Jacobsen’s complexes are famous for their usability for enantioselective epoxidations. However, the applicability of this catalytic system has been severely limited by several practical problems such as deactivation and separation after reaction. Grafting of Jacobsen-type complexes on solid supports is an attractive way to overcome these problems but led to a decrease in selectivity. A combined theoretical and experimental approach is presented to unravel the factors governing enantioselectivity. The importance of different substituents was determined by analyzing the transition state for the oxygen transfer using the full system as a model. An analysis of the asymmetric complex has shown an inherent tendency for a decreased selectivity due to the lack of specific bulky groups. Experimentally an immobilized Jacobsen catalyst on a metal organic framework (MIL-101) was synthesized which confirms the computational tendencies but the decrease in selectivity is limited, indicating that the MIL-101(Cr) is a suitable carrier for this complex.