Organoselenium Chemistry Synthesis and Reactions
, by Wirth, ThomasNote: Supplemental materials are not guaranteed with Rental or Used book purchases.
- ISBN: 9783527329441 | 3527329447
- Cover: Hardcover
- Copyright: 12/12/2011
Filling the gap for a comprehensive handbook and ready reference with a focus on synthetic methods, 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.
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. Ciese he obtained his habilitation on stereoselective oxidations 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 microreaders.
Preface | p. XI |
List of Contributor | p. XIII |
Electrophilic Selenium | p. 1 |
General Introduction | p. 1 |
Synthesis of Electrophilic Selenium Reagents | p. 3 |
Reactivity and Properties | p. 7 |
Addition Reactions to Double Bonds | p. 11 |
Addition Reaction Involving Oxygen Centered Nucleophiles | p. 11 |
Addition Reaction Involving Nitrogen Centered Nucleophiles | p. 22 |
Addition Reactions Involving Carbon Centered Nucleophiles | p. 26 |
Addition Reaction Involving Chiral Nucleophiles or Chiral Substrates | p. 28 |
Selenocyclizations | p. 30 |
Oxygen Nucleophiles | p. 31 |
Nitrogen Nucleophiles | p. 35 |
Competition between Oxygen and Nitrogen Nucleophiles | p. 40 |
Carbon Nucleophiles | p. 42 |
Double Cyclization Reactions | p. 44 |
References | p. 45 |
Nucleophilic Selenium | p. 53 |
Introduction | p. 53 |
Development of Nucleophilic Selenium Reagents | p. 53 |
Examples of Recent Applications | p. 54 |
Properties of Selenols and Selenolates | p. 56 |
Electronegativity of Selenium | p. 56 |
Tautomerism of Selenols | p. 57 |
Nudeophilicity of Selenolates | p. 58 |
Inorganic Nucleophilic Selenium Reagents | p. 59 |
Conventional Reagents | p. 59 |
New Reagents | p. 61 |
Organic Nucleophilic Selenium Reagents | p. 65 |
Preparation | p. 65 |
Structure | p. 66 |
Ammonium Selenolates (NH4+) | p. 67 |
Selenolates of Group 1 Elements (Li, Na, K, and Cs) | p. 67 |
Selenolates of Group 2 Elements (Mg, Ca, and Ba) | p. 70 |
Selenolates of Group 3 Elements (Sm, Ce, Pr, Nb, and U) | p. 71 |
Selenolates of Group 4 Elements (Ti, Zr, and Hf) | p. 73 |
Selenolates of Group 5 Elements (V, Nb, and Ta) | p. 74 |
Selenolates of Group 6 Elements (Mo and W) | p. 75 |
Selenolates of Group 7 Elements (Mn and Re) | p. 76 |
Selenolates of Group 8 Elements (Fe,Ru, and Os) | p. 78 |
Selenolates of Group 9 Elements (Co, Rh, and Ir) | p. 81 |
Selenolates of Group 10 Elements (Ni,Pd, and Pt) | p. 84 |
Selenolates of Group 11 Elements (Cu, Ag, and Au) | p. 90 |
Selenolates of Group 12 Elements (Zn, Cd, and Hg) | p. 92 |
Selenolates of Group 13 Elements (B, Al, Ga, and In) | p. 95 |
Selenolates of Group 14 Elements (Si, Ge, Sn, and Pb) | p. 97 |
Selenolates of Group 15 Elements (P, As, Sb, and Bi) | p. 200 |
References | p. 102 |
Selenium Compounds in Radical Reactions | p. 111 |
Homolytic Substitution at Selenium to Generate Radical Precursors | p. 111 |
Bimolecular SH2 Reactions: Synthetic Considerations | p. 112 |
Radical Reagents | p. 115 |
Alkyl Radicals from Selenide Precursors | p. 115 |
Acyl Radicals from Acyl Selenide Precursors | p. 119 |
Imidoyl Radicals from Imidoyl Selenides | p. 123 |
Other Radicals from Selenide Precursors | p. 125 |
Selenide Building Blocks | p. 126 |
Solid Phase Synthesis | p. 128 |
Selenide Precursors in Radical Domino Reactions | p. 130 |
Homolytic Substitution at Selenium for the Synthesis of Se Containing Products | p. 132 |
Intermolecular SH2 onto Se | p. 132 |
Intramolecular SH2: Cyclization onto Se | p. 132 |
Seleno Group Transfer onto Alkenes and Alkynes | p. 134 |
Seleno Selenation | p. 135 |
Seleno Sulfonation | p. 136 |
Seleno Alkylation | p. 137 |
PhSeH in Radical Reactions | p. 138 |
Radical Clock Reactions | p. 138 |
Problem of Unwanted Trapping of Intermediate Radicals | p. 138 |
Catalysis of Starrnane-Mediated Reactions | p. 139 |
Selenium Radical Anions, SRN1 Substitutions | p. 141 |
References | p. 143 |
Selenium Stabilized Carbanions | p. 147 |
Introduction | p. 147 |
Preparation of Selenium-Stabilized Carbanions | p. 149 |
Deprotonation of Selenides | p. 149 |
Element Lithium Exchange | p. 154 |
Conjugate Addition of Organometallics to Vinyl and Alkynylselenides | p. 158 |
Reactivity of the Selenium-Stabilized Carbanions with Electrophiles and Synthetic Transformations of the Products | p. 161 |
Reaction of Selernum Stabilized Carbanions with Electrophiles | p. 166 |
Selenium Based Transformations on the Reaction Products of Selenium Stabilized Carbanions with Electrophiles | p. 167 |
Stereochemical Aspects | p. 168 |
Cyclic Selenium Stabilized Carbanions | p. 173 |
Acyclic Selenium Stabilized Carbanions | p. 176 |
Application of Selenium Stabilized Carbanions in Total Synthesis | p. 176 |
Examples Using Alkylation Reactions of Selenium Stabilized Carbanions | p. 177 |
Examples Using the Addition of Selenium-Stabilized Carbanions to Carbonyl Compounds | p. 180 |
Examples Using 1,4 Addition of Selenium-Stabihzed Carbanions to a,p-Unsaturated Carbonyl Compounds | p. 184 |
Conclusion | p. 186 |
References | p. 187 |
Selenium Compounds with Valency Higher than Two | p. 191 |
Introduction | p. 191 |
Trivalent, Dicoordinated Selenonium Salts | p. 192 |
Trivalent, Tricoordinated Derivatives | p. 194 |
Tetravalent, Dicoordinated Derivatives | p. 211 |
Tetravalent, Tricoordinated Derivatives | p. 225 |
Pentavalent Derivatives | p. 239 |
Hexavalent, Tetracoordinated Derivatives | p. 240 |
Hypervalent Derivatives | p. 244 |
Selenuranes | p. 244 |
Selenurane Oxides | p. 249 |
Perselenuranes | p. 250 |
Acknowledgment | p. 251 |
References | p. 251 |
Selenocarbonyls | p. 257 |
Overview | p. 257 |
Theoretical Aspects of Selenocarbonyls | p. 259 |
Molecular Structure of Selenocarbonyls | p. 261 |
Synthetic Procedures of Selenocarbonyls | p. 261 |
Manipulation of Selenocarbonyls | p. 270 |
Metal Complexes of Selenocarbonyls | p. 278 |
Future Aspects | p. 280 |
References | p. 281 |
Selenoxide Elimination and [2,3]-Sigmatropic Rearrangement | p. 287 |
Introduction | p. 287 |
Preparation and Properties of Chiral Selenoxides | p. 288 |
Selenoxide Elimination | p. 292 |
Enantioselective Selenoxide Elimination Producing Chiral Allenes and Unsaturated Ketones | p. 293 |
Diastereoselective Selenoxide Elimination Producing Chiral Allenecarboxylic Esters | p. 295 |
2,3-Sigmatropic Rearrangement via Allylic Selenoxides | p. 297 |
Enanrioselective [2,3]-Sigmatropic Rearrangement Producing Chiral Allylic Alcohols | p. 297 |
Diastereoselective [2,3]-Sigmatropic Rearrangement Producing Chiral Allylic Alcohols | p. 299 |
2,3-Sigmatropic Rearrangement via Allylic Selenimides | p. 305 |
Preparation and Properties of Chiral Selenimides | p. 307 |
Enanrioselective [2,3]-Sigmatropic Rearrangement Producing Chiral Allylic Amines | p. 309 |
Diastereoselective [2,3]-Sigmatropic Rearrangements Producing Chiral Allylic Amines | p. 310 |
2,3-Sigmatropic Rearrangement via Allylic Selenium Ylides | p. 311 |
Preparation and Properties of Optically Active Selenium Ylides | p. 312 |
Enantioselective [2,3]-Sigmatropic Rearrangements via Allylic Selenium Ylides | p. 313 |
Diastereoselective [2,3]-Sigmatropic Rearrangement via Allylic Selenium Ylides | p. 315 |
Summary | p. 317 |
References | p. 317 |
Selenium Compounds as Ligands and Catalysts | p. 321 |
Introduction | p. 321 |
Selenium-Catalyzed Reactions | p. 321 |
Stereoselective Addition of Diorganozinc Reagents to Aldehydes | p. 322 |
Diethylzinc Addition | p. 322 |
Diphenylzinc Addition | p. 323 |
Selenium-Ligated Transition Metal-Catalyzed Reactions | p. 324 |
Selenium-Ligated Stereoselective Hydrosilylation of Ketones | p. 324 |
Selenium-Ligated Copper-Catalyzed Addition of Organometallic Reagents to Enones | p. 325 |
Selenium-Ligated Palladium-Catalyzed Asymmetric Allylic Alkylation | p. 326 |
Selenium-Ligands in Palladium-Catalyzed Mizoroki-Heck Reactions | p. 328 |
Selenium-Ligands in Palladium-Catalyzed Phenylselenenylation of Organohalides | p. 330 |
Selenium-Ligands in Palladium-Catalyzed Substitution Reactions | p. 331 |
Selenium-Ligands in the Palladium-Catalyzed Allylation of Aldehydes | p. 331 |
Selenium-Ligands in Palladium-Catalyzed Condensation Reactions | p. 332 |
Ruthenium-Catalyzed Substitution Reactions | p. 333 |
Selenium-Ligands in Zinc-Catalyzed Intramolecular Hydroaminations | p. 334 |
Selenium-Ligands in Organocatalytic Asymmetric Aldol Reactions | p. 334 |
Selenium-Ligands in Stereoselective Darzens Reactions | p. 334 |
Selenium-Catalyzed Carbonylation Reactions | p. 335 |
Selective Reduction of a,p-Unsaturated Carbonyl Compounds | p. 336 |
Selenium-Catalyzed Halogenations and Halocyclizations | p. 336 |
Selenium-Catalyzed Staudinger-Vilarrasa Reaction | p. 337 |
Selenium-Catalyzed Elimination Reactions of Diols | p. 338 |
Selenium-Catalyzed Hydrostannylation of Alkenes | p. 339 |
Selenium-Catalyzed Radical Chain Reactions | p. 340 |
Selenium-Catalyzed Oxidation Reactions | p. 342 |
Selenium-Catalyzed Epoxidation of Alkenes | p. 342 |
Selenium-Catalyzed Dihydroxylation of Alkenes | p. 344 |
Selenium-Catalyzed Oxidation of Alcohols | p. 346 |
Baeyer-Villiger Oxidation | p. 347 |
Selenium-Catalyzed Allylic Oxidation of Alkenes | p. 349 |
Selenium-Catalyzed Oxidation of ArylAlkyl Ketones | p. 350 |
Selenium-Catalyzed Oxidation of Primary Aromatic Amines | p. 350 |
Selenium-Catalyzed Oxidation of Alkynes | p. 351 |
Selenium-Catalyzed Oxidation of Halide Anions | p. 352 |
Stereoselective Catalytic Selenenylation-Elimination Reactions | p. 353 |
Selenium-Catalyzed Diels-Alder Reactions | p. 355 |
Selenium-Catalyzed Synthesis of Thioacetals | p. 355 |
Selenium-Catalyzed Baylis-Hillman Reaction | p. 356 |
References | p. 356 |
Biological and Biochemical Aspects of Selenium Compounds | p. 361 |
Introduction | p. 361 |
Biological Importance of Selenium | p. 361 |
Selenocysteine: The 21st Amino Acid | p. 362 |
Biosynthesis of Selenocysteine | p. 363 |
Chemical Synthesis of Selenocysteine | p. 366 |
Chemical Synthesis of Sec-Containing Proteins and Peptides | p. 367 |
Selenoenzymes | p. 369 |
Glutathione Peroxidases | p. 369 |
Iodothyronine Deiodinase | p. 379 |
Synthetic Mimics of IDs | p. 384 |
Thioredoxirn Reductase | p. 387 |
Summary | p. 389 |
References | p. 392 |
öSe NMR Values | p. 397 |
Index | p. 435 |
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