Catalysis in Ionic Liquids Vasile I. Pa ˆ rvulescu* ,† and Christopher Hardacre* ,‡ Department of Chemical Technology and Catalysis, University of Bucharest, B-dul Regina Elisabeta 4-12, Bucharest 030016, Romania and The QUILL Centre/School of Chemistry and Chemical Engineering, Queen’s University Belfast, Belfast BT9 5AG, Northern Ireland, United Kingdom Received August 9, 2006 Contents 1. Introduction 2616 2. Nanostabilized Catalysts in ILs 2617 2.1. ILs as Solvents for Synthesis of Nanoparticles 2617 2.2. Active Complexes of Metal Compounds with ILs 2619 2.3. Supported IL-Stabilized Catalysts 2619 2.4. ILs as Templates for Heterogeneous Catalysts 2621 2.5. Stabilization of IL Emulsions by Nanoparticles 2623 3. Hydrogenations in ILs 2623 3.1. Hydrogenation on IL-Stabilized Nanoparticles 2623 3.1.1. Hydrogenation of 1,3-Butadiene 2623 3.1.2. Hydrogenation of Alkenes and Arenes 2624 3.1.3. Hydrogenation of Ketones 2624 3.2. Homogeneous Catalytic Hydrogenation in ILs 2624 3.3. Hydrogenation of Functionalized ILs 2625 3.3.1. Selective Hydrogenation of Polymers 2625 3.4. Asymmetric Hydrogenations 2626 3.4.1. Enantioselective Hydrogenation 2626 3.5. Role of the ILs Purity in Hydrogenation Reactions 2628 3.6. Hydrogenation via Heterogeneous Catalysis in ILs 2628 3.7. Biocatalysis in ILs for Reduction of Organic Molecules 2630 3.8. Hydrogen-Transfer Reactions in ILs 2630 4. Catalytic Oxidation in ILs 2631 4.1. ILs as a Media for Organic Oxidations 2631 4.2. Homogeneous Catalytic Oxidation in ILs 2632 4.2.1. Glaser Oxidative Coupling 2632 4.2.2. Epoxidation 2632 4.2.3. Hydrocarbons to Other Oxygenated Compounds 2632 4.2.4. Alcohols to Carbonyl and Carbonyl to Carboxylate Compounds 2633 4.2.5. Oxidation of CdNOH Bonds 2634 4.2.6. Oxidation of Thiols 2634 4.2.7. Oxybromination 2635 4.3. Homogeneous Asymmetric Catalytic Oxidation in ILs 2635 4.4. ILs in Kinetic Resolution Reactions 2635 4.5. Heterogeneous Catalytic Oxidation in ILs 2635 4.6. Electrochemical Oxidation in ILs 2636 4.7. Biooxidation in ILs 2637 5. Acid-Base-Catalyzed Reactions in ILs 2638 5.1. Acid-Catalyzed C-C and C-X Bond-Forming Reactions 2638 5.1.1. Sakurai Reaction 2639 5.1.2. Henry Reaction 2639 5.1.3. Carbonyl Allylation of Aldehydes and Ketones 2639 5.1.4. Stille Coupling 2639 5.2. Sulfonylation Reactions of Aromatics 2639 5.3. Silylstannations of R,-Unsaturated Carbonyl Compounds 2640 5.4. Debromination of 2-Bromoketones 2640 5.5. Protection of Carbonyls to Acetals and Ketals 2640 5.6. Deprotection 2640 5.7. Ligand Substitution Reactions: Fluorination Reactions 2640 5.8. Isomerization 2641 5.9. Acid-Catalyzed Reactions in ILs Using Heterogeneous Catalysts 2641 5.10. Deoximation 2641 5.11. Acid-Catalyzed Reactions with Task-Specific ILs 2642 5.12. Base-Catalyzed Reactions 2642 5.13. Enzymatic Catalyzed Aldol Reactions in ILs 2643 6. Carbonylation and Hydroformylation 2643 6.1. Carbonylation 2643 6.1.1. Carbonylation of Aromatic Hydrocarbons via Homogeneous Catalysis 2643 6.1.2. Carbonylation of Aryl Halides and Terminal Alkynes via Homogeneous Catalysis 2643 6.1.3. Pauson-Khand Reaction 2644 6.1.4. Carbonylation of Alcohols via Homogeneous Catalysis 2644 6.1.5. Carbonylation of Amines and Nitrobenzene via Homogeneous Catalysis 2644 6.2. Carbonylation via Heterogeneous Catalysis 2645 6.2.1. Carbonylation of Amines and Nitrobenzene 2645 6.3. Hydroformylation 2645 6.4. Hydroformylation via Heterogeneous Catalysis 2646 7. Dimerization 2646 7.1. Diels-Alder Reactions 2648 8. Polymerization 2648 8.1. Radical Polymerization in ILs 2649 8.2. Charge-Transfer Polymerization 2649 * To whom correspondence should be addressed. E-mail: v_parvulescu@ chem.unibuc.ro (V.I.P.) and c.hardacre@qub.ac.uk (C.H.). † University of Bucharest. ‡ Queen’s University Belfast. 2615 Chem. Rev. 2007, 107, 2615-2665 10.1021/cr050948h CCC: $65.00 © 2007 American Chemical Society Published on Web 05/23/2007 Downloaded by BEIJING UNIV OF CHEMICAL TECHNOLOGY at 19:14:04:902 on July 01, 2019 from https://pubs.acs.org/doi/10.1021/cr050948h.