Ionic Liquids in Biotransformations and Organocatalysis – Solvents and Beyond

Pablo Dominguez De Maria is Group Leader at the Institute of Technical and Macromolecular Chemistry (ITMC), RWTH Aachen University in Germany. He was previously affiliated with AkzoNobel NV in the Netherlands and Degussa AG in Germany. Dr. Dominguez de Maria has also worked as a technical freelance advisor on emerging technologies (e.g., catalysis) applied to sustainable chemistry (www.sustainable-momentum.net). He was awarded the Young Scientist Prize by the Iberoamerican Academy of Pharmacy.

Foreword by Prof. Dr. Roger Sheldon xiii Preface xv Contributors xvii PART I FUNDAMENTALS 1 1 IONIC LIQUIDS: DEFINITION, APPLICATIONS, AND CONTEXT FOR BIOTRANSFORMATIONS AND ORGANOCATALYSIS 3 Pablo Dominguez de Maria 1.1 Ionic Liquids: Definition, Development, and Overview of Current Main Applications 3 1.2 On the Greenness of ILs: Toward the Third Generation of ILs and DES 6 1.3 Context of ILs in Biotransformations and Organocatalysis 12 References 13 2 IONIC LIQUIDS AND PROTEINS: ACADEMIC AND SOME PRACTICAL INTERACTIONS 15 Zhen Yang 2.1 Introduction 17 2.2 Ionic Liquids, Water, and Proteins 18 2.3 Hofmeister Effects on Biocatalysis 26 2.4 Impact of Ionic Liquids on Enzymes and Proteins 41 2.5 Protein Extraction by Means of Ionic Liquids 52 2.6 Proper Selection of Ionic Liquids for Biocatalysis 57 2.7 Concluding Remarks 65 PART II IONIC LIQUIDS IN BIOTRANSFORMATIONS 73 3 IONIC LIQUIDS IN BIOTRANSFORMATIONS: MOTIVATION AND DEVELOPMENT 75 Christina Kohlmann and Lasse Greiner 3.1 First Uses of Ionic Liquids in Biotransformations 75 3.2 Motivation to Use IL in Biotransformations 80 3.3 Challenges for the Use of IL in Biotransformations 91 4 IONIC LIQUIDS AND OTHER NONCONVENTIONAL SOLVENTS IN BIOTRANSFORMATIONS: MEDIUM ENGINEERING AND PROCESS DEVELOPMENT 103 Pedro Lozano and Eduardo Garcia-Verdugo 4.1 Introduction: Toward Greener Catalytic Processes 103 4.2 The Importance of the Medium Engineering in Biotransformations 106 4.3 Biocatalysis in Monophasic ILs Systems 110 4.4 (Bio)catalytic Processes in SCFs 118 4.5 Multiphase Biotransformations 124 4.6 Prospects 140 5 IONIC LIQUIDS AS (CO-)SOLVENTS FOR HYDROLYTIC ENZYMES 151 Hua Zhao 5.1 Introduction 152 5.2 State-of-the-art: Lipases, Esterases, Proteases in ILs as (co-)Solvents 155 5.3 Use of ILs for (dynamic) Kinetic Resolutions ((D)KRs) 183 5.4 Hydrolase-Catalyzed Esterifi cations of Saccharides and Cellulose Derivatives in ILs 205 5.5 ILs for Glycosidases 210 5.6 Prospects 212 6 IONIC LIQUIDS AS (CO-)SOLVENTS FOR NONHYDROLYTIC ENZYMES 229 Daniela Gamenara, Patricia Saenz Mendez, Gustavo Seoane, and Pablo Dominguez de Maria 6.1 Ionic Liquids and Nonhydrolytic Enzymes 231 6.2 Use of ILs in Oxidoreductase-Catalyzed Enzymatic Reactions 232 6.3 ILs in Lyase-Catalyzed Reactions 253 6.4 Prospects 256 7 IONIC LIQUIDS AND WHOLE-CELL-CATALYZED PROCESSES 261 Danielle Dennewald and Dirk Weuster-Botz 7.1 Ionic Liquids Compatible with Whole-Cell Biocatalysis: Fundamentals and Design 263 7.2 Biocompatibility, Tolerance, and Accumulation in the Cell 272 7.3 State of the Art 281 7.4 Prospects 308 8 NONSOLVENT APPLICATIONS OF IONIC LIQUIDS IN BIOTRANSFORMATIONS 315 Pablo Dominguez de Maria and Christina Kohlmann 8.1 Introduction 315 8.2 Ionic Liquids as Additives in Biotransformations 316 8.3 Ionic Liquids for Coating Enzymes: The ILCE Concept 318 8.4 Ionic Liquids Combined with Membranes and Biotransformations 321 8.5 Ionic Liquids Anchoring Substrates 321 8.6 Ionic Liquids and Bioelectrochemistry 324 PART III IONIC LIQUIDS IN ORGANOCATALYSIS 331 9 IONIC LIQUIDS AS (CO-)SOLVENTS AND CO-CATALYSTS FOR ORGANOCATALYTIC REACTIONS 333 Stefan Toma and Radovan Sebesta 9.1 Nontraditional Media in Organocatalysis 333 9.2 Early Organocatalytic Reactions in Ionic Liquids 334 9.3 Ionic Liquids as Solvents for Organocatalytic Reactions 335 9.4 Ionic Liquids as Co-catalysts for Organocatalytic Reactions: Toward New Reactivities and Selectivities 353 9.5 Key Factors in Choosing Ionic Liquids for Organocatalysis and Prospects 355 10 "NONSOLVENT" APPLICATIONS OF IONIC LIQUIDS IN ORGANOCATALYSIS 361 Michelangelo Gruttadauria, Francesco Giacalone, Paola Agrigento, and Renato Noto 10.1 Introduction 361 10.2 Immobilizing Ionic Liquids and Organocatalysts 363 10.3 Anchoring of Organocatalyst to Ionic Liquids 378 10.4 Ionic Liquids as Organocatalysts 409 10.5 Conclusions 414 References 414 Index 419