Broadening the catalytic region from the cavity to windows by M₆L₁₂ nanospheres in cyclizations

Supramolecular cages have received tremendous attention as they can contain catalysts that exhibit confinement effects in the cavity, leading to excellent performances. Herein, we report an example wherein the catalytic region is extended from the cage cavity to the windows, and investigate its confinement effect by utilizing the Pd₆L^Au₁₂ cage that contains rigidly fixed and isolated gold complexes at the windows. Pd₆L^Au₁₂ exhibit three features of particular interest while assessing their properties in gold-catalyzed cyclization reactions. First, the catalysts experience a cage effect as they display higher reactivity and selectivity compared to the monomeric analogue, as a result of substrate pre-organization at the windows. Second, the metal complexes are physically separated by the cage structure, preventing the formation of less active dinuclear gold complexes making it more stable under hydrous conditions. Third, the cage windows present the characteristics of enzymatic catalysis via Michaelis-Menten-type mechanism analysis. This contribution presents an alternative way to engineer supramolecular catalysts through extending the catalytic region.