Extension and functionalization of an encapsulating macrobicyclic ligand using palladium-catalyzed Suzuki-Miyaura and Sonogashira reactions of iron(ii) dihalogenoclathrochelates with inherent halogen substituents.

A new approach for performing Suzuki-Miyaura and Sonogashira reactions of iron(ii) dihalogenoclathrochelates, optimizing their reaction conditions (such as temperature, solvent and a palladium-containing catalyst) and the nature of other reagents (such as arylboron components) is elaborated. These palladium-catalyzed reactions are very sensitive to the nature of the macrobicyclic substrates. The reactivity of the leaving halogen atoms correlates with their ability to undergo an oxidative addition, decreasing in the order: I > Br > Cl, and iron(ii) diiodoclathrochelate underwent these C-C cross-couplings under their "classical" conditions.