Computational characterization of the mechanism for the light-driven catalytic trichloromethylation of acylpyridines

被引：0
作者：
Fernandez-Alvarez V.M. [1 ]
Maseras F. [1 ,2 ]
机构：
[1] Institute of Chemical Research of Catalonia, Barcelona Institute for Science and Technology, Av. Paisos Catalans 16, Tarragona Catalonia
[2] Departament de Química, Universitat Autònoma de Barcelona, Bellaterra Catalonia
来源：
Maseras, Feliu (fmaseras@iciq.es) | 1600年 / Royal Society of Chemistry卷 / 15期
关键词：
Enantiomers - Enantioselectivity - Iridium - Precious metal compounds - Refractory metal compounds - Transition metals;
D O I：
10.1039/c7ob01826f
中图分类号：
学科分类号：
摘要：
The computational characterization of the mechanism for complex reactions involving the photoactivation of transition metal compounds remains a challenge for theoretical chemistry. In this work we show how the application of DFT and ONIOM(DFT:MM) methods can characterize the photoinduced iridium-catalyzed enantioselective trichloromethylation of 2-acylpyridines that was recently reported by Meggers and co-workers. This is a complex process, as it involves two linked catalytic cycles and yields the product with high enantioselectivity. Calculations succeed in reproducing all available experimental data, including the sign and value of the enantiomeric excess. The detailed mechanistic picture that is obtained leads to the identification of the origin of selectivity as the steric repulsion between an attacking trichloromethyl radical and the ligands at iridium in the path leads to the minor enantiomer. © The Royal Society of Chemistry 2017.
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页码：8641 / 8647
页数：6
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