A powerful aluminum catalyst for the synthesis of highly functional organic carbonates.

An aluminum complex based on an amino triphenolate ligand scaffold shows unprecedented high activity (initial TOFs up to 36,000 h(-1)), broad substrate scope, and functional group tolerance in the formation of highly functional organic carbonates prepared from epoxides and CO(2). The developed catalytic protocol is further characterized by low catalyst loadings and relative mild reaction conditions using a cheap, abundant, and nontoxic metal.

[1]  M. North,et al.  Bimetallic aluminium(acen) complexes as catalysts for the synthesis of cyclic carbonates from carbon dioxide and epoxides , 2011 .

[2]  J. A. Castro‐Osma,et al.  Synthesis of cyclic carbonates using monometallic, and helical bimetallic, aluminium complexes , 2012 .

[3]  G. Coates,et al.  Cobalt catalysts for the alternating copolymerization of propylene oxide and carbon dioxide: combining high activity and selectivity. , 2005, Journal of the American Chemical Society.

[4]  D. Darensbourg,et al.  A facile catalytic synthesis of trimethylene carbonate from trimethylene oxide and carbon dioxide , 2010 .

[5]  D. Darensbourg,et al.  Mechanistic studies of the copolymerization reaction of oxetane and carbon dioxide to provide aliphatic polycarbonates catalyzed by (Salen)CrX complexes. , 2008, Journal of the American Chemical Society.

[6]  I. Goldberg,et al.  Exploring Routes to Tantalum(V) Alkylidene Complexes Supported by Amine Tris(phenolate) Ligands , 2005 .

[7]  B. Rieger,et al.  Transformation of carbon dioxide with homogeneous transition-metal catalysts: a molecular solution to a global challenge? , 2011, Angewandte Chemie.

[8]  R. He,et al.  Syntheses of cyclic carbonates from carbon dioxide and epoxides with metal phthalocyanines as catalyst , 2000 .

[9]  J. Hedrick,et al.  A simple and efficient synthesis of functionalized cyclic carbonate monomers using a versatile pentafluorophenyl ester intermediate. , 2010, Journal of the American Chemical Society.

[10]  Arjan W. Kleij,et al.  An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions , 2012 .

[11]  Hui Wang,et al.  Chemical fixation of carbon dioxide to cyclic carbonates under extremely mild conditions with highly active bifunctional catalysts , 2004 .

[12]  M. Aresta,et al.  Utilisation of CO2 as a chemical feedstock: opportunities and challenges. , 2007, Dalton transactions.

[13]  A. Dibenedetto,et al.  A general and expedient synthesis of 5- and 6-membered cyclic carbonates by palladium-catalyzed oxidative carbonylation of 1,2- and 1,3-diols. , 2011, ChemSusChem.

[14]  Arjan W. Kleij,et al.  Salen-complex-mediated formation of cyclic carbonates by cycloaddition of CO2 to epoxides. , 2010, Angewandte Chemie.

[15]  Yugen Zhang,et al.  Copper- and copper–N-heterocyclic carbene-catalyzed C─H activating carboxylation of terminal alkynes with CO2 at ambient conditions , 2010, Proceedings of the National Academy of Sciences.

[16]  M. North,et al.  Mechanism of Cyclic Carbonate Synthesis from Epoxides and CO2** , 2009, Angewandte Chemie.

[17]  D. Darensbourg,et al.  Tuning the Selectivity of the Oxetane and CO2 Coupling Process Catalyzed by (Salen)CrCl/n-Bu4NX: Cyclic Carbonate Formation vs Aliphatic Polycarbonate Production , 2010 .

[18]  T. Ema,et al.  A bifunctional catalyst for carbon dioxide fixation: cooperative double activation of epoxides for the synthesis of cyclic carbonates. , 2012, Chemical communications.

[19]  Michael North,et al.  Synthesis of cyclic carbonates from epoxides and CO2 , 2010 .

[20]  M. North,et al.  Cyclic carbonate synthesis catalysed by bimetallic aluminium-salen complexes. , 2010, Chemistry.

[21]  Hiroyuki Yasuda,et al.  Transformation of carbon dioxide. , 2007, Chemical reviews.

[22]  T. Endo,et al.  Substituent Effect on the Anionic Equilibrium Polymerization of Six-Membered Cyclic Carbonates , 1998 .

[23]  S. Sujith,et al.  A highly active and recyclable catalytic system for CO2/propylene oxide copolymerization. , 2008, Angewandte Chemie.

[24]  T. Sakakura,et al.  The synthesis of organic carbonates from carbon dioxide. , 2009, Chemical communications.

[25]  D. Darensbourg,et al.  Formation of Cyclic Carbonates from Carbon Dioxide and Epoxides Coupling Reactions Efficiently Catalyzed by Robust, Recyclable One-Component Aluminum-Salen Complexes , 2012 .

[26]  H. Kricheldorf,et al.  Polylactones. 16. Cationic Polymerization of Trimethylene Carbonate and Other Cyclic Carbonates , 1989 .

[27]  M. Ree,et al.  Copolymerization of carbon dioxide and propylene oxide using an aluminum porphyrin system and its components , 1999 .

[28]  M. North,et al.  Synthesis of Cyclic Carbonates from Atmospheric Pressure Carbon Dioxide Using Exceptionally Active Aluminium(salen) Complexes as Catalysts , 2007 .

[29]  S. Minakata,et al.  Atmospheric CO2 fixation by unsaturated alcohols using tBuOI under neutral conditions. , 2010, Angewandte Chemie.

[30]  Mikkel Jørgensen,et al.  The teraton challenge. A review of fixation and transformation of carbon dioxide , 2010 .

[31]  O. Jacquet,et al.  Recycling of carbon and silicon wastes: room temperature formylation of N-H bonds using carbon dioxide and polymethylhydrosiloxane. , 2012, Journal of the American Chemical Society.

[32]  D. Darensbourg,et al.  Making plastics from carbon dioxide: salen metal complexes as catalysts for the production of polycarbonates from epoxides and CO2. , 2007, Chemical reviews.

[33]  Charlotte K. Williams,et al.  A bimetallic iron(III) catalyst for CO2/epoxide coupling. , 2011, Chemical communications.

[34]  S. Nguyen,et al.  Chemical CO2 Fixation: Cr(III) Salen Complexes as Highly Efficient Catalysts for the Coupling of CO2 and Epoxides , 2001 .

[35]  Charlotte K. Williams,et al.  Highly active dizinc catalyst for the copolymerization of carbon dioxide and cyclohexene oxide at one atmosphere pressure. , 2009, Angewandte Chemie.

[36]  D. Darensbourg,et al.  Metal salen derivatives as catalysts for the alternating copolymerization of oxetanes and carbon dioxide to afford polycarbonates. , 2006, Inorganic chemistry.

[37]  Olivier Jacquet,et al.  A diagonal approach to chemical recycling of carbon dioxide: organocatalytic transformation for the reductive functionalization of CO2. , 2012, Angewandte Chemie.

[38]  B. Ko,et al.  Trimetallic magnesium complexes bearing amine-bis(benzotriazole phenolate) derivatives as bifunctional catalysts for ring-opening polymerization and CO2/epoxide coupling. , 2012, Chemical communications.

[39]  M. Aresta.  Carbon dioxide as chemical feedstock , 2010 .

[40]  A. Kleij,et al.  Ambient Fixation of Carbon Dioxide using a ZnIIsalphen Catalyst , 2011 .

[41]  D. Darensbourg,et al.  Cobalt catalysts for the coupling of CO2 and epoxides to provide polycarbonates and cyclic carbonates. , 2012, Chemical Society reviews.

[42]  B. Lee,et al.  Coupling Reaction of CO 2 with Epoxides by Binary Catalytic System of Lewis Acids and Onium Salts , 2006 .

[43]  A. Kleij,et al.  Myth or reality? Fixation of carbon dioxide into complex organic matter under mild conditions. , 2011, ChemSusChem.