New Strategies in Chemical Synthesis and Catalysis -- Contents -- Preface -- List of Contributors -- Part I Synthetic Methods -- 1 Electrospray and Cryospray Mass Spectrometry: From Serendipity to Designed Synthesis of Supramolecular Coordination and Polyoxometalate Clusters -- 1.1 Introduction -- 1.2 Background to ESI-MS -- 1.2.1 Background to CSI-MS -- 1.3 Application of High-Resolution ESI-MS and CSI-MS to Polyoxometalate Cluster Systems -- 1.3.1 Probing Protonation Versus Heteroatom Inclusion with ESI -- 1.3.2 Solution Identification of Functionalized POMs -- 1.3.3 Solution Identification of New Isopolyoxotungstates and Isopolyoxoniobates -- 1.3.4 Solution Identification and Isolation of Mixed-Metal/Valence POMs with CSI-MS -- 1.3.5 Mixed-Metal/Valence Hetero-POMs V2 {M17V1} -- 1.3.6 Periodate-Containing POMs -- 1.3.7 Probing the Formation of POM-Based Nano-Structures -- 1.3.8 Mechanistic Insights into POM Self-Assembly Using ESI- and CSI-MS -- 1.4 Species Identification and Probing Structural Transformations in Multi-Metallic Systems -- 1.5 Future Challenges and Conclusions -- References -- 2 Efficient Synthesis of Natural Products Aided by Automated Synthesizers and Microreactors -- 2.1 Efficient Synthesis of Natural Products Aided by Automated Synthesizers -- 2.1.1 The Process of Automating the Supply of Synthetic Intermediates -- 2.1.2 Efficient Synthesis of a Cyanohydrin Key Intermediate for Taxol Using Automated Synthesizers -- 2.1.3 Efficient Synthesis of a Cyclic Ether Key Intermediate for Nine-Membered Masked Enediyne, Using an Automated Synthesizer -- 2.1.4 List of Reactions Successfully Performed in Automated Synthesizers -- 2.2 Continuous-Flow Synthesis of Vitamin D3 -- 2.3 Conclusions -- Acknowledgments -- References -- 3 Chemoselective Reduction of Amides and Imides -- 3.1 Introduction -- 3.2 Reduction of Tertiary Amides.

3.3 Reduction of Secondary Amides -- 3.4 Dehydration of Primary Amides -- 3.5 Reduction of Imides -- 3.6 Conclusion -- Acknowledgment -- References -- 4 Ionic Ozonides - From Simple Inorganic Salts to Supramolecular Building Blocks -- 4.1 The Forgotten Oxygen Anion -- 4.2 The Synthesis of Ionic Ozonides -- 4.3 The Structural Variety of Ionic Ozonides -- 4.3.1 Simple Binary and Pseudo-Binary Ozonides -- 4.3.2 Cs5([12]crown-4)2(O3)5 - from Simple Salts to Supramolecular Building Blocks -- 4.4 Magnetic Properties -- 4.5 Conclusions and Perspectives -- References -- 5 Chemistry and Biological Properties of Amidinoureas: Strategies for the Synthesis of Original Bioactive Hit Compounds -- 5.1 Amidinoureas: an Introduction -- 5.2 Amidinoureas in Chemistry -- 5.3 Synthetic Strategies for the Preparation of Amidinoureas -- 5.3.1 Hydrolysis of Biguanides -- 5.3.2 Reaction of Guanidines with Isocyanates -- 5.3.3 Hydrolysis of Cyanoguanidines -- 5.3.4 Reaction of Acyl-S-Methylisothiourea with Amines -- 5.3.5 Reaction of Di-Boc-Guanidines with Amines -- 5.4 Macrocyclic Amidinoureas -- 5.4.1 Guanylated Polyamines -- 5.4.2 Conversion of Di-Boc-Guanylated Diamines into Amidinoureas -- 5.4.3 Synthesis of Cyclic Amidinoureas -- 5.4.4 Synthesis of Macrocyclic Amidinoureas from Di-Boc-Monoguanylated Triamines -- 5.4.5 Biological Properties of Cyclic Amidinoureas -- 5.5 Perspectives -- Acknowledgments -- References -- Part II Catalysis -- 6 DNA Catalysts for Synthetic Applications in Biomolecular Chemistry -- Abbreviations -- 6.1 Introduction -- 6.2 In vitro Selection of Deoxyribozymes -- 6.3 Scope of DNA-Catalyzed Reactions -- 6.4 Synthetic Applications of RNA-Cleaving Deoxyribozymes -- 6.5 DNA-Catalyzed Linear Ligation of RNA -- 6.6 DNA-Catalyzed Synthesis of 2_,5_-Branched Nucleic Acids -- 6.6.1 2',5'-Branched RNA.

6.6.2 2',5'-Branched Nucleic Acids Containing RNA as Scaffold and DNA as Adaptor -- 6.6.3 2',5'-Branched DNA -- 6.6.4 2',5'-Branched Nucleic Acids Containing DNA as Scaffold and RNA as "Adaptor" -- 6.7 DNA-Catalyzed Synthesis of Nucleopeptide Conjugates -- 6.8 Mechanistic Aspects of DNA Catalysis -- 6.9 Conclusions and Outlook -- References -- 7 Iron-Catalyzed Csp3 -H Oxidation with H2O2: Converting a Radical Reaction into a Selective and Efficient Synthetic Tool -- 7.1 Introduction and Scope -- 7.2 Environmentally Benign C-H Oxidation -- 7.3 Inspiration from Nature -- 7.4 Mechanistic Considerations -- 7.5 Bioinspired C-H Oxidation Catalysts -- 7.5.1 Porphyrinic Catalysts -- 7.5.2 Non-porphyrinic Mononuclear Iron Catalysts -- 7.6 Perspectives -- References -- 8 Hydrogen Bonds as an Alternative Activation -- 8.1 Introduction -- 8.1.1 Chiral Thiourea/Urea Organocatalysts -- 8.2 Thiourea Catalysts -- 8.2.1 Friedel-Crafts Alkylation Reaction -- 8.2.2 Michael Addition Reactions -- 8.2.2.1 Michael Addition Reaction of N,N-Dialkylhydrazones to Nitroalkenes -- 8.2.2.2 Michael Addition Reaction of Formaldehyde N,N-Dialkylhydrazones to ß, y-Unsaturated a-Keto Esters -- 8.2.2.3 Hydrophosphonylation Reaction of Nitroalkenes -- 8.2.3 Aza-Henry Reaction -- 8.3 Conclusions -- Acknowledgments -- References -- 9 Electrosynthesized Structured Catalysts for H2 Production -- 9.1 Introduction -- 9.2 Preparation of Structured Catalysts -- 9.3 Electrosynthesis -- 9.4 Electrosynthesis of Hydrotalcite-Type Compounds -- 9.4.1 Experimental -- 9.4.2 Ni/Al and Rh/Mg/Al HT Compounds on FeCrAlloy Foams -- 9.4.3 Catalysts -- 9.4.4 Steam Reforming and Catalytic Partial Oxidation of Methane -- 9.5 Summary and Outlook -- References -- 10 Microkinetic Analysis of Complex Chemical Processes at Surfaces -- Notation -- Greek letters -- 10.1 Introduction.

10.2 Time and Length Scales in Heterogeneous Catalysis -- 10.3 Hierarchical Multiscale Approach for Microkinetic Model Development -- 10.3.1 Microkinetic Model Development -- 10.3.1.1 Prediction of Activation Energies Using the UBI-QEP Semiempirical Method -- 10.3.1.2 First-Principles Assessment of the UBI-QEP Semiempirical Method -- 10.3.2 Meso-Scale and Macroscale: Reaction and Reactor Engineering -- 10.3.3 Hierarchical Multiscale Refinement of the Microkinetic Model -- 10.4 Show Case: Microkinetic Analysis of CH4 Partial Oxidation on Rh -- 10.4.1 Microkinetic Model for the Conversion of CH4 to Syngas -- 10.4.2 Microkinetic Analysis of Isothermal CPOX Data in Annular Reactor -- 10.4.3 Microkinetic Analysis of Autothermal CPOX Data on Foams -- 10.5 Conclusions -- Acknowledgments -- References -- 11 Synthetic Potential behind Gold-Catalyzed Redox Processes -- 11.1 Introduction -- 11.2 Gold-Catalyzed Reactions Involving Oxygen Functionalities -- 11.2.1 Oxidation of Alkanes -- 11.2.2 Oxidation of Alcohols to Carbonyl Compounds -- 11.2.3 Oxidation of Alkenes -- 11.2.4 Oxidation of Sulfides to Sulfoxides -- 11.2.5 Oxidation of Gold-Carbene Intermediates -- 11.2.6 Substrates as Internal Oxidants -- 11.3 Gold-Catalyzed Reactions Involving Nitrogen Functionalities -- 11.4 Gold-Catalyzed Reactions Involving C-C Bond Formation -- 11.4.1 Ethynylation Reactions -- 11.4.2 Homocoupling Reactions -- 11.4.3 Cross-Coupling Involving B and Si Reagents -- 11.5 Gold-Catalyzed Reactions Involving Alkene Difunctionalization -- 11.6 Gold-Catalyzed Reactions Involving Halogen Functionalities -- 11.7 Summary and Outlook -- References -- 12 Transition-Metal Complexes in Supported Liquid Phase and Supercritical Fluids -A Beneficial Combination for Selective Continuous-Flow Catalysis with Integrated Product Separation.

12.1 Strategies for Catalyst Immobilization Using Permanent Separation Barriers -- 12.2 Supported Liquid-Phase Catalysts Based on Organic Solvents (SLP) -- 12.3 Supported Aqueous-Phase Catalysts (SAP) -- 12.4 Supported Ionic Liquid-Phase Catalysts (SILP) -- 12.4.1 Synthetic Methods -- 12.4.2 Characteristics -- 12.4.3 Gas-Phase Applications -- 12.4.4 Liquid-Phase Applications -- 12.5 Supported Liquid-Phase Catalysts and Supercritical Fluids -- 12.6 Conclusion -- References -- Part III Combinatorial and Chemical Biology -- 13 Inhibiting Pathogenic Protein Aggregation: Combinatorial Chemistry in Combating Alpha-1 Antitrypsin Deficiency -- 13.1 Introduction -- 13.2 a1-Antitrypsin Deficiency -- 13.2.1 a1-Antitrypsin and Serpin -- 13.2.2 The Polymerization Pathways of Serpins -- 13.2.3 Emerging Therapeutic Strategies -- 13.3 Targeting the s4A Site with the Peptide Annealing Method -- 13.3.1 Functional and Structural Studies of RCLs -- 13.3.2 Smaller RCL-Derived and Non-RCL Serpin-Binding Peptides -- 13.4 Expanding the Molecular Diversity -- 13.4.1 Alanine Scanning, Truncation, and D-Amino Acid Scanning Libraries -- 13.4.2 The ß-Strand-Directed Library -- 13.4.3 The Positional Scanning Library -- 13.5 Characterization of the Combinatorially Selected Peptide -- 13.5.1 Validation of the Binding by SPR -- 13.5.2 Cytotoxicity of the Identified Peptide and the Proposed Structure of the Binary Complex -- 13.6 Conclusion and Outlook -- Acknowledgments -- References -- 14 Synthesis and Application of Macrocycles Using Dynamic Combinatorial Chemistry -- 14.1 Supramolecular Chemistry -- 14.2 Dynamic Combinatorial Chemistry -- 14.2.1 The Next Step: Applications -- 14.3 Ion Transport across Membranes Mediated by a Dynamic Combinatorial Library -- References -- 15 Toward Tomorrow's Drugs: the Synthesis of Compound Libraries by Solid-Phase Chemistry -- Abbreviations.

15.1 Introduction.