Guo Wentao, Tantillo Dean J
Department of Chemistry, University of California, Davis, Davis, California 95616, United States.
J Am Chem Soc. 2024 Mar 13;146(10):7039-7051. doi: 10.1021/jacs.4c00382. Epub 2024 Feb 28.
A special type of C-H functionalization can be achieved through C-H insertion combined with Cope rearrangement (CHCR) in the presence of dirhodium catalysts. This type of reaction was studied using density functional theory and molecular dynamics simulations, the results of which pointed to the dynamic origins of low yields observed in some experiments. These studies not only reveal intimate details of the complex reaction network underpinning CHCR reactions but also further cement the generality of the importance of nonstatistical dynamic effects in controlling RhL-promoted reactions.
在二铑催化剂存在下，通过碳氢键插入与科普重排（CHCR）相结合可实现一种特殊类型的碳氢键官能化。利用密度泛函理论和分子动力学模拟对这类反应进行了研究，其结果指出了一些实验中低产率的动力学根源。这些研究不仅揭示了支撑CHCR反应的复杂反应网络的详细信息，还进一步巩固了非统计动力学效应在控制铑配合物促进反应中的重要性这一普遍性。
