Metal–organic frameworks catalyzed C–C and C–heteroatom coupling reactions

Metal organic frameworks (MOFs) are porous crystalline solids whose structure is formed by metal ions or clusters of a few metal ions held in place by bi- or multipodal organic linkers. In some cases, the metal nodes in MOFs have exchangeable coordination positions that allow them to participate as active sites promoting organic reactions. There is much current interest in exploiting the advantages that MOFs offer as catalysts, including a large surface area, high metal content, flexibility in the design of the active sites in the framework, together with the easy synthesis of these materials. In the present review we describe the use of MOFs as catalysts to promote cross-coupling reactions involving organometallic reaction intermediates and catalysis by Lewis acid sites. These types of reactions are of large synthetic utility due to the high yields achieved, mild conditions and compatibility with other functional groups. The content includes C-C bond forming reactions, such as Suzuki-Miyaura, Mizoroki-Heck, Sonogashira, Stille and Ullmann, but also C-O and C-N cross-couplings. The final section summarizes our views on future developments and targets in these types of reactions. The core of the review is references that have appeared in 2010 or after, which give an idea of the novelty and current interest in this area.