Modular Approach for the Development of Supported,Monofunctionalized,Salen Catalysts

摘要

We report a modular approach toward polymer-supported,metalated,salen catalysts.This strategy is based on the synthesis of monofunctionalized Mn- and Co-salen complexes attached to a norbornene monomer via a stable phenylene-acetylene linker.The resulting functionalized monomers can be polymerized in a controlled fashion using ring-opening metathesis polymerization.This polymerization method allows for the synthesis of copolymers,resulting in an unprecedented control over the catalyst density and catalytic-site isolation.The obtained polymeric manganese and cobalt complexes were successfully used as supported catalysts for the asymmetric epoxidation of olefins and the hydrolytic kinetic resolution of epoxides.All polymeric catalysts showed outstanding catalytic activities and selectivities comparable to the original catalysts reported by Jacobsen.Moreover,the copolymer-supported catalysts are more active and selective than their homopolymer analogues,providing further proof that catalyst density and site isolation are key toward highly active and selective supported salen catalysts.