Recent decades have witnessed remarkable progress in ligand-promoted C-H activation with palladium catalysts. While a number of transformations have been achieved with a fairly broad substrate scope, the general requirements for high palladium loadings and enormous challenges in catalyst recycling severely limit the practical applications of C-H activation methodologies in organic synthesis. Herein, we incorporate N,C-ligand-chelated palladacycles into rigid, porous, and crystalline covalent organic frameworks for the C-H arylation of indole and pyrrole derivatives. These heterogeneous palladium catalysts exhibit superior stability and recyclability compared to their homogeneous counterparts. We not only produce several highly reactive palladacycles embedded on new framework supports to facilitate C-H activation/C-C bond-forming reactions but also reassign heterogenized palladium species on frameworks containing a benzaldehyde-derived imine moiety as imine-based palladacycles via comprehensive characterization. Our findings provide guidance for the rational design of framework-supported metallacycles in the development of heterogeneous transition-metal catalysis.
© 2024 The Authors. Published by American Chemical Society.