Sulfur-Centered Reactive Intermediates in Chemistry and Biology

Front Matter....Pages i-xi
Force-Field and Molecular Orbital Calculations in Organosulfur Chemistry....Pages 1-6
Electronic Transitions in Sulfur-Centered Radicals by Means of MSXα Calculations....Pages 7-12
The Electronic Properties of Sulfur-Containing Substituents and Molecules: An ab initio Study....Pages 13-18
Reactivity of Sulfur-Centered Nucleophiles Towards Dia- and Paramagnetic Reagents. The Frontier Orbitals Approach....Pages 19-30
Alkanethiylperoxyl Radicals....Pages 31-36
Thermochemistry of Sulfur-Centered Intermediates....Pages 37-52
Experimental Procedures in Electrolysis....Pages 53-67
Single Electron Transfer in Aliphatic Nucleophilic Substitution....Pages 69-82
Electrochemistry as a Tool for the Study of Reactive Intermediates....Pages 83-92
Electrochemical Reduction of Some Sulfur Compounds....Pages 93-102
Photocatalytic Formation of Sulfur-Centered Radicals by One-Electron Redox Processes on Semiconductor Surfaces....Pages 103-120
Applications of Pulse Radiolysis for the Study of Short-Lived Sulphur Species....Pages 121-134
Structure and Reaction Mechanisms in Sulphur-Radical Chemistry Revealed by E.S.R. Spectroscopy....Pages 135-154
Sulfur-Centered Three-Electron Bonded Radical Species....Pages 155-172
Radical Cations of Conjugated Cyclic Disulfides....Pages 173-183
Beam Experiments as a Means for the Generation of Elusive Sulfur-Containing Molecules....Pages 185-192
Dications from Cyclic Polythioethers....Pages 193-196
Sulfenylium Cation Carriers in Chemistry and Biochemistry....Pages 197-211
Neighboring Group Participation: General Principles and Application to Sulfur-Centered Reactive Species....Pages 213-226
Design, Synthesis, and Conformational Analysis of Compounds Tailored for the Study of Sulfur-Centered Reactive Intermediates....Pages 227-238
The Stereochemical Course of Sulphate Activation and Transfer....Pages 239-256
Anionic Organosulfur Compounds in Synthesis: New Applications of the Ramberg-Bäcklund Reaction....Pages 257-267
The Synthesis and Metal Complexes of Sulfur-Containing Models for Nitrogenase Enzymes....Pages 269-281
Biologically Active Organosulfur Compounds from Garlic and Onions: The Search for New Drugs....Pages 283-290
Free Radical Processes in the Reactions of Organometallics with Organic Sulfur Compounds....Pages 291-302
The Invention of Radical Chain Reactions of Value in Organic Synthesis....Pages 303-317
Recent Advances in the Chemistry of Compounds Containing S-SI Moieties....Pages 319-325
Reaction Kinetics of Sulfur-Centered Radicals....Pages 327-340
Redox Systems with Sulphur-Centered Species....Pages 341-351
Electrochemistry of Thioethers as Models for Biological Electron Transfer....Pages 353-357
Free-Radical Reactions Involving Thiols and Disulphides....Pages 359-366
Hydrogen Abstraction by Thiyl Radicals from Activated C-H-Bonds of Alcohols, Ethers and Polyunsaturated Fatty Acids....Pages 367-376
Thiyl Free Radicals: Electron Transfer, Addition or Hydrogen Abstraction Reactions in Chemistry and Biology, and the Catalytic Role of Sulphur Compounds....Pages 377-387
Free Radical Transfer Involving Sulphur Peptide Functions....Pages 389-399
Electron Spin Resonance Investigation of the Thiyl Free Radical Metabolites of Cysteine, Glutathione, and Drugs....Pages 401-408
Sulphur Compounds and “Chemical Repair” in Radiation Biology....Pages 409-414
Thiol Reactivity Towards Drugs and Radicals: Some Implications in the Radiotherapy and Chemotherapy of Cancer....Pages 415-427
In Vivo Hemoglobin Thiyl Radical Formation as a Consequence of Hydrazine-Based Drug Metabolism....Pages 429-434
The Biological Actions of the Glutathione/Disulfide System: An Overview....Pages 435-443
Back Matter....Pages 445-451