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    Streamlining free radical green chemistry / V. Tamara Perchyonok, Ioannis Lykakis, Al Postigo.

    • Title:Streamlining free radical green chemistry / V. Tamara Perchyonok, Ioannis Lykakis, Al Postigo.
    •    
    • Author/Creator:Perchyonok, V. Tamara.
    • Other Contributors/Collections:Lykakis, Ioannis.
      Postigo, Al.
      Royal Society of Chemistry (Great Britain)
    • Published/Created:Cambridge : RSC Publishing, ©2012.
    • Holdings

       
    • Library of Congress Subjects:Free radicals (Chemistry)
      Free radical reactions.
      Free radicals (Chemistry)--Industrial applications.
    • Description:xxiv, 779 p. : ill. ; 24 cm.
    • Notes:Includes bibliographical references and index.
    • ISBN:9781849733328
      1849733325
    • Contents:Machine generated contents note: ch. 1 Development of Free Radical Green Chemistry and Technology: Journey through Times, Solvents, Causes, Effects and Assessments
      1.1. Introduction
      1.2. Major Use of Free Radical Green Chemistry from the Beginning
      1.3. Alternative Feedstocks
      1.3.1. Innocuous or More Innocuous
      1.3.2. Renewable
      1.3.3. Light
      1.3.4. Solve Other Environmental Problems
      1.3.5. Biocatalysis
      1.4. Benign Reagents/Synthetic Pathways
      1.4.1. Innocuous or More Innocuous
      1.4.2. Generates Less Waste
      1.4.3. Selective
      1.4.4. Catalytic
      1.5. Biomass: Utilization and Sustainability
      1.6. Green Chemical Syntheses and Processes
      1.7. Basic Radical Chemistry: Structure, Reactions and Rates
      1.7.1. General Aspects of Synthesis with Radicals: Advantages and Traditions
      1.7.2. Reactions Between Radicals
      1.7.3. Reaction Between a Radical and a Non-radical
      1.7.4. Reactivity and Selectivity
      1.7.5. Enthalpy: In Brief
      1.7.6. Entropy
      1.7.7. Steric Effects
      1.7.8. Stereoelectronic Effects
      1.7.9. Polarity
      1.8. Solvent Effect and Free Radical Transformations: General Understanding
      1.9. Why Water as a Solvent? Reasons and Advantages
      1.9.1. Solubility of Organic Compounds in Water
      1.9.2. Organic Cosolvents
      1.9.3. Ionic Derivatization (pH Control)
      1.9.4. Surfactants
      1.9.5. Hydrophilic Auxiliaries
      1.9.6. Summary
      1.10. Classical Synthesis in Modern Solvents
      1.10.1. Perfluorinated Solvents
      -a Novel Reaction Medium in Organic Chemistry: General Introduction
      1.10.2. Benzotrifluoride and Derivatives: Useful Solvents for Organic Synthesis and Fluorous Synthesis
      1.10.3. Reactions in Supercritical Carbon Dioxide (scCO2) as a Novel Reaction Medium
      1.10.4. Solvent-free Reactions as an Alternative: General Interest for Solvent-free Processes
      1.11. Methods of Generating Free Radicals
      1.11.1. Thermal Cracking
      1.11.2. Homolysis of Peroxides and Azo Compounds
      1.11.3. Photolytic Bond Homolysis
      1.11.4. Electron Transfer
      1.11.5. Hydrogen and Halogen Atom Abstraction
      1.11.6. Configuration of Free Radicals
      1.11.7. Elementary Reaction Steps between Radicals and Non-radicals: Reactions of Free Radicals
      1.12. Sustainable "hemistry Metrics and Radical Chemistry: Comparative Approach
      1.12.1. Classical Metrics of Chemical Reactions
      1.12.2. How do Contemporary Free Radical Transformations Hold Up? Focus on Sustainability, Atom Efficiency and Advantages
      1.13. Classics and Catalysis in Free Radical Chemistry: Reagents, Reactants and Protocols
      1.14. Radical cascades and Free Radical Green Chemistry
      1.15. Artificial Enzymes in Free Radical Synthetic Chemistry: the Chemist's Perspective
      1.16. Future Challenges and Opportunities for the Chemical Profession and the Science of Chemistry
      1.17. Environmentally Friendly Economy from Green Chemistry
      1.17.1. Renewable Energy Sources
      1.17.2. Renewable Feedstocks
      1.17.3. Pollution Reduction
      1.17.4. Interdisciplinary Approach
      1.18. Conclusion and Future Direction
      References
      ch. 2 Classical Synthetic Free Radical Transformations in Alternative Media: Supercritical CO2, Ionic Liquids and Fluorous Media
      2.1. Introduction
      2.2. Radicals in Synthetic Chemistry in the Nutshell
      2.3. Reactions between Radicals
      2.4. Elementary Reaction Steps between Radicals and Non-radicals
      2.4.1. Additions
      2.4.2. Substitution (Abstraction) Reactions
      2.4.3. Elimination Reactions
      2.4.4. Rearrangement Reactions
      2.4.5. Termination/Electron Transfer Reactions
      2.5. Reactivity and Selectivity
      2.6. Chain vs. Non-chain Free Radical Processes: Reasons, Relevance and Outlook
      2.7. Radical Reactions in Supercritical Fluids
      2.7.1. Radical Reactions and Supercritical CO2: Is There a Hidden Advantage?
      2.7.2. Radical Reactions in Supercritical Carbon Dioxide in Detail
      2.7.3. Future Directions
      2.8. Radical Reactions in Ionic Liquids
      2.8.1. Ionic Liquids and Alternative Media: General Introduction
      2.8.2. Radical Chain Reactions in Ionic Liquids: Triethylborane-induced Radical Reactions
      2.8.3. Radical Additions of Thiols to Alkenes and Alkynes in Ionic Liquids
      2.9. Radical Non-Chain Reactions in Ionic Liquids
      2.9.1. Formation of Radicals by Oxidation with Transition Metal Salts: General Perspective
      2.9.2. Oxidations involving Mn(III) in Ionic Liquids
      2.9.3. Supported Ionic Liquids: Versatile Reaction and Separation Media
      -the Latest Developments
      2.9.4. Conclusions and Future Directions
      2.10. Fluorous Chemistry as an Alternative Reaction Medium for Free Radical Transformations
      2.10.1. Fluorous Separation Techniques: from "Liquid-Liquid" to "Solid-Liquid" and "Light Fluorous"
      2.10.2. Fluorous Chemistry and Radicals
      -Combined Efforts to the Rescue
      2.10.3. Fluorous Radical Carbonylation Reactions: from Synthetic Approach to Practical Applications
      2.11. Ishii Oxidation in Detail
      2.12. From Phase-separation to Phase-vanishing Methods based on Fluorous-phase Screen: a Simple Way for the Efficient Execution of Organic Synthesis
      2.13. Conclusions and Future Directions in Fluorous Chemistry
      2.14. General Conclusion
      References
      ch. 3 Solvent-Free Carbon-Carbon Bond Formations in Ball Mills and in the Solid State
      3.1. Introduction
      3.2. Radical Additions to Imines Mediated by Mn(III)
      3.3. Solid-phase Homolytic Substitution in Action
      3.4. Future Directions
      References
      ch. 4 Microwaves in Synthesis: How do Microwaves Promote the Reaction in Conventional and Alternative Media?
      4.1. Introduction
      4.2. Microwave-assisted Fluorous Synthesis
      4.3. Nitroxide-mediated Radical Cyclization and Intramolecular Addition Reactions in Microwaves
      4.3.1. Persistent Radical Effect: General Introduction
      4.4. Radical Addition to C=N bonds in the Microwave
      4.5. Microwave-assisted Generation of Alkoxyl Radicals and their Use in Additions, β-Fragmentations and Remote Functionalization
      4.6. Atom-transfer Reactions as Efficient and Novel Benzannulation Reactions in the Microwave
      4.7. Conclusions and Future Directions
      References
      ch. 5 Asymmetric Free-Radical Reductions Mediated by Chiral Stannanes, Germanes, and Silanes
      5.1. Introduction
      5.2. Stoichiometric Free Radical Reductions
      5.3. Scope and Limitations
      5.4. Examples Relevant to the Fine Chemical Industry
      5.5. Strategies for the Avoidance of Tin Waste
      5.6. Immobilization of Tin Reagents
      5.7. Catalytic Reductions in Tin
      5.8. Reducing Agents based on Germanium and Silicon
      5.9. Summary
      References
      ch. 6 Organic Radical Reductions in Water: Water as a Hydrogen Atom Source
      6.1. Introduction
      6.2. Water-soluble Organosilanes and Synthesis
      6.3. Tris(trimethylsilyl)silane in Water and "on Water"
      6.4. Triethylborane-Water Complex as a Reducing Agent
      6.5. Titanium(III)-Water as a Reducing Agent
      6.6. Summary
      References
      ch. 7 Tin-Free Radical Reactions Mediated by Organoboron Compounds
      7.1. Introduction
      7.2. Organoboranes as Radical Initiators
      7.3. In Reductive Processes
      7.3.1. Reduction of Halides and Related Compounds
      7.3.2. Reductive Addition of Heteroatom-centered Radicals to Alkynes and Alkenes
      7.3.3. In Fragmentation Processes
      7.4. In Atom-transfer Processes
      7.4.1. Iodine Atom Transfer
      7.4.2. Bromine Atom Transfer
      7.4.3. Chlorine Atom Transfer
      7.5. Organoboron Compounds as a Source of Carbon-centered Radicals
      7.5.1. Conjugated Additions to Enones and Enals
      7.5.2. Conjugate Addition to Activated Olefins
      7.5.3. Addition to Imine Derivatives
      7.5.4. C-C Bond Formation via β-Fragmentation Processes
      7.6. Organoboranes as Chain-transfer Reagents
      7.6.1. Via Iodine Atom Transfer
      7.6.2. Via Hydrogen Atom Transfer
      7.7. Organoboron Compounds as Radical-reducing Agents
      7.7.1. Complexes with Tertiary Amines
      7.7.2. Complexes with Water and Alcohols
      7.8. Conclusions
      References
      ch. 8 Thiols as Efficient Hydrogen Atom Donors in Free Radical Transformations in Aqueous Media
      8.1. Introduction
      8.2. Tris(trimethylsilyl)silane (TMS3SiH)/thiol System is an Efficient Radical Hydrogen Donor "on Water"
      8.3. Thiol/Azo Initiator System in cis-trans Isomerization of Double Bonds in Aqueous Media
      8.4. Thiols in Peptides: Degradation in Aqueous Media
      8.5. Thiols in C-C Bond Formation in Water
      8.6. Thiol-Ene Coupling as a Click Process for Materials and Bioorganic Chemistry
      8.7. Hydrogen Sulfide in Oxidation and/or Reduction of Organic Compounds
      8.8. Thiyl Radicals and the Influence of Antioxidants/Vitamins
      8.9. Conclusions
      References
      ch. 9 Advances in the Use of Phosphorus-centered Radicals in Organic Synthesis in Conventional Flasks: Advantages, Reasons and Applications
      9.1. Introduction
      9.2. Physical Organic Aspects
      9.3. Use of P-centered Radicals as Mediators
      9.4. Synthetic Applications of P-centered Radical Additions
      9.4.1. Phosphinyl Radicals
      9.4.2. Phosphonyl Radicals
      9.5. Radicals from Hypophosphites and Phosphinates
      9.6. Phosphinoyl Radicals
      9.6.1. Thiophosphonyl and Other Sulfurcontaining Radicals
      9.7. Elimination of Organophosphorus Radicals
      9.7.1. Phosphoranyl Radicals
      9.7.2. β-Elimination of P-centered Radicals
      9.8. Conclusion and Perspectives
      References
      Contents note continued: ch. 10 Metal-based Homogeneous Catalysis and Free Radical Synthesis: Advantages, Developments and Scope
      10.1. Introduction
      10.2. Metal-mediated Reduction and Oxidation Reactions in Water
      10.3. Metal-radical-mediated Carbon-Carbon Bond Formation Reactions in Water
      10.3.1. Metal-mediated Radical Cyclizations in Water
      10.3.2. Reformatzky Reactions in Water
      10.3.3. Alkylation of Carbonyl Compounds, Imine Derivatives and Electron-deficient Alkenes in Water
      10.3.4. Allylation of Carbonyl Compounds and Imine-derivatives in Water
      10.3.5. Radical Conjugate Additions to α,β-Unsaturated Carbonyl Compounds in Water
      10.3.6. Synthesis of α,β-Unsaturated Ketones
      10.3.7. Metal-mediated Mannich-type Reactions in Water
      10.3.8. Pinacol and Other Coupling Reactions in Water
      10.4. Conclusion and Future Direction
      Acknowledgments
      References
      ch. 11 Radicals and Transition-metal Catalysis: a Complementary Solution to Increase Reactivity and Selectivity in Organic Chemistry
      11.1. Introduction
      11.2. Radical Cyclizations Terminated by Ir-catalyzed Hydrogen-atom Transfer
      11.3. Conclusion
      References
      ch. 12 Reagent Control in Transition-metal-initiated Radical Reactions
      12.1. Introduction
      12.2. Reagent Control in Transition-metal-initiated Radical Reactions
      12.3. Carbonyl Compounds as Radical Sources: Pinacol Couplings
      12.3.1. Stoichiometric Reagent-controlled Couplings
      12.3.2. From Stoichiometric to Catalytic Pinacol Couplings
      12.4. Protonation of Metal-Oxygen Bonds in Catalytic Radical Reactions
      12.5. Carbonyl Compounds as Radical Precursors: Additions of Ketyl Radicals to C-C and C-X Bonds
      12.6. Epoxides as Radical Precursors
      12.6.1. Stoichiometric Reagents
      12.6.2. Titanocene-catalyzed Epoxide Openings
      12.6.3. Catalytic Enantioselective Epoxide Openings
      12.7. Conclusion and Future Direction
      References
      ch. 13 Enantioselective Radical Reactions and Organocatalysis
      13.1. Introduction
      13.2. Organic Reagents and Organocatalysts in Stereoselective Radical Chemistry
      13.2.1. Chiral Lewis Acid Activation
      13.3. Enantioselective Hydrogen Atom Transfer
      13.4. Aminocatalysis/Enamine Activation
      13.5. Future Directions for Organocatalysis in Radical Chemistry
      13.6. Conclusion
      References
      ch. 14 Sunny Side of Chemistry: Green Synthesis by Solar Light
      14.1. Introduction
      14.2. Historical Background
      14.3. Synthesis using Non-concentrated Sunlight
      14.4. Photocatalytic/Photomediated Processes
      14.5. Photodimerization
      14.6. Cycloadditions
      14.7. Cyclizations
      14.8. Photopinacolization (Photoreduction)
      14.9. Synthesis via Elimination of a Group
      14.10. Arylation Reactions
      14.11. Isomerizations
      14.12. Halogenations
      14.13. Synthesis of Endoperoxides
      14.14. Oxidations/Oxygenations
      14.15. Concentrated Sunlight
      14.15.1. General Remarks
      14.15.2. Photooxidations and Photooxygenations
      14.15.3. Cycloadditions
      14.16. Photocatalytic Reactions
      14.17. Photoacylations
      14.18. EIZ Isomerizations
      14.19. Potential Industrial Applications
      14.20. Conclusion and Future Direction
      References
      ch. 15 Sonochemistry: Ultrasound Application in Radical Synthesis
      15.1. Introduction
      15.2. Energy Efficiency
      15.3. Sonochemical Initiation of Radical Chain Reactions: Hydrostannation and Hydroxystannation of C-C Multiple Bonds
      15.4. Homogeneous Sonochemistry of Hydrostannation in Detail
      15.5. Sonication-induced Halogenative Decarboxylation of Thiohydroxamic Esters
      15.6. Aerobic Conversion of Organic Halides to Alcohols: an Oxygenative Radical Cyclization
      15.7. New Method for Nitration of Alkenes to α,β-Unsaturated Nitroalkenes
      15.8. Conclusion and Future Direction
      References
      ch. 16 Black-light-initiated Free Radical Reactions for Synthetic Applications, Micro-reactors and Modified Nucleoside Synthesis
      16.1. Introduction: Why Black Light is so Important
      16.2. C2',3'-Cyclic Carbonates Derived from Nucleosides Why They are Important
      16.3. C5' General Comments and History
      16.4. Black-light induced Radical Cyclization Approach to Cyclonucleosides: an Independent Approach
      16.5. Radical Cyclization "Tin-free" Approach to C2',C3'-Cyclic Carbonates Derived from Nucleosides: an Independent Approach
      16.6. Black-light-induced Direct Generation of C2'-Nucleosidyl Radicals in Adenosine, Thymidine and Uridine in Organic and Aqueous Media
      16.7. Black-light-induced Radical/Ionic Hydroxymethylation of Alkyl Iodides with Atmospheric CO in the Presence of Tetrabutylammonium Borohydride
      16.8. Towards the Synthesis of Alkyl Alkynyl Ketones by Pd/Light-induced Three-component Coupling Reactions of Iodoalkanes, CO, and 1-Alkynes
      16.9. Vicinal C-Functionalization of Alkenes: Pd/Light-induced Multicomponent Coupling Reactions Leading to Functionalized Esters and Lactones
      16.10. Closing the Gap: from Single Molecule Synthesis the Conventional Way to Microreactors
      -the Power of Black Light
      16.11. Synthesis in Microchemical Systems
      16.12. Microflow Photo-radical Chlorination of Cycloalkanes
      16.13. Continuous Microflow Chlorination of Cyclohexane with Molecular Chlorine in Detail
      16.14. Microflow Chlorination with Sulfuryl Chloride and Black Light
      16.15. Barton Reaction Using a Microreactor and Black Light: Continuous-flow Synthesis of a Key Steroid Intermediate for an Endothelin Receptor Antagonist
      16.16. Conclusion
      References
      ch. 17 Photo-catalysis and Metal-Oxygen-anion Cluster Decatungstate in Organic Chemistry: a Manifold Concept for Green Chemistry
      17.1. Introduction
      17.2. C-C Bond Formation via C-H Bond Fragmentation under Anaerobic Conditions
      17.2.1. Functionalization of Alkanes by Homolytic C-H Bond Cleavage
      17.2.2. Functionalization of Aldehydes by Homolytic C-H Bond Cleavage
      17.2.3. Functionalization of Amides by Homolytic C-H Bond Cleavage
      17.2.4. Functionalization of Toluenes, Anisoles and Thioanisole by Homolytic C-H Bond Cleavage
      17.3. Homogeneous Oxidation of Organic Compounds by Decatungstate
      17.3.1. Oxidation of Aliphatic Alcohols and Alkanes
      17.3.2. Oxidation of Aromatic Alcohols and Alkanes
      17.3.3. Oxidation of Aliphatic and Aromatic Alkenes
      17.4. Heterogeneous Oxidation of Organic Compounds by Decatungstate
      17.4.1. Immobilization on a Solid Support
      17.4.2. Immobilization inside the Silica or Zirconia Network
      17.4.3. Immobilization on Silica containing Ammonium Cations
      17.4.4. Immobilization onto Organic Ion-exchange Resins
      17.4.5. Immobilization with Organic Sensitizers
      17.4.6. Immobilization in Polymeric Membranes
      17.5. Degradation of Organic Pollutants by Decatungstate
      17.6. Conclusion and Future Directions
      References
      ch. 18 Radical Domino Reactions: Intermolecular Telescopic Reactions
      18.1. Introduction: Advantages and Limits
      18.2. Radical/Radical Domino Processes in Synthesis
      18.3. Conclusion and Future Direction
      References
      ch. 19 Telescopic Reactions and Free Radical Synthesis: Focus on Radical and Radical-Ionic Multicomponent Processes
      19.1. General Introduction: Advantages and Limitations
      19.2. Mnemonic Classification
      19.3. Three-component Radical Reactions
      19.3.1. 3-CR-ADA
      19.3.2. 3-CR-DAD
      19.3.3. 3-CR-DAA
      19.3.4. 3-CR-DDA
      19.4. Four- and Five-Component Radical Reactions
      19.4.1. 4-CR-DAAD
      19.4.2. 4-CR-ADAA
      19.4.3. 4-CR-AADA
      19.5. Multicomponent Radical-Ionic Reactions
      19.5.1. Multicomponent Radical-Anionic Reactions
      19.5.2. Multicomponent Radical-Cationic Reactions
      19.5.3. Sequential Multicomponent Radical-Polar Crossover Reactions
      19.6. Conclusion and Future Direction
      References
      ch. 20 Radical-Radical-Radical Telescopic Reactions: from Rules through Reasons to Applications
      20.1. Introduction
      20.2. "Round Trip" Strategy in Action
      20.3. Conclusion and Future Direction
      References
      ch. 21 Applications of Conventional Free Radicals and Advances in Total Synthesis: from the Bench to the Future through the Vinyl Radical
      21.1. Vinyl Radical, a Precious Tool for Radical Cascades in 5-exo-dig Cyclizations
      21.2. Linear Triquinanes from Acyclic Precursors
      21.3. First Total Synthesis of Natural Protoilludane, epi-Illudol
      21.4. Asymmetric Intramolecular Radical Vinylation using Enantiopure Sulfoxides as Temporary Chiral Auxiliaries
      21.5. Conclusion and Summary
      References
      ch. 22 Streamlining Organic Free Radical Synthesis through Modern Molecular Technology: from Polymer-supported Synthesis to Microreactors and Beyond
      22.1. Free Radicals: a Brief Introduction and Why they are Important
      22.2. Polymer-supported Reagents and Free Radical Synthesis: a Few Initial Remarks and Approaches
      22.2.1. PEG-bound Reagents and Free Radical Transformations to Date: the Journey Has Begun
      22.2.2. Solid-state Radical Reactions
      22.3. Ultraporous Materials as Possible Microreactors and Free Radical Synthesis
      22.3.1. Few Words About Polarity Reversal Catalysis and its Advantages in Free Radical Transformations in PolyHIPEs
      22.4. Microreactor-controlled Selectivity in Organic Photochemical Reactions: Molecular Sieve Zeolites to the Rescue
      22.4.1. Photochemistry of Phenyl Phenylacetates Included Within Zeolites and Nafion Membranes
      Contents note continued: 22.4.2. Zeolites and LDPE Films as Hosts for the Preparation of Large Ring Compounds: Intramolecular Photocycloaddition of Diaryl Compounds
      22.4.3. Summary
      22.5. Microflow Systems for Practical Free Radical Synthesis and Polymerization
      22.6. Free Radical Polymerization in Microreactors: New Advantages and Extra Control
      22.7. Conclusion
      References
      ch. 23 Radical Reactions and β-Cyclodextrin as a Molecular Ferrari: Is There a Hidden Advantage of Speed, Power and Class? From Fundamental Reactions to Potential Applications
      23.1. Introduction
      23.2. Cyclodextrin Reaction Media
      23.3. β-Cyclodextrin-based Molecular Reactors for Free Radical Chemistry in Aqueous Media and Chain Reactions
      23.4. On the Use of β-Cyclodextrins as Molecular Reactors for the Radical Cyclizations under Tin-free Conditions: Chain and Non-chain Reactions
      23.5. Radical Cyclizations in β-Cyclodextrins in Aqueous Media under Photolytic Conditions
      23.6. Mn(OAc)3 Radical Cyclizations in β-Cyclodextrin
      23.7. Cu(OAc)2 Radical Cyclizations in β-Cyclodextrins
      23.8. On the Scope of β-Cyclodextrin-Ionic Liquid-based Molecular Reactors for Free Radical Chemistry in Bio-compatible and Alternative Media
      23.9. β-Cyclodextrin-Ionic Liquids and Conventional Free Radical Reactions: Hydrogen Atom Transfer Reactions
      23.10. β-Cyclodextrin-Ionic Liquid (MIM-β-CDOTs) and Conventional Free Radical Reactions: Radical Additions, Atom Transfer, Hydrosilylation and Hydrostannylation Reactions in Aqueous Media
      23.11. Potential Practical Application: Towards the Development of Novel Drug Delivery Prototype Devices for Targeted-Delivery Drug Therapy at the Molecular Level in Aqueous Media
      23.11.1. Path a in Detail: β-Cyclodextrin-Prodrug as an Efficient Prototype Molecular Carrier in Water Aimed at Transporting Radical-affording Species (RAS) in Aqueous Media
      23.11.2. Path B in Detail: Investigation of Free Radical-quenching Species (RQS) from a β-Cyclodextrin-Phenol "Molecular Antioxidant Prototype" in Water as Antioxidant Delivery to the Radical Reaction Mixture
      23.12. Towards Streamlining Conventional Radical Reactions through the Development of β-Cyclodextrin-based Batch, Flow-through and "Teabag" Prototype Molecular Reactors
      23.12.1. β-Cyclodextrins as Molecular Batch Reactors
      23.12.2. β-Cyclodextrin Molecular Flow-through Reactor for Streamlining Organic Synthesis in a Continuous and Reusable Fashion
      23.12.3. "Teabag" Methodology and Radical Reactions: Screening the Scope and Flexibility
      23.13. Conclusion and Future Direction
      References
      ch. 24 Artificial Enzymes and Free Radicals: the Chemist's Perspective
      24.1. Introduction
      24.2. Transition State Theory: a Brief Introduction
      24.3. "Design Approach"
      24.3.1. Cyclodextrins as Enzyme Mimics
      24.3.2. Vitamin B12 Functions: Enzymatic Reactions
      24.3.3. Model Reactions with Apoenzyme Functions
      24.4. "Transition State Analogue Selection" Approach
      24.4.1. Transition State Analogue Selection Approach: General Introduction
      24.4.2. Molecular-imprinted Polymers as a Method in the Transition State Analogue Selection Approach
      24.4.3. Imprinting an Artificial Proteinase
      24.4.4. Bioimprinting
      24.5. "Catalytic Activity Selection Approach": General Introduction
      24.5.1. Combinatorial Polymers as Enzyme Mimics
      24.5.2. Directed Evolution of Enzymes
      24.5.3. Catalysis with Imprinted Silicas and Zeolites
      24.5.4. Catalytic Antibodies and a Few Examples of Radical Transformations
      24.6. Conclusion
      References
      ch. 25 Applications of Conventional Free Radicals and Advances in Total Synthesis: from the Bench to Nature through SmI2 Radicals as an Efficient Trigger for Radical Cascades, a Journey from Orsay to the 21st Century
      25.1. Mechanisms of SmI2-mediated Reactions: the Basics
      25.2. Radicals and Anions from Organohalides
      25.3. SmI2-mediated Cyclizations in Natural Product Synthesis
      25.4. Four-membered Ring Formation Using SmI2
      25.4.1. Synthesis of Paeoniflorin
      25.4.2. Approach to the Pestalotiopsin and Taedolidol Skeletons
      25.5. Five-membered Ring Formation Using SmI2: the Synthesis of (-)-Hypnophilin and the Formal Synthesis of (-)-Coriolin
      25.5.1. Synthesis of Grayanotoxin III
      25.5.2. Synthesis and Structural Revision of (-)-Laurentristich-4-ol
      25.5.3. Approach to (-)-Welwitindolinone a Isonitrile
      25.6. Six-membered Ring Formation Using SmI2: an Approach to Marine Polycyclic Ethers
      25.6.1. Synthesis of Pradimicinone
      25.6.2. Synthesis of (+)-Microcladallene B
      25.6.3. Synthesis of Botcinins C, D and F
      25.7. Seven-membered Ring Formation Using SmI2: Syntheses of (-)-Balanol
      25.8. Eight-membered Ring Formation Using SmI2: A Synthesis of Paclitaxel (Taxol)
      25.8.1. Synthesis of (+)-Isoschizandrin
      25.9. Nine-membered Ring Formation Using SmI2: An Approach to Ciguatoxin
      25.10. Forming Larger Rings Using SmI2: A Synthesis of Diazonamide A
      25.10.1. Synthesis of β-Araneosene
      25.10.2. Synthesis of Kendomycin
      25.11. Modifying Biomolecules Using SmI2
      25.11.1. Introduction
      25.11.2. Modifying Carbohydrates Using SmI2
      25.11.3. Modifying Amino Acids and Peptides Using SmI2
      25.12. Summary
      References
      ch. 26 Innovative Reactions Mediated by Zirconocene: Advantages and Scope
      26.1. Background of Zirconium in Organic Synthesis
      26.2. Triethylborane-induced Radical Reaction with Schwartz Reagent
      26.3. Radical Cyclization Reactions with a Zirconocene(alkene) Complex as an Efficient Single Electron Transfer Agent
      26.4. Triethylborane-induced Radical Allylation Reaction with a Zirconocene(alkene) Complex
      26.5. Conclusion
      References
      ch. 27 Applications of Conventional Free Radicals and Advances in Total Synthesis: Radical Cascades in Bio-inspired Terpene Synthesis
      27.1. Introduction
      27.2. Antecedents
      27.3. Recent Developments
      27.3.1. Acyclic Terpenes
      27.3.2. Radical Polyprene Cyclizations
      27.3.3. Photo-induced Electron Transfer (PET) Reactions as Initiation
      27.3.4. Acylselenium Derivatives as Substrates
      27.4. Transition-metal-mediated Transformations
      27.4.1. Manganese(III)-mediated Cyclizations
      27.4.2. Ti(III)-mediated Epoxypolyprene Cyclizations
      27.5. SOMO Organocatalysis and Terpenes
      27.6. Conclusions.
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