Hypervalent Iodine Chemistry

Viktor V. Zhdankin was born in Ekaterinburg, Russian Federation. He obtained his BS/MS, 1978 Moscow State University, Ph.D., 1981, Moscow State University, Dr.Chem.Sci., 1987, Moscow State University and Senior Research Associate, 1990-1993, University of Utah.

• Preface ix 1 Introduction and General Overview of Polyvalent Iodine Compounds 11.1 Introduction 11.2 Classification and Nomenclature of Polyvalent Iodine Compounds 31.3 Hypervalent Bonding 41.4 General Structural Features 81.4.1 Experimental Structural Studies 91.4.2 Computational Studies 111.5 General Principles of Reactivity 121.5.1 Ligand Exchange and Reductive Elimination 131.5.2 Radical Reactions 141.5.3 Single-Electron Transfer (SET) Reactions 15References 152 Preparation, Structure, and Properties of Polyvalent Iodine Compounds 212.1 Iodine(III) Compounds 212.1.1 Inorganic Iodine(III) Derivatives 212.1.2 Organoiodine(III) Fluorides 232.1.3 Organoiodine(III) Chlorides 272.1.4 Organo-Iodosyl Compounds 312.1.5 Organoiodine(III) Carboxylates 352.1.6 [Hydroxy(Organosulfonyloxy)Iodo]Arenes 432.1.7 Organoiodine(III) Derivatives of Strong Acids 482.1.8 Iodine(III) Heterocycles 502.1.9 Iodonium Salts 762.1.10 Iodonium Ylides 992.1.11 Iodine(III) Species with Three Carbon Ligands 1072.1.12 Iodine(III) Species with I–N Bonds 1072.2 Iodine(V) Compounds 1142.2.1 Inorganic Iodine(V) Derivatives 1142.2.2 Noncyclic and Pseudocyclic Iodylarenes 1152.2.3 Iodine(V) Heterocycles 1202.2.4 Organoiodine(V) Fluorides 1262.3 Iodine(VII) Compounds 127References 1283 Hypervalent Iodine Reagents in Organic Synthesis 1453.1 Reactions of Iodine(III) Compounds 1453.1.1 Fluorinations 1463.1.2 Chlorinations 1523.1.3 Brominations 1583.1.4 Iodinations 1603.1.5 Oxidation of Alcohols 1643.1.6 Oxidative Functionalization of Carbonyl Compounds 1683.1.7 Oxidative Functionalization of Silyl Enol Ethers 1713.1.8 Oxidation of Alkenes and Alkynes 1733.1.9 Oxidations at the Benzylic or Allylic Position 1813.1.10 Oxidative Functionalization of Aromatic Compounds 1823.1.11 Oxidative Dearomatization of Phenols and Related Substrates 1833.1.12 Oxidative Coupling of Aromatic Substrates 1963.1.13 Oxidative Cationic Cyclizations, Rearrangements, and Fragmentations 2013.1.14 Oxidations at Nitrogen, Sulfur, and other Heteroatoms 2163.1.15 Azidations 2223.1.16 Aminations 2303.1.17 Thiocyanations and Arylselenations 2323.1.18 Radical Fragmentations, Rearrangements, and Cyclizations 2363.1.19 Reactions via Alkyliodine(III) Intermediates 2483.1.20 Transition Metal Catalyzed Oxidations 2503.1.21 Transition Metal Catalyzed Aziridinations and Amidations 2533.1.22 Reactions of Iodonium Salts and C-Substituted Benziodoxoles 2603.1.23 Reactions of Iodonium Ylides 2783.2 Synthetic Applications of Iodine(V) Compounds 2823.2.1 Noncyclic and Pseudocyclic Iodylarenes 2833.2.2 2-Iodoxybenzoic Acid (IBX) 2883.2.3 Dess–Martin Periodinane (DMP) 2963.2.4 Inorganic Iodine(V) Reagents 3023.3 Synthetic Applications of Iodine(VII) Compounds 303References 3074 Hypervalent Iodine Catalysis 3374.1 Catalytic Cycles Based on Iodine(III) Species 3374.1.1 Oxidative Functionalization of Carbonyl Compounds 3384.1.2 Oxidative Functionalization of Alkenes and Alkynes 3424.1.3 Oxidative Bromination of Aromatic Compounds 3464.1.4 Oxidative Amination of Aromatic Compounds 3474.1.5 Oxidation of Phenolic Substrates to Quinones and Quinols 3494.1.6 Oxidative Spirocyclization of Aromatic Substrates 3504.1.7 Carbon–Carbon Bond-Forming Reactions 3544.1.8 Hofmann Rearrangement of Carboxamides 3554.1.9 Oxidation of Anilines 3574.2 Catalytic Cycles Based on Iodine(V) Species 3584.3 Tandem Catalytic Systems Involving Hypervalent Iodine and other Co-catalysts 3644.4 Catalytic Cycles Involving Iodide Anion or Elemental Iodine as Pre-catalysts 368References 3775 Recyclable Hypervalent Iodine Reagents 3815.1 Polymer-Supported Iodine(III) Reagents 3815.2 Polymer-Supported Iodine(V) Reagents 3895.3 Recyclable Nonpolymeric Hypervalent Iodine(III) Reagents 3915.3.1 Recyclable Iodine(III) Reagents with Insoluble Reduced Form 3935.3.2 Recovery of the Reduced Form of a Hypervalent Iodine Reagent Using Ion-Exchange Resins 3975.3.3 Ionic-Liquid-Supported Recyclable Hypervalent Iodine(III) Reagents 4005.3.4 Magnetic Nanoparticle-Supported Recyclable Hypervalent Iodine(III) Reagent 4015.3.5 Fluorous Recyclable Hypervalent Iodine(III) Reagents 4025.4 Recyclable Nonpolymeric Hypervalent Iodine(V) Reagents 4055.5 Recyclable Iodine Catalytic Systems 406References 4096 Reactions of Hypervalent Iodine Reagents in Green Solvents and under Solvent-Free Conditions 4136.1 Reactions of Hypervalent Iodine Reagents in Water 4136.2 Reactions of Hypervalent Iodine Reagents in Recyclable Organic Solvents 4186.3 Reactions of Hypervalent Iodine Reagents under Solvent-Free Conditions 420References 4227 Practical Applications of Polyvalent Iodine Compounds 4257.1 Applications of Inorganic Polyvalent Iodine Derivatives 4257.2 Applications of Hypervalent Iodine(III) Compounds as Polymerization Initiators 4267.3 Application of Iodonium Salts for Fluoridation in Positron Emission Tomography (PET) 4317.4 Biological Activity of Polyvalent Iodine Compounds 440References 443Index