Conformational Control of Organocatalyst in Strongly Brønsted‐Acidic Metal‐Organic Frameworks for Enantioselective Catalysis

Abstract

AbstractChiral imidodiphosphates (IDPs) have emerged as strong Brønsted acid catalysts for many enantioselective processes. However, the dynamic transformation between O,O‐syn and O,O‐anti conformers typically results in low enantioselectivity. Here we demonstrate that topologies of metal‐organic frameworks (MOFs) can be exploited to control IDP conformations and local chiral microenvironments for enantioselective catalysis. Two porous Dy‐MOFs with different topologies are obtained from an enantiopure 1,1′‐biphenol IDP‐based tetracarboxylate ligand. While the ligand adopts a 4‐ or 3‐connected (c) binding mode, all IDPs are rigidified to get only a single O,O‐syn conformation and display greatly enhanced Brønsted acidity relative to the free IDP. The MOF with the 4‐c IDP that has a relatively less compact shape than the 3‐c IDP can be an efficient and recyclable heterogeneous Brønsted acid catalysing the challenging asymmetric O,O‐acetalization reaction with up to 96 % enantiomeric excess.