Covalent immobilization of chiral dienes in mesoporous solids for asymmetric heterogeneous catalysis is highly attractive. In order to study confinement effects in bimolecular vs monomolecular reactions, a series of pseudo-C₂-symmetrical tetrahydropentalenes was synthesized and immobilized via click reaction on different mesoporous solids (silica, carbon, covalent organic frameworks) and compared with homogeneous conditions. Two types of Rh-catalyzed reactions were studied: (a) bimolecular nucleophilic 1,2-additions of phenylboroxine to N-tosylimine and (b) monomolecular isomerization of isoxazole to 2H-azirne. Polar support materials performed better than non-polar ones. Under confinement, bimolecular reactions showed decreased yields, whereas yields in monomolecular reactions were only little affected. Regarding enantioselectivity the opposite trend was observed, i. e. effective enantiocontrol for bimolecular reactions but only little control for monomolecular reactions was found.