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

Author:: Perchyonok, V. Tamara
Published:: Cambridge : RSC Publishing, [2012]
Copyright Date:: ©2012
Physical Description:: xxiv, 779 pages : illustrations ; 24 cm
Additional Creators:: Lykakis, Ioannis, Postigo, Al., and Royal Society of Chemistry (Great Britain)

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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.The 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.The 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.An 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.The 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.The 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 -- 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 --, Contents note continued: 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 The 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.A 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.The 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.The "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.The 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.A 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 -- 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.The 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 --, and Contents note continued: 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.The "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.The "Transition State Analogue Selection" Approach -- 24.4.1.The 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.The "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.A Synthesis of Paeoniflorin -- 25.4.2.An 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.A Synthesis of Grayanotoxin III -- 25.5.2.A Synthesis and Structural Revision of (-)-Laurentristich-4-ol -- 25.5.3.An Approach to (-)-Welwitindolinone a Isonitrile -- 25.6.Six-membered Ring Formation Using SmI2: an Approach to Marine Polycyclic Ethers -- 25.6.1.A Synthesis of Pradimicinone -- 25.6.2.A Synthesis of (+)-Microcladallene B -- 25.6.3.A 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.A 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.A Synthesis of β-Araneosene -- 25.10.2.A 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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9781849733328
1849733325

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