Ionic Liquids in Biotransformations and Organocatalysis

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 xvContributors xviiPART I FUNDAMENTALS 11 IONIC LIQUIDS: DEFINITION, APPLICATIONS, AND CONTEXT FOR BIOTRANSFORMATIONS AND ORGANOCATALYSIS 3Pablo Domínguez de María1.1 Ionic Liquids: Definition, Development, and Overview of Current Main Applications 31.2 On the Greenness of ILs: Toward the Third Generation of ILs and DES 61.3 Context of ILs in Biotransformations and Organocatalysis 12References 132 IONIC LIQUIDS AND PROTEINS: ACADEMIC AND SOME PRACTICAL INTERACTIONS 15Zhen Yang2.1 Introduction 172.2 Ionic Liquids, Water, and Proteins 182.3 Hofmeister Effects on Biocatalysis 262.4 Impact of Ionic Liquids on Enzymes and Proteins 412.5 Protein Extraction by Means of Ionic Liquids 522.6 Proper Selection of Ionic Liquids for Biocatalysis 572.7 Concluding Remarks 65PART II IONIC LIQUIDS IN BIOTRANSFORMATIONS 733 IONIC LIQUIDS IN BIOTRANSFORMATIONS: MOTIVATION AND DEVELOPMENT 75Christina Kohlmann and Lasse Greiner3.1 First Uses of Ionic Liquids in Biotransformations 753.2 Motivation to Use IL in Biotransformations 803.3 Challenges for the Use of IL in Biotransformations 914 IONIC LIQUIDS AND OTHER NONCONVENTIONAL SOLVENTS IN BIOTRANSFORMATIONS: MEDIUM ENGINEERING AND PROCESS DEVELOPMENT 103Pedro Lozano and Eduardo García-Verdugo4.1 Introduction: Toward Greener Catalytic Processes 1034.2 The Importance of the Medium Engineering in Biotransformations 1064.3 Biocatalysis in Monophasic ILs Systems 1104.4 (Bio)catalytic Processes in SCFs 1184.5 Multiphase Biotransformations 1244.6 Prospects 1405 IONIC LIQUIDS AS (CO-)SOLVENTS FOR HYDROLYTIC ENZYMES 151Hua Zhao5.1 Introduction 1525.2 State-of-the-art: Lipases, Esterases, Proteases in ILs as (co-)Solvents 1555.3 Use of ILs for (dynamic) Kinetic Resolutions ((D)KRs) 1835.4 Hydrolase-Catalyzed Esterifi cations of Saccharides and Cellulose Derivatives in ILs 2055.5 ILs for Glycosidases 2105.6 Prospects 2126 IONIC LIQUIDS AS (CO-)SOLVENTS FOR NONHYDROLYTIC ENZYMES 229Daniela Gamenara, Patricia Saenz Méndez, Gustavo Seoane, and Pablo Domínguez de María6.1 Ionic Liquids and Nonhydrolytic Enzymes 2316.2 Use of ILs in Oxidoreductase-Catalyzed Enzymatic Reactions 2326.3 ILs in Lyase-Catalyzed Reactions 2536.4 Prospects 2567 IONIC LIQUIDS AND WHOLE-CELL–CATALYZED PROCESSES 261Danielle Dennewald and Dirk Weuster-Botz7.1 Ionic Liquids Compatible with Whole-Cell Biocatalysis: Fundamentals and Design 2637.2 Biocompatibility, Tolerance, and Accumulation in the Cell 2727.3 State of the Art 2817.4 Prospects 3088 NONSOLVENT APPLICATIONS OF IONIC LIQUIDS IN BIOTRANSFORMATIONS 315Pablo Domínguez de María and Christina Kohlmann8.1 Introduction 3158.2 Ionic Liquids as Additives in Biotransformations 3168.3 Ionic Liquids for Coating Enzymes: The ILCE Concept 3188.4 Ionic Liquids Combined with Membranes and Biotransformations 3218.5 Ionic Liquids Anchoring Substrates 3218.6 Ionic Liquids and Bioelectrochemistry 324PART III IONIC LIQUIDS IN ORGANOCATALYSIS 3319 IONIC LIQUIDS AS (CO-)SOLVENTS AND CO-CATALYSTS FOR ORGANOCATALYTIC REACTIONS 333Štefan Toma and Radovan Šebesta9.1 Nontraditional Media in Organocatalysis 3339.2 Early Organocatalytic Reactions in Ionic Liquids 3349.3 Ionic Liquids as Solvents for Organocatalytic Reactions 3359.4 Ionic Liquids as Co-catalysts for Organocatalytic Reactions: Toward New Reactivities and Selectivities 3539.5 Key Factors in Choosing Ionic Liquids for Organocatalysis and Prospects 35510 "NONSOLVENT" APPLICATIONS OF IONIC LIQUIDS IN ORGANOCATALYSIS 361Michelangelo Gruttadauria, Francesco Giacalone, Paola Agrigento, and Renato Noto10.1 Introduction 36110.2 Immobilizing Ionic Liquids and Organocatalysts 36310.3 Anchoring of Organocatalyst to Ionic Liquids 37810.4 Ionic Liquids as Organocatalysts 40910.5 Conclusions 414References 414Index 419