Dutta Bishal, Mahajan Mayank, Ghosh Animesh, Dajek Maciej, Kowalczyk Rafal, Mondal Bhaskar, Ge Haibo, Maiti Debabrata
Department of Chemistry, Indian Institute of Technology Bombay, Mumbai, India.
School of Chemical Sciences, Indian Institute of Technology Mandi, Kamand, Himachal Pradesh, India.
Nat Commun. 2024 Aug 30;15(1):7543. doi: 10.1038/s41467-024-51764-1.
Regioselective distal C-H functionalization of nitroarenes by overriding proximal C-H activation has remained an unsolved challenge. Herein, we present a palladium-catalyzed meta-C-H alkenylation of nitroarene substrate, achieved through leveraging the non-covalent hydrogen bonding interactions. Urea-based templates comprising an elongated biphenyl linker designed in such a way that it interacts with nitro group via strong hydrogen bonding interaction, while a cyano based directing group is attached along the template to coordinate with the palladium center, thereby facilitating the activation of the remote meta-C-H bond of nitrobenzene. Computational mechanistic investigation and the analysis of non-covalent interaction deciphers the crucial role of H-bonding in regulating the regioselectivity.
通过优先进行近端C-H活化实现硝基芳烃的区域选择性远端C-H官能化仍然是一个未解决的挑战。在此，我们展示了一种钯催化的硝基芳烃底物间位C-H烯基化反应，该反应通过利用非共价氢键相互作用实现。基于尿素的模板包含一个细长的联苯连接基，其设计方式使其通过强氢键相互作用与硝基相互作用，同时一个基于氰基的导向基团沿着模板连接以与钯中心配位，从而促进硝基苯远程间位C-H键的活化。计算机理研究和非共价相互作用分析揭示了氢键在调节区域选择性中的关键作用。
