Sulfur-Centered Reactive Intermediates in Chemistry and Biology (Nato Science Series A: (197))

A wonderfully successful NATO Advanced Study Institute on "Sulfur-Centered Reactive Intermediates in Chemistry and Biology" was held 18-30 June, 1989, at the Hotel Villa del Mare in Maratea, Italy. Despite the beautiful setting with mountains behind us and over­ looking the clear blue Mediterranean Sea under a cloudless sky (and with a private beach available), the lectures were extremely well attended. While some credit can go to the seriousness of the students, more must go to the calibre of speakers and the high quality of C. Chatgilialoglu, and Co-Director, Professor K. -D. their presentations. The Director, Dr. Asmus, are to be congratulated for putting together such an outstanding scientific program. Dr. Chatgilialoglu is also to be commended for arranging an equally stimulating social pro­ gram which included bus, train and boat trips to many local sites of interest. It was particularly fitting that a meeting on the chemistry and biochemistry of sulfur should be held in Italy since Italian chemists have made major contributions to our under­ standing of the organic chemistry of sulfur, including the chemistry of its reactive inter­ mediates. The early Italian interest in sulfur chemistry arose from the fact that Italy, or more specifically, Sicily, was a major world producer of sulfur prior to the development and exploitation of the Frasch process in Texas and Louisiana. 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 A wonderfully successful NATO Advanced Study Institute on "Sulfur-Centered Reactive Intermediates in Chemistry and Biology" was held 18-30 June, 1989, at the Hotel Villa del Mare in Maratea, Italy. Despite the beautiful setting with mountains behind us and overƯ looking the clear blue Mediterranean Sea under a cloudless sky (and with a private beach available), the lectures were extremely well attended. While some credit can go to the seriousness of the students, more must go to the calibre of speakers and the high quality of C. Chatgilialoglu, and Co-Director, Professor K.-D. their presentations. The Director, Dr. Asmus, are to be congratulated for putting together such an outstanding scientific program. Dr. Chatgilialoglu is also to be commended for arranging an equally stimulating social proƯ gram which included bus, train and boat trips to many local sites of interest. It was particularly fitting that a meeting on the chemistry and biochemistry of sulfur should be held in Italy since Italian chemists have made major contributions to our underƯ standing of the organic chemistry of sulfur, including the chemistry of its reactive interƯ mediates. The early Italian interest in sulfur chemistry arose from the fact that Italy, or more specifically, Sicily, was a major world producer of sulfur prior to the development and exploitation of the Frasch process in Texas and Louisiana