for decarboxylation and carbopalladation employing the experimentally least efficient ligand. The DFT investigation also showed that the relative free energies of the transition states were lowered in polar solvent, and preparative experiments confirmed that a nonoptimal ligand could be greatly improved by addition of water to the reaction system.