Increased Efficacies of an Individual Catalytic Site in Clustered Multivalent Dendritic Catalysts

In the studies reported so far on dendrimer‐mediated catalysis, the efficacies of the catalytic units were studied and compared primarily across the generations. In order to identify the efficacy of an individual catalytic unit with respect to the number of such units present within a given generation, a series of catalysts were prepared within a generation. Dendrimers incorporated with phosphine‐metal complexes were chosen for the study and as many as 11 catalysts within three generations were synthesized. The CC bond‐forming reactions, namely, the Heck and the Suzuki coupling reactions, were then selected to study the catalytic efficiencies of the series of partially and fully phosphine‐metal complex functionalized dendrimers. The efficacies of the formation of cinnamate and biphenyl, catalyzed by the dendritic catalysts, were compared. The comparative analyses show that an individual catalytic site is far more effective in its catalytic activity when presented in multiple numbers, i.e., in a multivalent dendritic system, than as a single unit within the same generation, i.e., in a monovalent dendritic system. The study identifies the beneficial effects of the multivalent presentation of the catalytic moieties, both within and across the dendrimer generations.