Chiral Nanoporous Metal–Metallosalen Frameworks for Hydrolytic Kinetic Resolution of Epoxides

Chiral nanoporous metal–organic frameworks are constructed by using dicarboxyl-functionalized chiral Ni­(salen) and Co­(salen) ligands. The Co­(salen)-based framework is shown to be an efficient and recyclable heterogeneous catalyst for hydrolytic kinetic resolution (HKR) of racemic epoxides with up to 99.5% ee. The MOF structure brings Co­(salen) units into a highly dense arrangement and close proximity that enhances bimetallic cooperative interactions, leading to improved catalytic activity and enantioselectivity in HKR compared with its homogeneous analogues, especially at low catalyst/substrate ratios.