Recyclable organocatalysts based on hybrid silicas

The quest for efficient and “greener” catalysts for chemical processes has set a precedent for the development of reliable methods for their synthesis. These methods, based on heterogeneous platforms, present an excellent opportunity because they allow recyclability and easy work-up and handling. Hybrid organosilica-based materials are of interest particularly as heterogeneous platforms, which can operate with a synergy between the well-defined properties of the organocatalytic fragments and the structural and mechanical stability as well as the presumed chemical inertness of the silica matrices. This review focuses on recent advances in the incorporation methods to strongly bind organocatalysts into organosilica scaffolds and their promising applications in supported organocatalysis.

[1]  G. Hutchings,et al.  Towards heterogeneous organocatalysis: chiral iminium cations supported on porous materials for enantioselective alkene epoxidation , 2013 .

[2]  A. Gervasini,et al.  Hybrid Inorganic‐Organic Materials Carrying Tertiary Amine and Thiourea Residues Tethered on Mesoporous Silica Nanoparticles: Synthesis, Characterization, and Co‐Operative Catalysis , 2009 .

[3]  M. Finn,et al.  Click Chemistry: Diverse Chemical Function from a Few Good Reactions. , 2001 .

[4]  V. S. Lin,et al.  Organosulfonic acid-functionalized mesoporous silicas for the esterification of fatty acid , 2003 .

[5]  P. Pescarmona,et al.  Synthesis and high-throughput testing of multilayered supported ionic liquid catalysts for the conversion of CO2 and epoxides into cyclic carbonates , 2014 .

[6]  D. Vos,et al.  Sulfonic acid functionalised ordered mesoporous materials as catalysts for condensation and esterification reactions , 1998 .

[7]  R. Ryoo,et al.  Improvement of Hydrothermal Stability of MCM-41 Using Salt Effects during the Crystallization Process , 1997 .

[8]  G. Guillena,et al.  Solvent-free enantioselective Friedländer condensation with wet 1,1'-binaphthalene-2,2'-diamine-derived prolinamides as organocatalysts. , 2013, The Journal of organic chemistry.

[9]  Xiaoyu Wang,et al.  Core–shell silica magnetic microspheres supported proline as a recyclable organocatalyst for the asymmetric aldol reaction , 2012 .

[10]  T. Asefa,et al.  Optimizing acid-base bifunctional mesoporous catalysts for the henry reaction: effects of the surface density and site isolation of functional groups. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[11]  R. Maggi,et al.  Cycloaddition of CO2 to epoxides over both homogeneous and silica-supported guanidine catalysts , 2003 .

[12]  A. Pascall,et al.  Acid-base bifunctional and dielectric outer-sphere effects in heterogeneous catalysis: a comparative investigation of model primary amine catalysts. , 2006, Journal of the American Chemical Society.

[13]  A. Studer,et al.  Bifunctional mesoporous silica nanoparticles as cooperative catalysts for the Tsuji-Trost reaction--tuning the reactivity of silica nanoparticles. , 2013, Chemical communications.

[14]  A. Khalafi‐Nezhad,et al.  A new silica-supported organocatalyst based on L-proline: An efficient heterogeneous catalyst for one-pot synthesis of spiroindolones in water , 2013 .

[15]  Canxiong Guo,et al.  9-Thiourea Cinchona alkaloid supported on mesoporous silica as a highly enantioselective, recyclable heterogeneous asymmetric catalyst. , 2008, Chemical communications.

[16]  A. Puglisi,et al.  Stereoselective organic reactions promoted by immobilized chiral catalysts in continuous flow systems , 2013 .

[17]  M. Benaglia,et al.  Recoverable and recyclable chiral organic catalysts , 2006 .

[18]  Lina Han,et al.  Ionic liquids containing carboxyl acid moieties grafted onto silica: Synthesis and application as heterogeneous catalysts for cycloaddition reactions of epoxide and carbon dioxide , 2011 .

[19]  S. Inagaki,et al.  Enhanced sol–gel polymerization of organoallylsilanes by solvent effect , 2011 .

[20]  Yaping Li,et al.  Exploration of Dependence of Organo-Catalyzed Enantioselective Michael Addition on the Pore Size of Mesoporous Host , 2012 .

[21]  Sayam Sen Gupta,et al.  “Clickable” SBA-15 mesoporous materials: synthesis, characterization and their reaction with alkynes , 2009 .

[22]  Mark E. Davis,et al.  Nanoscale organization of thiol and arylsulfonic acid on silica leads to a highly active and selective bifunctional, heterogeneous catalyst. , 2008, Journal of the American Chemical Society.

[23]  N. R. Shiju,et al.  Mesoporous Silica with Site-Isolated Amine and Phosphotungstic Acid Groups: A Solid Catalyst with Tunable Antagonistic Functions for One-Pot Tandem Reactions** , 2011, Angewandte Chemie.

[24]  R. Corriu,et al.  From molecular chemistry to hybrid nanomaterials. Design and functionalization. , 2011, Chemical Society reviews.

[25]  Q. Huo,et al.  Organization of Organic Molecules with Inorganic Molecular Species into Nanocomposite Biphase Arrays , 1994 .

[26]  T. Asefa,et al.  Efficient bifunctional nanocatalysts by simple postgrafting of spatially isolated catalytic groups on mesoporous materials. , 2007, Angewandte Chemie.

[27]  Miss A.O. Penney (b) , 1974, The New Yale Book of Quotations.

[28]  Y. Shao,et al.  Synthesis, characterization and catalytic activity of acid–base bifunctional materials by controlling steric hindrance , 2010 .

[29]  Mi-Kyung Lee,et al.  Imidazolium derivatives functionalized MCM-41 for catalytic conversion of carbon dioxide to cyclic carbonate , 2009 .

[30]  F. A. Luzzio,et al.  The Henry reaction: recent examples , 2001 .

[31]  Bradley F. Chmelka,et al.  Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures , 1998 .

[32]  Xin Li,et al.  Equilibrium acidities of proline derived organocatalysts in DMSO. , 2015, Organic letters.

[33]  O. Terasaki,et al.  Synthesis and Characterization of the Amphoteric Amino Acid Bifunctional Mesoporous Silica , 2007 .

[34]  P. Dalko,et al.  In the golden age of organocatalysis. , 2004, Angewandte Chemie.

[35]  J. Alemán,et al.  Applications of asymmetric organocatalysis in medicinal chemistry. , 2013, Chemical Society reviews.

[36]  T. Asefa,et al.  Controlled Synthesis of the Henry Reaction Products: Nitroalcohol Versus Nitrostyrene by a Simple Change of Amino-Groups of Aminofunctionalized Nanoporous Catalysts , 2008 .

[37]  Y. Liu,et al.  Synthesis of Ionic Liquid Functionalized SBA‐15 Mesoporous Materials as Heterogeneous Catalyst toward Knoevenagel Condensation under Solvent‐Free Conditions , 2006 .

[38]  A. Puglisi,et al.  Polymer-supported organic catalysts. , 2003, Chemical reviews.

[39]  J. Croissant,et al.  Click approaches in sol–gel chemistry , 2013, Journal of Sol-Gel Science and Technology.

[40]  A. Fernández-Mayoralas,et al.  Asymmetric aldol reaction using immobilized proline on mesoporous support , 2005 .

[41]  D. Vos,et al.  1,5,7-Triazabicyclo[4.4.0]dec-5-ene Immobilized in MCM-41: A Strongly Basic Porous Catalyst† , 1997 .

[42]  T. Asefa,et al.  Substituent‐ and Catalyst‐Dependent Selectivity to Aldol or Nitrostyrene Products in a Heterogeneous Base‐Catalyzed Henry Reaction , 2010 .

[43]  V. S. Lin,et al.  Controlling the selectivity of competitive nitroaldol condensation by using a bifunctionalized mesoporous silica nanosphere-based catalytic system. , 2004, Journal of the American Chemical Society.

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

[45]  T. Sakakura,et al.  Synergistic hybrid catalyst for cyclic carbonate synthesis: remarkable acceleration caused by immobilization of homogeneous catalyst on silica. , 2006, Chemical communications.

[46]  Peng Zhang,et al.  Schiff base supported MCM-41 catalyzed the Knoevenagel condensation in water , 2013 .

[47]  S. Burgard ISR , 1999 .

[48]  P. Pihko,et al.  Asymmetric Organocatalytic Diels–Alder Reactions on Solid Support , 2002 .

[49]  S. Shylesh,et al.  Mesoporous organosilicas with acidic frameworks and basic sites in the pores: an approach to cooperative catalytic reactions. , 2010, Angewandte Chemie.

[50]  Lei Wang,et al.  Asymmetric aldol reactions catalyzed by efficient and recyclable silica-supported proline-based peptides. , 2009, Chirality.

[51]  Nicolas J. Rahier,et al.  Silica-supported l-proline organocatalysts for asymmetric aldolisation , 2009 .

[52]  Y. Iwasawa,et al.  Bifunctional heterogeneous catalysis of silica-alumina-supported tertiary amines with controlled acid-base interactions for efficient 1,4-addition reactions. , 2009, Chemistry.

[53]  F. Giacalone,et al.  New ionic liquid-modified silica gels as recyclable materials for L-proline- or H–Pro–Pro–Asp–NH2-catalyzed aldol reaction , 2007 .

[54]  Neil Genzlinger A. and Q , 2006 .

[55]  J. Clark,et al.  Catalysis of the Knoevenagel reaction by γ-aminopropylsilica , 1997 .

[56]  G. Chuah,et al.  Organic–inorganic hybrid catalysts for acid- and base-catalyzed reactions , 2000 .

[57]  Lei Wang,et al.  Silica gel supported pyrrolidine-based chiral ionic liquid as recyclable organocatalyst for asymmetric Michael addition to nitrostyrenes , 2008 .

[58]  Alessandro Massi,et al.  Asymmetric organocatalysis: from infancy to adolescence. , 2008, Angewandte Chemie.

[59]  K. Wu,et al.  Acid–base bi-functionalized, large-pored mesoporous silica nanoparticles for cooperative catalysis of one-pot cellulose-to-HMF conversion , 2012 .

[60]  Shuguo Wang Amino groups immobilized on MCM-48: an efficient heterogeneous catalyst for the Knoevenagel reaction , 2003 .

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

[62]  Dong Yang,et al.  Controlled Synthesis of Magnetite−Silica Nanocomposites via a Seeded Sol−Gel Approach , 2009 .

[63]  Amália Monge-Marcet,et al.  Recyclable silica-supported prolinamide organocatalysts for direct asymmetric Aldol reaction in water , 2012 .

[64]  A. Alexakis,et al.  Chiral amines as organocatalysts for asymmetric conjugate addition to nitroolefins and vinyl sulfones via enamine activation. , 2007, Chemical communications.

[65]  Nirmalya Moitra,et al.  Click approaches to functional water-sensitive organotriethoxysilanes. , 2011, The Journal of organic chemistry.

[66]  J. Choi,et al.  Heterogeneous organocatalysis for the asymmetric desymmetrization of meso-cyclic anhydrides using silica gel-supported bis-cinchona alkaloids , 2004 .

[67]  Sang-Wook Park,et al.  Immobilization of ionic liquid on hybrid MCM-41 system for the chemical fixation of carbon dioxide on cyclic carbonate , 2008 .

[68]  Shengyu Feng,et al.  Multifunctional alkoxysilanes prepared by thiol–yne “click” chemistry: their luminescence properties and modification on a silicon surface , 2014 .

[69]  John D. Bass,et al.  Bifunctional Surface Imprinting of Silica: Thermolytic Synthesis and Characterization of Discrete Thiol−Amine Functional Group Pairs , 2006 .

[70]  S. Schaus,et al.  Asymmetric Morita-Baylis-Hillman reactions catalyzed by chiral Brønsted acids. , 2003, Journal of the American Chemical Society.

[71]  Esmail Doustkhah,et al.  Nanoporous silica-supported organocatalyst: a heterogeneous and green hybrid catalyst for organic transformations , 2014 .

[72]  Mark E. Davis,et al.  Studies on mesoporous materials II. Synthesis mechanism of MCM-41 , 1993 .

[73]  Carles Rodríguez-Escrich,et al.  Organocatalysis on Tap: Enantioselective Continuous Flow Processes Mediated by Solid‐Supported Chiral Organocatalysts , 2015 .

[74]  M. Lakshmi Kantam,et al.  One-pot synthesis of conjugated nitroalkenes by diamino-functionalised mesoporous material , 1999 .

[75]  Sang-Eon Park,et al.  Asymmetric Catalysis in Confined Space Provided by l-Proline Functionalized Mesoporous Silica with Plugs in the Pore , 2010 .

[76]  S. Inagaki,et al.  Syntheses, properties and applications of periodic mesoporous organosilicas prepared from bridged organosilane precursors. , 2011, Chemical Society reviews.

[77]  P. Hesemann,et al.  Pore size control and organocatalytic properties of nanostructured silica hybrid materials containing amino and ammonium groups , 2011 .

[78]  A. Mandoli,et al.  Silicone-Supported Cinchona Alkaloid Derivatives as Insoluble Organocatalysts in the Enantioselective Dimerization of Ketenes , 2012 .

[79]  F. Zaera,et al.  Interference of the surface of the solid on the performance of tethered molecular catalysts. , 2012, Journal of the American Chemical Society.

[80]  Omar Pandoli,et al.  Toward the optimization of continuous-flow aldol and α-amination reactions by means of proline-functionalized silicon packed-bed microreactors , 2011 .

[81]  Bradley F. Chmelka,et al.  Direct Syntheses of Ordered SBA-15 Mesoporous Silica Containing Sulfonic Acid Groups , 2000 .

[82]  Antony E. Fernandes,et al.  Application of CuAAC for the covalent immobilization of homogeneous catalysts , 2014 .

[83]  Jian Liu,et al.  The nanocomposites of SO3H-hollow-nanosphere and chiral amine for asymmetric aldol reaction , 2009 .

[84]  J. Guan,et al.  The effect of the distance between acidic site and basic site immobilized on mesoporous solid on the activity in catalyzing aldol condensation , 2011 .

[85]  Xiaomei Wang,et al.  Synthesis, Characterization and Catalytic Properties of Chiral BINOL Functionalized Mesoporous Silicas for Enantioselective Morita-Baylis-Hillman Reaction , 2008 .

[86]  X. Cattoën,et al.  A general method for preparing bridged organosilanes with pendant functional groups and functional mesoporous organosilicas. , 2014, Chemistry.

[87]  Niki Baccile,et al.  Introducing ecodesign in silica sol–gel materials , 2009 .

[88]  M. Antonietti,et al.  Chloride ion pairs as catalysts for the alkylation of aldehydes and ketones with C-H acidic compounds , 2009 .

[89]  Jiantai Ma,et al.  Silica-supported pyrrolidine–triazole, an insoluble, recyclable organocatalyst for the enantioselective Michael addition of ketones to nitroalkenes , 2008 .

[90]  D. Macquarrie Direct preparation of organically modified MCM-type materials. Preparation and characterisation of aminopropyl–MCM and 2-cyanoethyl–MCM , 1996 .

[91]  J. Rosenholm,et al.  On the nature of the Brønsted acidic groups on native and functionalized mesoporous siliceous SBA-15 as studied by benzylamine adsorption from solution. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[92]  M. Head‐Gordon,et al.  Tailoring the Cooperative Acid–Base Effects in Silica‐Supported Amine Catalysts: Applications in the Continuous Gas‐Phase Self‐Condensation of n‐Butanal , 2014 .

[93]  Toshio Suzuki,et al.  Immobilization of MacMillan Imidazolidinone as Mac-SILC and its Catalytic Performance on Sustainable Enantioselective Diels-Alder Cycloaddition , 2010 .

[94]  K. Kuroda,et al.  The preparation of alkyltrimethylammonium-kanemite complexes and their conversion to microporous materials. , 1990 .

[95]  G. Celentano,et al.  Continuous-flow stereoselective organocatalyzed Diels-Alder reactions in a chiral catalytic "homemade" HPLC column. , 2013, Organic letters.

[96]  A. Corma,et al.  Silica-Bound Homogenous Catalysts as Recoverable and Reusable Catalysts in Organic Synthesis , 2006 .

[97]  Xinyong Li,et al.  Clickable periodic mesoporous organosilicas: synthesis, click reactions, and adsorption of antibiotics. , 2014, Chemistry.

[98]  Jiaqing Wang,et al.  The synthesis of cyclohexenone using L-proline immobilized on a silica gel catalyst by a continuous-flow approach , 2014 .

[99]  F. Renzo,et al.  Improved stability of MCM-41 through textural control , 1994 .

[100]  A. Bhaumik,et al.  Triazine functionalized ordered mesoporous organosilica as a novel organocatalyst for the facile one-pot synthesis of 2-amino-4H-chromenes under solvent-free conditions , 2012 .

[101]  R. Baharfar,et al.  Immobilization of 1,4-Diazabicyclo[2.2.2]Octane (DABCO) over Mesoporous Silica SBA-15: An Efficient Approach for the Synthesis of Functionalized Spirochromenes , 2014 .

[102]  Linlin Li,et al.  Mesoporous Silica Nanoparticles: Synthesis, Biocompatibility and Drug Delivery , 2012, Advanced materials.

[103]  D. B. Jackson,et al.  Aminopropylated MCMs as base catalysts: a comparison withaminopropylated silica , 1997 .

[104]  Nirmalya Moitra,et al.  Hybrid materials: versatile matrices for supporting homogeneous catalysts , 2010 .

[105]  E. Brunet Asymmetric induction under confinement. , 2002, Chirality.

[106]  F. Renzo,et al.  Preferential grafting of alkoxysilane coupling agents on the hydrophobic portion of the surface of micelle-templated silica , 2000 .

[107]  V. S. Lin,et al.  Bifunctionalized mesoporous materials with site-separated Brønsted acids and bases: catalyst for a two-step reaction sequence. , 2011, Angewandte Chemie.

[108]  Wenbin Lin,et al.  Molecular building block approaches to chiral porous zirconium phosphonates for asymmetric catalysis , 2004 .

[109]  Jian Liu,et al.  L-Prolinamide functionalized mesoporous silicas: Synthesis and catalytic performance in direct aldol reaction , 2009 .

[110]  M. Kantam,et al.  Knoevenagel and aldol condensations catalysed by a new diamino-functionalised mesoporous material , 1999 .

[111]  Jingping Qu,et al.  N-Heterocyclic carbene functionalized MCM-41 as an efficient catalyst for chemical fixation of carbon dioxide , 2011 .

[112]  Shuangxi Liu,et al.  Mesoporous SBA-15 with Short Mesochannels Immobilized Natural Quinine for Asymmetric Michael Addition of Chalcones , 2011 .

[113]  X. Cattoën,et al.  Tailoring the hydrophilic/lipophilic balance of clickable mesoporous organosilicas by the copper-catalyzed azide-alkyne cycloaddition click-functionalization. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[114]  K. Jørgensen,et al.  Organocatalysis--after the gold rush. , 2009, Chemical Society reviews.

[115]  A. Fuchs,et al.  Experiment and theory of low-pressure nitrogen adsorption in organic layers supported or grafted on inorganic adsorbents: toward a tool to characterize surfaces of hybrid organic/inorganic systems. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[116]  A. Bhaumik,et al.  Functionalized mesoporous materials as efficient organocatalysts for the syntheses of xanthenes , 2012 .

[117]  V. Dufaud,et al.  A New Step Towards Solid Base Catalysis: Azidoproazaphosphatranes Immobilized in Nanopores of Mesoporous Silica , 2011 .

[118]  J. S. Beck,et al.  Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism , 1992, Nature.

[119]  Jing He,et al.  Heterogeneous asymmetric Henry-Michael one-pot reaction synergically catalyzed by grafted chiral bases and inherent achiral hydroxyls on mesoporous silica surface. , 2012, Chemical communications.

[120]  D. Yin,et al.  Task-specific basic ionic liquid immobilized on mesoporous silicas: Efficient and reusable catalysts for Knoevenagel condensation in aqueous media , 2010 .

[121]  D. Seebach,et al.  Preparation of dendritic and non-dendritic styryl-substituted Salens for cross-linking suspension copolymerization with styrene and multiple use of the corresponding Mn and Cr complexes in enantioselective epoxidations and hetero-Diels-Alder reactions. , 2001, Chemistry.

[122]  Christopher W. Jones,et al.  Cooperative Catalysis with Acid–Base Bifunctional Mesoporous Silica: Impact of Grafting and Co-condensation Synthesis Methods on Material Structure and Catalytic Properties , 2012 .

[123]  A. Corma,et al.  In situ preparation of a multifunctional chiral hybrid organic–inorganic catalyst for asymmetric multicomponent reactions , 2013 .

[124]  Zhou Zhou,et al.  Hybrid mesoporous materials containing covalently anchored N-phenylthiazolium salts as organo catalysts , 2009 .

[125]  R. Pleixats,et al.  Organic–inorganic hybrid silica materials containing imidazolium and dihydroimidazolium salts as recyclable organocatalysts for Knoevenagel condensations , 2009 .

[126]  D. Vos,et al.  Mesoporous Sulfonic Acids as Selective Heterogeneous Catalysts for the Synthesis of Monoglycerides , 1999 .

[127]  Jian Liu,et al.  Chirally functionalized hollow nanospheres containing L-prolinamide: synthesis and asymmetric catalysis. , 2010, Chemistry.

[128]  Alex Wagner,et al.  Cooperative acid-base effects with functionalized mesoporous silica nanoparticles: applications in carbon-carbon bond-formation reactions. , 2009, Chemistry.

[129]  Mark E. Davis,et al.  Multifunctional heterogeneous catalysts: SBA-15-containing primary amines and sulfonic acids. , 2006, Angewandte Chemie.

[130]  C. Gommes,et al.  Quantitative Characterization of Pore Corrugation in Ordered Mesoporous Materials Using Image Analysis of Electron Tomograms , 2009 .

[131]  A. Bhaumik,et al.  Covalently anchored organic carboxylic acid on porous silica nano particle: A novel organometallic catalyst (PSNP-CA) for the chromatography-free highly product selective synthesis of tetrasubstituted imidazoles , 2013 .

[132]  Jing He,et al.  Synergic catalytic effects in confined spaces. , 2012, Chemical communications.

[133]  Fredrickson,et al.  Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores , 1998, Science.

[134]  A. Cavazzini,et al.  Silica-supported 5-(pyrrolidin-2-yl)tetrazole: development of organocatalytic processes from batch to continuous-flow conditions , 2012 .

[135]  K. Oh,et al.  Orthogonal enantioselectivity approaches using homogeneous and heterogeneous catalyst systems: Friedel-Crafts alkylation of indole. , 2010, Angewandte Chemie.

[136]  J. B. Higgins,et al.  A new family of mesoporous molecular sieves prepared with liquid crystal templates , 1992 .

[137]  J. Ying,et al.  Enantioselective Catalysis over Chiral Imidazolidin‐4‐one Immobilized on Siliceous and Polymer‐Coated Mesocellular Foams , 2006 .

[138]  C. Enjalbal,et al.  From protected trialkoxysilyl-peptide building blocks to bioorganic-silica hybrid materials. , 2013, Journal of materials chemistry. B.

[139]  Zhou Zhou,et al.  Sustainable, green protocols for heterogenized organocatalysts: N-Phenylthiazolium salts heterogenized on organic–inorganic hybrid mesoporous supports , 2010 .

[140]  Jianxiong Jiang,et al.  Ionic liquid-functionalized SBA-15 mesoporous material: efficient heterogeneous catalyst in versatile organic reactions , 2007 .

[141]  Mark E. Davis,et al.  Enhanced cooperative, catalytic behavior of organic functional groups by immobilization , 2006 .

[142]  G. Wang,et al.  Efficient solid-base catalysts for aldol reaction by optimizing the density and type of organoamine groups on nanoporous silica , 2009 .

[143]  A. Corma,et al.  Chiral copper(II) bisoxazoline covalently anchored to silica and mesoporous MCM-41 as a heterogeneous catalyst for the enantioselective Friedel-Crafts hydroxyalkylation. , 2002, Chemical communications.

[144]  Nirmalya Moitra,et al.  Convenient route to water-sensitive sol-gel precursors using click chemistry. , 2010, Chemical communications.

[145]  J. Clark,et al.  Green, transition-metal-free aerobic oxidation of alcohols using a highly durable supported organocatalyst. , 2007, Angewandte Chemie.

[146]  V. S. Lin,et al.  Urea and Thiourea-Functionalized Mesoporous Silica Nanoparticle Catalysts with Enhanced Catalytic Activity for Diels–Alder Reaction , 2010 .

[147]  Douglas A. Loy,et al.  BRIDGED POLYSILSESQUIOXANES. HIGHLY POROUS HYBRID ORGANIC-INORGANIC MATERIALS , 1995 .

[148]  Takeshi Kobayashi,et al.  Substrate inhibition in the heterogeneous catalyzed aldol condensation: A mechanistic study of supported organocatalysts , 2012 .

[149]  M. Maynadier,et al.  Mixed Periodic Mesoporous Organosilica Nanoparticles and Core–Shell Systems, Application to in Vitro Two-Photon Imaging, Therapy, and Drug Delivery , 2014 .

[150]  M. Jaroniec,et al.  Determination of Pore Size and Pore Wall Structure of MCM-41 by Using Nitrogen Adsorption, Transmission Electron Microscopy, and X-ray Diffraction , 2000 .

[151]  Sang-Eon Park,et al.  trans-1,2-Diaminocyclohexane mesoporous silica for asymmetric catalysis: enhancement of chirality through confinement space by the plug effect. , 2012, Chemical communications.

[152]  A. Corma,et al.  Multisite organic-inorganic hybrid catalysts for the direct sustainable synthesis of GABAergic drugs. , 2014, Angewandte Chemie.

[153]  Sang-Eon Park,et al.  Chiral enhancement in diethyl malonate addition by morphosynthesized L-proline mesoporous silica. , 2008, Chemical communications.

[154]  B. Trost,et al.  The direct catalytic asymmetric aldol reaction. , 2010, Chemical Society reviews.

[155]  Y. Zhang,et al.  Heterogeneous organocatalysis at work: functionalization of hollow periodic mesoporous organosilica spheres with MacMillan catalyst. , 2011, Chemistry.

[156]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[157]  Can Li,et al.  Chiral catalysis in nanopores of mesoporous materials. , 2007, Chemical communications.

[158]  J. Barrault,et al.  Significant enhancement on selectivity in silica supported sulfonic acids catalyzed reactions. , 2007, Chemical communications.

[159]  Jiajian Peng,et al.  Ionic liquid functionalized silica gel : novel catalyst and fixed solvent , 2006 .

[160]  C. Palomo,et al.  Asymmetric organocatalysis by chiral Brønsted bases: implications and applications. , 2009, Chemical Society reviews.

[161]  V. S. Lin,et al.  Cooperative catalysis by general acid and base bifunctionalized mesoporous silica nanospheres. , 2005, Angewandte Chemie.

[162]  J. Zou,et al.  A systematic study of long-range ordered 3D-SBA-15 materials by electron tomography , 2011 .

[163]  Amália Monge-Marcet,et al.  Prolinamide bridged silsesquioxane as an efficient, eco-compatible and recyclable chiral organocatalyst , 2011 .

[164]  P. Renzi,et al.  Non-asymmetric organocatalysis. , 2012, Chemical communications.

[165]  Jeffrey I Zink,et al.  Controlled multiple functionalization of mesoporous silica nanoparticles: homogeneous implementation of pairs of functionalities communicating through energy or proton transfers. , 2015, Nanoscale.

[166]  A. Corma,et al.  Immobilized Proton Sponge on Inorganic Carriers: The Synergic Effect of the Support on Catalytic Activity , 2002 .

[167]  S. Inagaki,et al.  A new synthetic approach for functional triisopropoxyorganosilanes using molecular building blocks , 2013 .

[168]  Ying Wan,et al.  On the controllable soft-templating approach to mesoporous silicates. , 2007, Chemical reviews.

[169]  R. Garrell,et al.  Thiol-ene click reaction as a general route to functional trialkoxysilanes for surface coating applications. , 2011, Journal of the American Chemical Society.

[170]  D. Macquarrie,et al.  Catalytic activity of aminopropyl xerogels in the selective synthesis of (E)-nitrostyrenes from nitroalkanes and aromatic aldehydes , 2004 .

[171]  B. Ma,et al.  Superparamagnetic Nanoparticle-Supported (S)-Diphenyl- prolinol Trimethylsilyl Ether as a Recyclable Catalyst for Asymmetric Michael Addition in Water , 2010 .

[172]  A. Fernández-Mayoralas,et al.  Asymmetric aldol reaction catalyzed by a heterogenized proline on a mesoporous support. The role of the nature of solvents. , 2007, The Journal of organic chemistry.

[173]  V. S. Lin,et al.  One-pot reaction cascades catalyzed by base- and acid-functionalized mesoporous silica nanoparticles , 2008 .

[174]  D. MacMillan,et al.  The advent and development of organocatalysis , 2008, Nature.

[175]  F. Giacalone,et al.  Supported proline and proline-derivatives as recyclable organocatalysts. , 2008, Chemical Society reviews.

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

[177]  R. Sebastián,et al.  Recoverable silica-gel supported binam-prolinamides as organocatalysts for the enantioselective solvent-free intra- and intermolecular aldol reaction , 2013 .

[178]  Christopher W. Jones,et al.  Tuning cooperativity by controlling the linker length of silica-supported amines in catalysis and CO2 capture. , 2012, Journal of the American Chemical Society.

[179]  Fang Zhang,et al.  Ordered Mesoporous Proline Organocatalyst with High Activity and Strong Durability in Promoting Intermolecular Cross‐Conjugated Additions , 2012 .

[180]  D. Shantz,et al.  Nitroaldol reactions catalyzed by amine-MCM-41 hybrids , 2010 .

[181]  O. Terasaki,et al.  An amphoteric mesoporous silica catalyzed aldol reaction , 2009 .

[182]  Ying Guo,et al.  l-Proline-Grafted Mesoporous Silica with Alternating Hydrophobic and Hydrophilic Blocks to Promote Direct Asymmetric Aldol and Knoevenagel–Michael Cascade Reactions , 2014 .

[183]  G. Guillena,et al.  Enantioselective direct aldol reaction: the blossoming of modern organocatalysis , 2007 .

[184]  Q. Huo,et al.  Highly ordered periodic mesoporous organosilica nanoparticles with controllable pore structures. , 2012, Nanoscale.

[185]  Yuhan Sun,et al.  Grafted ionic liquid: Catalyst for solventless cycloaddition of carbon dioxide and propylene oxide , 2009 .

[186]  YanagisawaTsuneo,et al.  The Preparation of Alkyltriinethylaininonium–Kaneinite Complexes and Their Conversion to Microporous Materials , 2006 .

[187]  D. Kordestani,et al.  Biguanide-Functionalized Fe 3 O 4 /SiO 2 Magnetic Nanoparticles: An Efficient Heterogeneous Organosuperbase Catalyst for Various Organic Transformations in Aqueous Media , 2012 .

[188]  Hengquan Yang,et al.  N-Heterocyclic carbene palladium complex supported on ionic liquid-modified SBA-16: an efficient and highly recyclable catalyst for the Suzuki and Heck reactions , 2009 .

[189]  Christopher W. Jones,et al.  Tuning acid–base cooperativity to create next generation silica-supported organocatalysts , 2013 .

[190]  E. Simanek,et al.  Engineering nanospaces: ordered mesoporous silicas as model substrates for building complex hybrid materials , 2005, Nanotechnology.

[191]  J. Croissant,et al.  One‐Pot Construction of Multipodal Hybrid Periodic Mesoporous Organosilica Nanoparticles with Crystal‐Like Architectures , 2015, Advanced materials.

[192]  S. Loebbecke,et al.  Use of immobilized organic base catalysts for continuous-flow fine chemical synthesis , 2008 .

[193]  Y. Iwasawa,et al.  Acid-base bifunctional catalysis of silica-alumina-supported organic amines for carbon-carbon bond-forming reactions. , 2008, Chemistry.

[194]  Y. Iwasawa,et al.  Cooperative catalysis of primary and tertiary amines immobilized on oxide surfaces for one-pot C-C bond forming reactions. , 2008, Angewandte Chemie.

[195]  J. Nakazawa,et al.  Controlled loadings in a mesoporous material: click-on silica. , 2008, Journal of the American Chemical Society.

[196]  K. Jørgensen,et al.  Hydrogen-bonding in aminocatalysis: from proline and beyond. , 2014, Chemistry.

[197]  R. Stephenson A and V , 1962, The British journal of ophthalmology.

[198]  Arne Thomas,et al.  Imidazolium functionalized SBA-15 type silica: efficient organocatalysts for Henry and cycloaddition reactions , 2013 .

[199]  T. Tatsumi,et al.  Further Investigations on the Promoting Effect of Mesoporous Silica on Base-Catalyzed Aldol Reaction , 2010 .

[200]  D. MacMillan,et al.  New Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels−Alder Reaction , 2000 .

[201]  M. Fröba,et al.  Vitalising porous inorganic silica networks with organic functions--PMOs and related hybrid materials. , 2011, Chemical Society reviews.

[202]  W. Marsden I and J , 2012 .

[203]  A. Bhaumik,et al.  Highly ordered acid functionalized SBA-15: a novel organocatalyst for the preparation of xanthenes. , 2011, Chemical communications.

[204]  G. Marin,et al.  Silanol‐Assisted Aldol Condensation on Aminated Silica: Understanding the Arrangement of Functional Groups , 2014 .

[205]  D. Brunel,et al.  Monoglyceride Synthesis by Heterogeneous Catalysis Using MCM-41 Type Silicas Functionalized with Amino Groups. , 1997, The Journal of organic chemistry.

[206]  S. Shylesh,et al.  Bifunctional Mesoporous Materials with Coexisting Acidic and Basic Sites for CC Bond Formation in Co‐operative Catalytic Reactions , 2010 .

[207]  T. Kristensen,et al.  Polymer-Supported Chiral Organocatalysts: Synthetic Strategies for the Road Towards Affordable Polymeric Immobilization , 2010 .

[208]  Brian J. Smith,et al.  Discrete complexes immobilized onto click-SBA-15 silica: controllable loadings and the impact of surface coverage on catalysis. , 2012, Journal of the American Chemical Society.

[209]  A. Studer,et al.  Preparation of bifunctional mesoporous silica nanoparticles by orthogonal click reactions and their application in cooperative catalysis. , 2012, Chemistry.

[210]  W. Ouellette,et al.  Toward efficient nanoporous catalysts: controlling site-isolation and concentration of grafted catalytic sites on nanoporous materials with solvents and colorimetric elucidation of their site-isolation. , 2008, Journal of the American Chemical Society.

[211]  Pablo Domínguez de María,et al.  Silica-immobilized piperazine: A sustainable organocatalyst for aldol and Knoevenagel reactions , 2010 .

[212]  Andrew G. Glen,et al.  APPL , 2001 .

[213]  F. Giacalone,et al.  A Liquid–Liquid Biphasic Homogeneous Organocatalytic Aldol Protocol Based on the Use of a Silica Gel Bound Multilayered Ionic Liquid Phase , 2012 .

[214]  P. Melchiorre Cinchona-based primary amine catalysis in the asymmetric functionalization of carbonyl compounds. , 2012, Angewandte Chemie.

[215]  Divya Sachdev,et al.  Sulfonic acid functionalized mesoporous SBA-15 for one-pot synthesis of substituted aryl-14H-dibenzo xanthenes and bis(indolyl) methanes , 2010 .

[216]  A. Puglisi,et al.  Stereoselective DielsAlder Reactions Promoted under Continuous‐Flow Conditions by Silica‐Supported Chiral Organocatalysts , 2014 .

[217]  Franco Cozzi Immobilization of Organic Catalysts: When, Why, and How , 2006 .

[218]  K. Shea,et al.  Organo-silica hybrid functional nanomaterials: how do organic bridging groups and silsesquioxane moieties work hand-in-hand? , 2011, Chemical Society reviews.

[219]  Mark E. Davis,et al.  Organized surface functional groups: cooperative catalysis via thiol/sulfonic acid pairing. , 2007, Journal of the American Chemical Society.

[220]  Nirmalya Moitra,et al.  Facile route to functionalized mesoporous silica nanoparticles by click chemistry , 2011 .

[221]  K. Nakanishi,et al.  Surface functionalization of silica by Si-H activation of hydrosilanes. , 2014, Journal of the American Chemical Society.

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

[223]  V. Srivastava,et al.  Organic–Inorganic Hybrid Materials for Enantioselective Organocatalysis , 2009 .

[224]  A. Corma,et al.  Heterogeneized Brönsted base catalysts for fine chemicals production : grafted quaternary organic ammonium hydroxides as catalyst for the production of chromenes and coumarins , 2000 .

[225]  C. Kresge,et al.  The discovery of mesoporous molecular sieves from the twenty year perspective. , 2013, Chemical Society reviews.