Selenium-based methods in synthetic chemistry have developed rapidly over the past years and are now offering highly useful tools for organic synthesis. Filling the gap for a comprehensive handbook and ready reference, this book covers all modern developments within the field, including biochemical aspects. The chemistry chapters are organized according to the different reactivities of various selenium compounds and reagents, with each chapter dealing with a special reaction type. Also includes a table with 77Se NMR shifts to aid in practical problems. From the Contents: * Electrophilic and Nucleophilic Selenium * Selenium Compounds in Radical Reactions * Selenium-Stabilized Carbanions * Selenium Compounds with Valency Higher than Two * Selenocarbonyls * Selenoxide Elimination and [2,3]-Sigmatropic Rearrangement * Selenium Compounds as Ligands and Catalysts * Biological and Biochemical Aspects of Selenium Compounds
Thomas Wirth is professor of organic chemistry at Cardiff University. After studying chemistry in Bonn and at the Technical University of Berlin, he obtained his PhD in 1992 with Professor S. Blechert. After a postdoctoral stay with Professor K. Fuji at Kyoto University a JSPS fellow, he started his independent research at the University of Basel (Switzerland). In the group of Professor B. Giese he obtained his habilitation on stereoselective oxidation reactions supported by various scholarships before taking up his current position at Cardiff University in 2000. He was invited as a visiting professor to a number of places including the University of Toronto/Canada (1999), Chuo University in Tokyo/Japan (2000), and Osaka University/Japan (2004) and was awarded the Werner-Prize from the New Swiss Chemical Society (2000). His main interests of research concern stereoselective electrophilic reactions, oxidative transformations with hypervalent iodine reagents including mechanistic investigations and organic synthesis performed in microreactors.
Preface ELECTROPHILIC SELENIUM General Introduction Addition Reactions to Double Bonds Selenocyclizations NUCLEOPHILIC SELENIUM Introduction Properties of Selenols and Selenolates Inorganic Nucleophilic Selenium Reagents Organic Nucleophilic Selenium Reagents SELENIUM COMPOUNDS IN RADICAL REACTIONS Homolytic Substitution at Selenium to Generate Radical Precursors Selenide Building Blocks Solid-Phase Synthesis Selenide Precursors in Radical Domino Reactions Homolytic Substitution at Selenium for the Synthesis of Se-Containing Products Seleno Group Transfer onto Alkenes and Alkynes PhSeH in Radical Reactions Selenium Radical Anions, Srn1 Substitutions SELENIUM-STABILIZED CARBANIONS Introduction Preparation of Selenium-Stabilized Carbanions Reactivity of the Selenium-Stabilized Carbanions with Electrophiles and Synthetic Transformations of the Products Stereochemical Aspects Application of Selenium-Stabilized Carbanions in Total Synthesis Conclusion SELENIUM COMPOUNDS WITH VALENCY HIGHER THAN TWO Introduction Trivalent, Dicoordinated Selenonium Salts Trivalent, Tricoordinated Derivatives Tetravalent, Dicoordinated Derivatives Tetravalent, Tricoordinated Derivatives Pentavalent Derivatives Hexavalent, Tetracoordinated Derivatives Hypervalent Derivatives SELENOCARBONYLS Overview Theoretical Aspects of Selenocarbonyls Molecular Structure of Selenocarbonyls Synthetic Procedures of Selenocarbonyls Manipulation of Selenocarbonyls Metal Complexes of Selenocarbonyls Future Aspects SELENOXIDE ELIMINATION AND [2,3]-SIGMATROPIC REARRANGEMENT Introduction Preparation and Properties of Chiral Selenoxides Selenoxide Elimination [2,3]-Sigmatropic Rearrangement via Allylic Selenoxides [2,3]-Sigmatropic Rearrangement via Allylic Selenimides [2,3]-Sigmatropic Rearrangement via Allylic Selenium Ylides Summary SELENIUM COMPOUNDS AS LIGANDS AND CATALYSTS Introduction Selenium-Catalyzed Reactions BIOLOGICAL AND BIOCHEMICAL ASPECTS OF SELENIUM COMPOUNDS Introduction Biological Importance of Selenium Selenocysteine: The 21st Amino Acid Biosynthesis of Selenocysteine Chemical Synthesis of Selenocysteine Chemical Synthesis of Sec-Containing Proteins and Peptides Selenoenzymes Summary