Recent advances in heterogeneous porous Metal-Organic Framework catalysis for Suzuki-Miyaura cross-couplings.

Suzuki-Miyaura coupling (SMC), a crucial C-C cross-coupling reaction, is still associated with challenges such as high synthetic costs, intricate work-ups, and contamination with homogeneous metal catalysts. Research intensely focuses on strategies to convert homogeneous soluble metal catalysts into insoluble powder solids, promoting heterogeneous catalysis for easy recovery and reuse as well as for exploring greener reaction protocols. Metal-Organic Frameworks (MOFs), recognized for their high surface area, porosity, and presence of transition metals, are increasingly studied for developing heterogeneous SMC. The molecular fence effect, attributed to MOF surface functionalization, helps preventing catalyst deactivation by aggregation, migration, and leaching during catalysis. Recent reports demonstrate the enhanced catalytic activity, selectivity, stability, application scopes, and potential of MOFs in developing greener heterogeneous synthetic methodologies. This review focuses on the catalytic applications of MOFs in SMC reactions, emphasizing developments after 2016. It critically examines the synthesis and incorporation of active metal species into MOFs, focusing on morphology, crystallinity, and dimensionality for catalytic activity induction. MOF catalysts are categorized based on their metal nodes in subsections, with comprehensive discussion on Pd incorporation strategies, catalyst structures, optimal SMC conditions, and application scopes, concluding with insights into challenges and future research directions in this important emerging area of MOF applications.