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      Metal–organic frameworks: advanced tools for multicomponent reactions

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          Abstract

          Metal–organic frameworks (MOFs) offering abundant catalytic sites in highly ordered crystalline skeletons have recently received considerable attention as green platforms for multicomponent reactions, which are discussed in this review.

          Abstract

          The increasing demand for simple, clean, and sustainable protocols for the preparation of complex organic molecules has continuously encouraged researchers to discover and design modern methodologies. Metal-catalyzed multicomponent reactions (MCRs) are versatile synthetic protocols frequently utilized in the preparation of numerous natural products and pharmaceuticals, offering perfect molecular diversity and high level of atom efficiency with energy saving in a single reaction step. Although most of the investigated metal-catalyzed MCRs are based on transition metal catalysts such as palladium and copper, the exploration of new sustainable catalytic systems is constantly the subject of intense research. In this regard, metal–organic frameworks (MOFs) have recently drawn significant interest as environmentally benign alternatives, providing abundant catalytic sites in highly ordered crystalline skeletons. Although this field of research is still in its infancy, MOFs have clearly exhibited their efficacy in multicomponent reactions. This review aims to outline the developments of MOFs for benign applications in multicomponent reactions.

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          Most cited references137

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          Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites.

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            A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability.

            Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation. Their unique properties are based on the molecular-scale porous character. However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications. Metal organic frameworks (MOFs) provided a breakthrough in this respect. New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare. Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability. The high stability is based on the combination of strong Zr-O bonds and the ability of the inner Zr6-cluster to rearrange reversibly upon removal or addition of mu3-OH groups, without any changes in the connecting carboxylates. The weak thermal, chemical, and mechanical stability of most MOFs is probably the most important property that limits their use in large scale industrial applications. The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.
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              Enantioselective catalysis with homochiral metal-organic frameworks.

              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.
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                Author and article information

                Contributors
                (View ORCID Profile)
                (View ORCID Profile)
                Journal
                GRCHFJ
                Green Chemistry
                Green Chem.
                Royal Society of Chemistry (RSC)
                1463-9262
                1463-9270
                November 2 2020
                2020
                : 22
                : 21
                : 7265-7300
                Affiliations
                [1 ]Department of Chemistry
                [2 ]Qom Branch
                [3 ]Islamic Azad University
                [4 ]Qom 37491-13191
                [5 ]I. R. Iran
                [6 ]The Institute of Scientific and Industrial Research (ISIR)
                [7 ]Osaka University
                [8 ]Osaka 567-0047
                [9 ]Japan
                Article
                10.1039/D0GC01767A
                62e8094f-30ff-4c78-92b0-f35baa06734a
                © 2020

                http://rsc.li/journals-terms-of-use

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