Cascade reactions catalyzed by metal organic frameworks.

Cascade or tandem reactions where two or more individual reactions are carried out in one pot constitute a clear example of process intensification, targeting the maximization of spatial and temporal productivity with mobilization of minimum resources. In the case of catalytic reactions, cascade processes require bi-/multifunctional catalysts that contain different classes of active sites. Herein, we show that the features and properties of metal-organic frameworks (MOFs) make these solids very appropriate materials for the development of catalysts for cascade reactions. Due to composition and structure, MOFs can incorporate different types of sites at the metal nodes, organic linkers, or at the empty internal pores, allowing the flexible design and synthesis of multifunctional catalysts. After some introductory sections on the relevance of cascade reactions from the point of view of competitiveness, sustainability, and environmental friendliness, the main part of the text provides a comprehensive review of the literature reporting the use of MOFs as heterogeneous catalysts for cascade reactions including those that combine in different ways acid/base, oxidation/reduction, and metal-organic centers. The final section summarizes the current state of the art, indicating that the development of a first commercial synthesis of a high-added-value fine chemical will be a crucial milestone in this area.

[1]  C. Oliver Kappe,et al.  Continuous flow organic synthesis under high-temperature/pressure conditions. , 2010, Chemistry, an Asian journal.

[2]  Asterios Gavriilidis,et al.  Technology and Applications of Microengineered Reactors , 2002 .

[3]  Y. Iwasawa,et al.  Heterogeneous organic base-catalyzed reactions enhanced by acid supports. , 2007, Journal of the American Chemical Society.

[4]  Guanghua Li,et al.  A strategy toward constructing a bifunctionalized MOF catalyst: post-synthetic modification of MOFs on organic ligands and coordinatively unsaturated metal sites. , 2012, Chemical communications.

[5]  Yingwei Li,et al.  Multifunctional catalysis by Pd@MIL-101: one-step synthesis of methyl isobutyl ketone over palladium nanoparticles deposited on a metal-organic framework. , 2010, Chemical communications.

[6]  K. Hara,et al.  Synthesis of sugar alcohols by hydrolytic hydrogenation of cellulose over supported metal catalysts , 2011 .

[7]  K. Nicolaou,et al.  Kaskadenreaktionen in der Totalsynthese , 2006 .

[8]  Jackie Y. Ying,et al.  Nanostructured catalysts for organic transformations. , 2013, Accounts of chemical research.

[9]  Mark E. Davis,et al.  The effect of acid–base pairing on catalysis: An efficient acid–base functionalized catalyst for aldol condensation , 2007 .

[10]  Y. Horiuchi,et al.  Application of an amino-functionalised metal–organic framework: an approach to a one-pot acid–base reaction , 2013 .

[11]  Paul Watts,et al.  Recent advances in micro reaction technology. , 2011, Chemical communications.

[12]  Zhiyong Tang,et al.  Core-shell palladium nanoparticle@metal-organic frameworks as multifunctional catalysts for cascade reactions. , 2014, Journal of the American Chemical Society.

[13]  Hong-Cai Zhou,et al.  Selective gas adsorption and separation in metal-organic frameworks. , 2009, Chemical Society reviews.

[14]  Michael O’Keeffe,et al.  Exceptional chemical and thermal stability of zeolitic imidazolate frameworks , 2006, Proceedings of the National Academy of Sciences.

[15]  M. Allendorf,et al.  Metal‐Organic Frameworks: A Rapidly Growing Class of Versatile Nanoporous Materials , 2011, Advanced materials.

[16]  R. Luque,et al.  From alkyl aromatics to aromatic esters: efficient and selective C-H activation promoted by a bimetallic heterogeneous catalyst. , 2012, ChemSusChem.

[17]  Qinghong Zhang,et al.  Conversion of Cellulose into Sorbitol over Carbon Nanotube-Supported Ruthenium Catalyst , 2009 .

[18]  Tom Van Gerven,et al.  Structure, energy, synergy, time - the fundamentals of Process Intensification , 2009 .

[19]  M. Monge,et al.  3D scandium and yttrium arenedisulfonate MOF materials as highly thermally stable bifunctional heterogeneous catalysts , 2009 .

[20]  Shourong Zhu,et al.  Metal-organic frameworks constructed from 2,4,6-Tris(4-pyridyl)-1,3,5-triazine. , 2008, Inorganic chemistry.

[21]  Mircea Dincă,et al.  Hydrogen storage in metal-organic frameworks. , 2009, Chemical Society reviews.

[22]  Gérard Férey,et al.  Hybrid porous solids: past, present, future. , 2008, Chemical Society reviews.

[23]  A. Corma,et al.  MOFs as multifunctional catalysts: one-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst. , 2012, Dalton transactions.

[24]  Perla B. Balbuena,et al.  A versatile metal-organic framework for carbon dioxide capture and cooperative catalysis. , 2012, Chemical communications.

[25]  H. García,et al.  Metal-organic frameworks as solid catalysts for the synthesis of nitrogen-containing heterocycles. , 2014, Chemical Society reviews.

[26]  Michael O'Keeffe,et al.  Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage , 2002, Science.

[27]  F. Dautzenberg,et al.  Process intensification using multifunctional reactors , 2001 .

[28]  A. Corma,et al.  Engineering metal organic frameworks for heterogeneous catalysis. , 2010, Chemical reviews.

[29]  G. Martra Lewis acid and base sites at the surface of microcrystalline TiO2 anatase: relationships between surface morphology and chemical behaviour , 2000 .

[30]  O. Lebedev,et al.  2 ) : Preparation and Microstructural Characterisation , 2011 .

[31]  R. Luque,et al.  A Tuneable Bifunctional Water‐Compatible Heterogeneous Catalyst for the Selective Aqueous Hydrogenation of Phenols , 2011 .

[32]  H. Xin,et al.  Metal–organic frameworks as a very suitable reaction inductor for selective solvent-free multicomponent reaction: IRMOF-3 as a heterogeneous nanocatalyst for Kabachnik–Fields three-component reaction , 2013 .

[33]  Hailian Li,et al.  Synthetic Strategies, Structure Patterns, and Emerging Properties in the Chemistry of Modular Porous Solids† , 1998 .

[34]  O. Lebedev,et al.  Au@ZIFs: Stabilization and Encapsulation of Cavity-Size Matching Gold Clusters inside Functionalized Zeolite Imidazolate Frameworks, ZIFs , 2010 .

[35]  D. Muller,et al.  A surfactant-free strategy for synthesizing and processing intermetallic platinum-based nanoparticle catalysts. , 2012, Journal of the American Chemical Society.

[36]  A. Corma,et al.  Intracrystalline diffusion in metal organic framework during heterogeneous catalysis: influence of particle size on the activity of MIL-100 (Fe) for oxidation reactions. , 2011, Dalton transactions.

[37]  Michael J Zaworotko,et al.  Design and synthesis of metal-organic frameworks using metal-organic polyhedra as supermolecular building blocks. , 2009, Chemical Society reviews.

[38]  M. O'keeffe,et al.  Design and synthesis of an exceptionally stable and highly porous metal-organic framework , 1999, Nature.

[39]  N. Toshima Capped Bimetallic and Trimetallic Nanoparticles for Catalysis and Information Technology , 2008 .

[40]  Susumu Kitagawa,et al.  Functional porous coordination polymers. , 2004, Angewandte Chemie.

[41]  A. Corma,et al.  MOFs as Multifunctional Catalysts: Synthesis of Secondary Arylamines, Quinolines, Pyrroles, and Arylpyrrolidines over Bifunctional MIL‐101 , 2013 .

[42]  C. Serre,et al.  A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area , 2005, Science.

[43]  H Li,et al.  Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate frameworks. , 2001, Accounts of chemical research.

[44]  Avelino Corma,et al.  Mono- and multisite solid catalysts in cascade reactions for chemical process intensification. , 2009, ChemSusChem.

[45]  A. Corma,et al.  A cascade aerobic epoxidation of alkenes over Au/CeO2 and Ti-mesoporous material by in situ formed peroxides , 2009 .

[46]  H. Xin,et al.  Simultaneously application of SBA-15 sulfonic acid nanoreactor and ultrasonic irradiation as a very useful novel combined catalytic system: An ultra-fast, selective, reusable and waste-free green approach , 2013 .

[47]  Stuart L James,et al.  Metal-organic frameworks. , 2003, Chemical Society reviews.

[48]  Kimoon Kim,et al.  Tandem catalysis with a bifunctional site-isolated Lewis acid-Brønsted base metal-organic framework, NH2-MIL-101(Al). , 2012, Chemical communications.

[49]  A. Corma,et al.  One‐Pot Multifunctional Catalysis with NNN‐Pincer Zr‐MOF: Zr Base Catalyzed Condensation with Rh‐Catalyzed Hydrogenation , 2013 .

[50]  Pengyan Wu,et al.  Luminescent Sensing and Catalytic Performances of a Multifunctional Lanthanide‐Organic Framework Comprising a Triphenylamine Moiety , 2011 .

[51]  Michael O'Keeffe,et al.  Reticular synthesis and the design of new materials , 2003, Nature.

[52]  Y. Horiuchi,et al.  Development of a novel one-pot reaction system utilizing a bifunctional Zr-based metal–organic framework , 2014 .

[53]  K C Nicolaou,et al.  Cascade reactions in total synthesis. , 2006, Angewandte Chemie.

[54]  P. Günter,et al.  Structure-Activity Relationship of New Organic NLO Materials Based on Push-Pull Azodyes. 1. Synthesis and molecular properties of the dyes , 1998 .

[55]  Carlo Lamberti,et al.  A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. , 2008, Journal of the American Chemical Society.

[56]  A. Corma,et al.  Synthesis of structured porous polymers with acid and basic sites and their catalytic application in cascade-type reactions , 2013 .

[57]  T. Akita,et al.  Deposition of gold clusters on porous coordination polymers by solid grinding and their catalytic activity in aerobic oxidation of alcohols. , 2008, Chemistry.

[58]  Avelino Corma,et al.  Catalysis using multifunctional organosiliceous hybrid materials. , 2013, Chemical Society reviews.

[59]  Ilkeun Lee,et al.  Core-shell nanostructured catalysts. , 2013, Accounts of chemical research.

[60]  Thomas Schwalbe,et al.  Chemical synthesis in microreactors , 2002 .

[61]  David Farrusseng,et al.  Metall‐organische Gerüste für die Katalyse , 2009 .

[62]  S. Kitagawa,et al.  Funktionale poröse Koordinationspolymere , 2004 .

[63]  C. Chai,et al.  Atmospheric pressure aminocarbonylation of aryl iodides using palladium nanoparticles supported on MOF-5. , 2012, Chemical communications.

[64]  Wei‐Yin Sun,et al.  Novel metal-organic frameworks with specific topology from new tripodal ligands: 1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene. , 2003, Inorganic chemistry.

[65]  J. Čejka,et al.  Metal organic frameworks as heterogeneous catalysts for the production of fine chemicals , 2013 .

[66]  A. Corma,et al.  Bifunctional Metal Organic Framework Catalysts for Multistep Reactions: MOF‐Cu(BTC)‐[Pd] Catalyst for One‐Pot Heteroannulation of Acetylenic Compounds , 2012 .

[67]  B. Shanks,et al.  Acid-base cooperativity in condensation reactions with functionalized mesoporous silica catalysts , 2009 .

[68]  R. Luque,et al.  Significant promoting effects of Lewis acidity on Au-Pd systems in the selective oxidation of aromatic hydrocarbons. , 2012, Chemical communications.

[69]  T. Montier,et al.  Silver-Phosphonate Based Metal Organic Frameworks: Synthesis and Antibacterial Action , 2013 .

[70]  Xinggui Zhou,et al.  Palladium Nanoparticles Confined in the Cages of MIL-101: An Efficient Catalyst for the One-Pot Indole Synthesis in Water , 2011 .

[71]  Longlong Ma,et al.  Conversion of cellulose and cellobiose into sorbitol catalyzed by ruthenium supported on a polyoxometalate/metal-organic framework hybrid. , 2013, ChemSusChem.

[72]  M. O'keeffe,et al.  Colossal cages in zeolitic imidazolate frameworks as selective carbon dioxide reservoirs , 2008, Nature.

[73]  Russell K. Feller,et al.  Structural diversity and chemical trends in hybrid inorganic-organic framework materials. , 2006, Chemical communications.

[74]  T. Akita,et al.  One-potN-alkylation of primary amines to secondary amines by gold clusters supported on porous coordination polymers , 2009 .

[75]  G. Hutchings,et al.  Solvent-Free Oxidation of Primary Carbon-Hydrogen Bonds in Toluene Using Au-Pd Alloy Nanoparticles , 2011, Science.

[76]  A. Cheetham,et al.  Anorganische Materialien mit offenen Gerüsten , 1999 .

[77]  H. García,et al.  Metal-Organic Frameworks (MOFs) as Heterogeneous Catalysts for the Chemoselective Reduction of Carbon-Carbon Multiple Bonds with Hydrazine , 2009 .

[78]  Mark E. Davis,et al.  Cooperative catalysis by silica-supported organic functional groups. , 2008, Chemical Society reviews.

[79]  A. Corma,et al.  Orthogonal C-N plus C-C tandem reaction of iodoanilines leading to styrylguanidines catalyzed by supported palladium nanoparticles. , 2012, Chemistry.

[80]  A. Corma,et al.  Bifunctional iridium-(2-aminoterephthalate)–Zr-MOF chemoselective catalyst for the synthesis of secondary amines by one-pot three-step cascade reaction ☆ , 2013 .

[81]  A. Corma,et al.  Designing bifunctional acid–base mesoporous hybrid catalysts for cascade reactions , 2013 .

[82]  Cheetham,et al.  Open-Framework Inorganic Materials. , 1999, Angewandte Chemie.

[83]  Ulrich Müller,et al.  Industrial applications of metal-organic frameworks. , 2009, Chemical Society reviews.

[84]  C. Pinel,et al.  Metal-organic frameworks: opportunities for catalysis. , 2009, Angewandte Chemie.

[85]  A. Corma,et al.  Multifunctional hybrid organic-inorganic catalytic materials with a hierarchical system of well-defined micro- and mesopores. , 2010, Journal of the American Chemical Society.

[86]  Michael O'Keeffe,et al.  A route to high surface area, porosity and inclusion of large molecules in crystals , 2004, Nature.

[87]  M. Willis,et al.  Carbon–carbon bond construction using boronic acids and aryl methyl sulfides: orthogonal reactivity in Suzuki-type couplings , 2013 .