Enantioselective catalysis with homochiral metal–organic frameworks

Abstract

This tutorial review presents recent developments of homochiral metal-organic frameworks (MOFs) in enantioselective catalysis. Following a brief introduction of the basic concepts and potential virtues of MOFs in catalysis, we summarize three distinct strategies that have been utilized to synthesize homochiral MOFs. Framework stability and accessibility of the open channels to reagents are then addressed. We finally survey recent successful examples of catalytically active homochiral MOFs based on three approaches, namely, homochiral MOFs with achiral catalytic sites, incorporation of asymmetric catalysts directly into the framework, and post-synthetic modification of homochiral MOFs. Although still in their infancy, homochiral MOFs have clearly demonstrated their utility in heterogeneous asymmetric catalysis, and a bright future is foreseen for the development of practically useful homochiral MOFs in the production of optically pure organic molecules.

The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene

“…Moreover, unlike traditional immobilized catalysts 9,10,11 , the active catalytic sites in MOFs are well protected by the coordination bonds which prevents leaching to a higher extent. Although the research in this field is relatively new, MOFs have been studied as catalysts in hydrogenation and oxidation reactions 12,13,14,15,16,17,18 enantioselective reactions 19,20,21 , photocatalysis 22 , carbonyl cyanosilylation 23,24,25 , hydrodesulfurization 26 and esterification 27 .…”

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

“…They have been successfully used as catalysts in hydrogenation and oxidation reactions 11 enantioselective reactions, 12 photo catalysis, 13 and hydrodesulfurization 14 . The highly tunable structure allows the MOF to act both as heterogeneous catalyst and as solid support.…”

Crystal structure of poly[dibromido-(μ 2–4,4′-bis-(pyrid-4-yl)biphenyl-κ 2 N:N′)lead(II)], C22H16N2PbBr2

“…In recent years, research on coordination complexes has made considerable progress in the elds of supramolecular chemistry and crystal engineering, owing to their intriguing architectures and functional applications, such as gas storage [1], catalysis [2], magnetism [3] and luminescence [4]. Studies in this eld have been focused on the rational design and synthesis of novel frameworks and the relationships between their structures and properties.…”