Engineering Metal-Organic Framework Catalysts for C-C and C-X Coupling Reactions: Advances in Reticular Approaches from 2014-2018.

Metal-organic frameworks (MOFs) are a class of crystalline porous materials that have been actively used for several industrial and synthetic applications. MOFs are spatially and geometrically extrapolated coordination polymers with intriguing properties such as tunable porosity and dimensionality. In terms of their catalytic efficiency, MOFs combine the easy recoverability of heterogeneous catalysts with the increased selectivity of biological catalysts. It is therefore not surprising that a lot of work on optimizing MOF catalysts for organic transformations has been carried out over the past decade. In this review, recent developments in MOF catalysis are summarized, with special attention being paid to C-C, C-N, and C-O coupling reactions. The influence of pore size, pore environment, and load on catalytic activity is described. Post-synthetic stabilization techniques and host-guest interactions in caged MOF scaffolds are detailed. Mechanistic aspects pertaining to the use of MOFs in asymmetric heterogeneous catalysis are highlighted and categorized.