Selective Catalysis for Renewable Feedstocks and Chemicals (Topics in Current Chemistry Book 353)

The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field. Preface 6 Contents 8 Top Chemical Opportunities from Carbohydrate Biomass: A Chemist ́s View of the Biorefinery 9 1 General Introduction to Biomass Conversion and Biorefineries 10 2 Introduction to Chemical Biomass Conversion Strategies 15 2.1 Chemical Conversion Routes to Biofuels 15 2.2 Chemical Conversion Routes to Bio-Derived Chemicals 16 3 A Chemist ́s View of the Selection of Viable Target Molecules and Their Formation in Cellulosic Biomass Conversion to Chemica... 18 3.1 Modification of van Krevelen Plots to Verify the Selection of Bio-Derived Chemicals 18 3.1.1 Introduction 18 3.1.2 The Original Van Krevelen Diagram 20 3.1.3 Introducing a New Parameter F, Describing the Molecular Functionality 22 3.1.4 The Functionality Index F:C 22 3.1.5 Modifying the Original Van Krevelen Plot: Functionality vs H-Index 27 3.1.6 Guidelines for the Selection of Carbohydrate-Derived Chemicals: Combining Functionality Index and Atom Economy 28 3.2 Justified Reaction Types for Cellulosic Biomass Conversion 32 3.2.1 Dehydration-Rehydration 32 3.2.2 Retro-Aldol Reaction 36 3.2.3 Partial Oxidation 37 3.2.4 Hydrogenation and Hydrogenolysis 38 3.2.5 Isomerization 38 3.3 Key Lessons of the Assessment 39 4 Summary, Conclusions, Outlook 40 References 41 Chemical-Catalytic Approaches to the Production of Furfurals and Levulinates from Biomass 49 1 Introduction 50 2 5-(Hydroxymethyl)furfural (HMF) 51 2.1 Synthesis: Introduction 51 2.2 Synthesis: Discussion 53 2.2.1 Feedstocks 53 2.2.2 Catalyst and Medium 54 2.3 Synthesis: Perspective 55 2.4 Derivatives 55 2.4.1 Simple Derivatization of the Hydroxymethyl or Aldehyde Group 56 2.4.2 Oxidation of the Hydroxymethyl and/or Aldehyde Group 57 2,5-Diformylfuran 57 Furancarboxylic Acids 57 2.4.3 Reduction Chemistry of HMF 58 2.4.4 Condensation Chemistry of HMF 59 2.4.5 Transformations Involving Cleavage of the Furan Ring 60 3 5-(Halomethyl)furfurals 61 3.1 Historical Efforts 61 3.2 Modern Synthetic Approaches 62 3.3 Derivatives of 5-(Halomethyl)furfurals 65 3.3.1 Conversion to HMF, Alkoxymethylfurfurals, LA, and Levulinic Esters 66 3.3.2 Substitution and Reduction Products 66 3.3.3 Condensation Chemistry of CMF 68 3.3.4 CMF Oxidation 68 3.3.5 Specialty Chemicals from CMF 69 XMFs as Key Starting Materials for Natural Product Synthesis 69 CMF as a Synthetic Intermediate in Pharmaceutical Lead Generation 70 Synthesis of delta-Aminolevulinic Acid from CMF 71 Synthesis of Ranitidine from CMF 71 Synthesis of Furan-Based Pyrethroids from CMF 72 4 Levulinic Acid 73 4.1 Introduction 73 4.2 Mechanism 74 4.3 Synthesis 74 4.4 Derivatives 76 4.4.1 Esters, Amides, Ketals, Alcohols, and Ethers 76 4.4.2 Transformation into Fuels 78 4.4.3 Miscellaneous Transformations Leading to Renewable Monomers, Solvents, and Specialty Chemicals 79 5 Conclusion and Future Prospects 80 References 81 Selective Catalysis for Cellulose Conversion to Lactic Acid and Other α-Hydroxy Acids 92 1 Introduction 93 2 Lactic Acid as a Platform Molecule 94 3 Lactic Acid as Key Monomer for Biodegradable Polyesters 99 4 Reaction Pathways and Catalytic Requirements 101 5 Catalytic Conversion of Mono- and Disaccharides into Lactates 105 5.1 Trioses to Lactic Acid and Its Esters 105 5.2 Hexose-Based Sugars: Sucrose, Glucose, Fructose 109 5.2.1 Reactions in Alcoholic Solvents 109 5.2.2 Reactions in Water 113 5.3 Other Carbohydrates, Pseudo-hemicellulose, and Glycolaldehyde 114 6 Direct Catalytic Conversion of Cellulose into Lactic Acid 115 7 Catalytic Synthesis of Other Biomass Derived α-Hydroxy Acids 118 7.1 C2: Glycolic Acid 118 7.2 C4: 4-Alkoxy-2-Hydroxybutanoates and Vinyl Glycolic Acid 119 7.3 C6: Furyl Glycolic Acid 121 8 Note on the Stereochemistry of Chemically Produced Lactates 122 9 Summary, Conclusions, Outlook 123 References 124 Selective Hydrogenolysis of C-O Bonds Using the Interaction of the Catalyst Surface and OH Groups 133 1 Introduction 134 1.1 Production of Biomass-Derived Chemicals 134 1.2 Conventional Hydrogenolysis of Glycerol and Tetrahydrofurfuryl Alcohol (THFA) 135 2 Hydrogenolysis of Glycerol and Tetrahydrofurfuryl Alcohol (THFA) Using Rh-MOx Catalysts 138 3 Structure of Rh-ReOx/SiO2 and Rh-MoOx/SiO2 Catalysts 141 4 Glycerol Hydrogenolysis to 1,3-Propanediol Over Ir-ReOx/SiO2 143 5 Substrate Scope of Ir-ReOx/SiO2 and the Reaction Kinetics in the Hydrogenolysis Reaction 146 6 Hydrogenolysis Reaction Mechanism Over Ir-ReOx/SiO2 148 7 Hydrogenolysis of Erythritol Using Ir-ReOx/SiO2 152 8 Relation Between the Hydrogenolysis Selectivity and Catalyst Structure of Rh-ReOx, Rh-MoOx, and Ir-ReOx 158 9 Complete C-O Hydrogenolysis of Sugars and Sugar Alcohols to Alkanes Using Ir-ReOx/SiO2 160 10 Conclusions and Outlook 164 References 165 Deoxydehydration of Polyols 169 1 Introduction 170 2 Uncatalyzed Didehydroxylation of Glycols 170 3 Oxo-Metal Promoted and Catalyzed Deoxydehydration 172 3.1 ReOx-Based Catalysts 172 3.1.1 Phosphine Reductants 172 3.1.2 H2 Reductant 176 3.1.3 Sulfite Reductant 177 3.1.4 Alcohol Reductants 180 3.1.5 Heterogeneous ReOx DODH Catalysts 186 3.2 Non-precious Metal Catalyzed DODH 186 4 Conclusions and Future Prospects 188 References 189 Polymerization of Nonfood Biomass-Derived Monomers to Sustainable Polymers 191 1 Introduction 193 2 Sustainable Polymers Based on Cellulose 195 2.1 Ethanol Platform 195 2.2 Lactic Acid Platform 196 2.2.1 Formation of Isotactic/Stereoblock PLA Materials from rac-LA 198 2.2.2 Formation of Sydiotactic PLA Materials from meso-LA 199 2.2.3 Formation of Heterotactic PLA Materials from rac-LA 200 2.3 Furfural and HMF Platform 201 2.4 Levulinic Acid Platform 206 2.4.1 Polymerizations of MBL, gammaMMBL, and betaMMBL by Rare Earth Metal Complexes 208 2.4.2 Polymerizations of MBL, gammaMMBL, and betaMMBL by Group 4 Metallocene Catalysts 210 2.4.3 Living Polymerization of MBL and gammaMMBL by Ambiphilic Silicon Propagators 212 2.4.4 Conjugate-Addition Organopolymerization by N-Heterocyclic Carbenes 214 2.4.5 Zwitterionic Polymerization by Classical and Frustrated Lewis Pairs 214 2.5 Sorbitol Platform 215 2.6 Dicarboxylic Acids Platform 220 3 Conclusions 223 References 224 Approaches to the Selective Catalytic Conversion of Lignin: A Grand Challenge for Biorefinery Development 234 1 Introduction 235 2 Catalytic Thermochemical Transformations of Lignin 239 2.1 Pyrolytic Transformations of Lignin 240 2.2 Lignin Hydrodeoxygenation 241 2.3 Lignin Hydrotreating (Hydrolysis) 243 3 Selective Catalytic Transformations of Lignin Models 245 3.1 Reductive beta-Aryl Ether Cleavage 245 3.2 Oxidative beta-Aryl Ether Cleavage 246 3.3 Oxidation of Lignin ́s Phenolic Functionality 249 4 More Highly Selective Lignin Transformations 251 4.1 Vanillin 251 4.2 Other More Highly Selective Conversions 252 5 Conclusions 254 References 255 Index 261 Front Matter....Pages i-vii Top Chemical Opportunities from Carbohydrate Biomass: A Chemist’s View of the Biorefinery....Pages 1-40 Chemical-Catalytic Approaches to the Production of Furfurals and Levulinates from Biomass....Pages 41-83 Selective Catalysis for Cellulose Conversion to Lactic Acid and Other α-Hydroxy Acids....Pages 85-125 Selective Hydrogenolysis of C–O Bonds Using the Interaction of the Catalyst Surface and OH Groups....Pages 127-162 Deoxydehydration of Polyols....Pages 163-184 Polymerization of Nonfood Biomass-Derived Monomers to Sustainable Polymers....Pages 185-227 Approaches to the Selective Catalytic Conversion of Lignin: A Grand Challenge for Biorefinery Development....Pages 229-255 Back Matter....Pages 257-261