Alain Krief, Laszlo Hevesi

Organoselenium Chemistry I

Functional Group Transformations

• Broschiertes Buch

Produktbeschreibung

During the last fifteen years organoselenium chemistry underwent a spectacular mutation: from an exotic area of science practised by a few specialists it became a relatively well mastered and widely used methodology of synthetic organic chemistry. The key to this success is that a fair number of selenium based reagents and reactions have been discovered, which are able to perform specific transformations selectively and often under very mild conditions. The aim of this volume is to present the different selenium containing reagents now available to chemists, to mention the scope as well as the limitations of their reactions, and to compare those which possess similar reactivities. The authors present the reagents in the order of increasing oxidation level around the selenium atom.

Produktdetails

• Verlag: Springer / Springer Berlin Heidelberg / Springer, Berlin
• Artikelnr. des Verlages: 978-3-642-73243-0
• Softcover reprint of the original 1st ed. 1988
• Seitenzahl: 236
• Erscheinungstermin: 6. Dezember 2011
• Englisch
• Abmessung: 244mm x 170mm x 13mm
• Gewicht: 414g
• ISBN-13: 9783642732430
• ISBN-10: 3642732437
• Artikelnr.: 36120694

Inhaltsangabe

1. Introduction.- 1.1 Historical Review.- 1.2 Abundance and Distribution of Selenium.- 1.3 Selenium in Plants.- 1.4 Selenium Toxicity in Animals.- 1.5 Enzymic Role of Selenium.- 1.6 Ecological Aspects of Selenium in Human Health.- 1.7 Extraction of Selenium.- 1.8 Industrial Uses of Selenium.- 1.9 Selenium: Structure, Physical and Chemical Properties.- 2. Reactions Involving Hydrogen Selenide, Selenols and Related Compounds.- 2.1 Reactions Involving the Nucleophilicity of Hydrogen Selenide, Selenols and Related Compounds.- 2.1.1 N-dealkylation of Quaternary Ammonium Salts.- 2.1.2 N-dealkylation of Amines.- 2.1.3 Dealkylation of Alkyl Aryl Ethers,-Sulfides and-Selenides.- 2.1.4 Synthesis of Carboxylic Acids From Esters.- 2.2 Reduction Reactions Involving Hydrogen Selenide, Selenols, Selenocyanates, Triphenylphosphine Selenide and Related Compounds.- 2.2.1 Reduction of Benzyl Halides to Aryl Alkanes and of Iodo- and of Selenoketones to Ketones.- 2.2.2 Reduction of vic-Diheterosubstituted Alkanes to Alkenes.- 2.2.2.1 Selenolate Mediated Reduction of vic-Dihalogenoalkanes and Bromohydrins to Olefins.- 2.2.2.2 Reduction of Epoxides and Thiiranes to Olefins.- 2.2.3 Reduction of Disulfides to Thiolates.- 2.2.4 Reduction of Sulfoxides, Selenoxides and Telluroxides to Sulfides, Selenides and Tellurides Respectively.- 2.2.5 Reduction of Nitro-, Nitroso-, Hydroxylamino-, Azo-, Hydrazo-aromatic Compounds to Aromatic Amines and Reduction of Aryldiazonium Salts to Hydrazinium Salts.- 2.2.6 Reduction of Schiff's Bases to Amines: Application to the one Pot Reductive Amination of the Carbonyl Group.- 2.2.7 Reduction of Aldehydes and Ketones to Alcohols.- 2.2.8 Reduction of the Carbon-Carbon Double Bond of Enones.- 2.2.9 Reduction of Benzyl Selenides to Aryl Alkanes and of Methylselenoacetals Derived From Aromatic Carbonyl Compounds to Benzyl Methyl Selenides.- 2.3 Use of Copper (I) Benzeneselenolate.- 2.3.1 As the Precursor of Mixed Alkyl Phenylselenocuprates.- 2.3.2 As a Catalyst in the Synthesis of ?-Selenoketones from Selenolesters and Diazomethane.- 2.4 Reduction of Dienes to Olefins With Dichloro Bis (Diphenyl Selenide) Platinum (II).- 3. Reactions Involving Metallic or Amorphous Selenium with Organic Molecules.- 3.1 Transformation of (Z) Alkenes to Their (E) Isomers.- 3.2 Oxidation of Cyclic and Poly cyclic Hydrocarbons and Heterocycles to Aromatic Compounds Using Elemental Selenium.- 3.3 Oxido-reduction Reactions of Hydrocarbons.- 3.4 Reactions Involving Carbon Monoxide and Catalytic Amounts of Selenium.- 3.4.1 Synthesis of Acylic Derivatives of Carbonic Acid.- 3.4.2 Synthesis of Heterocycles Derived from Carbonic Acid.- 3.4.3 Synthesis of Carbonohydrazides, Semicarbazides, Carbazates and Carbonates.- 3.4.4 Oxidation of Formates and Formamides to Carbonates and Carbamates.- 3.4.5 Synthesis of Hydrogen Selenide and Some of its Application.- 3.4.6 Oxidation of Hydrazine to Diimide: Application to the Cis Hydrogénation of Olefins.- 3.4.7 Carbonylation of Alkyl Aryl Ketones to 1,3-Dicarbonyl Compounds: Application to the Synthesis of 4-Hydroxycoumarins.- 4. Reactions Involving Selenoxides and Related Derivatives.- 4.1 Reactions Involving Selenoxides.- 4.1.1 Oxidation of Sulfides, Amines and Acyl Hydrazines to Sulfoxides, Aminoxides, and to Symmetrical Diacyl Hydrazines, Respectively.- 4.1.2 Oxidation of Enediols to Dicarbonyl Compounds.- 4.1.3 Oxidative Conversion of Thiocarbonyl Compounds to Carbonyl Compounds.- 4.1.4 Oxidation of Trivalent Phosphorus Compounds to Their Oxides and of Thio- and Selenophosphorus Derivatives to Their Oxygenated Analogues.- 4.1.5 Oxidation of Olefins to vic-Glycols with Osmium Tetroxide-Selenoxide Reagent.- 4.2 Oxidation of Alcohols to Carbonyl Compounds with Dimethylselenide/N-chlorosuccinimide.- 4.3 Oxidative Conversion of sec-Benzylamines to Imines and Tertiary Benzylamines to Iminium Salts by Diphenylselenium Bis(trifluoroacetate).- 5. Reactions Involving Selenenyl Halides and Related Compounds.- 5.1 Allylic Halogenation of Olefins.- 5.2 Ring Expansion of 1,3-Dithiolans and 1,3-Dithians.- 5.3 Oxidation of Alcohols to Carbonyl Compounds.- 5.4 Synthesis of Oligonucleotides and Nucleoside Phosphoramidates.- 6. Reactions Involving Benzeneseleninic Anhydride (BSA) and Related Reagents.- 6.1 Oxidation of Phenols, Pyrocatechols and Hydroquinones.- 6.2 Dehydrogenation of Ketones to Enones and Dienones.- 6.3 Dehydrogenation of Lactones and Lactams to ?, ?-Unsaturated Compounds.- 6.4 Oxidation of Alcohols to Carbonyl Compounds or to Enones and Dienones.- 6.4.1 With BSA.- 6.4.2 With Diphenyldiselenide and t-Butyl Hydroperoxide.- 6.5 Oxidative Conversion of Thiols to Disulfides, Sulfides to Sulfoxides and of Phosphines to Phosphinoxides.- 6.6 Oxidation of Amines.- 6.7 Oxidation of Hydrazines.- 6.8 Oxidation of Hydroxylamines.- 6.9 Oxidation of the Alkyl Chain of Aromatic and Heteroaromatic Compounds.- 6.10 Regeneration of Carbonyl Compounds.- 6.10.1 From Thioketones, Hydrazones and Oximes.- 6.10.2 From Thioacetals and Selenoacetals.- 6.10.3 From Xanthates, Thioesters, Thiocarbonates, Thioamides and Their Telluro Analogues.- 6.11 Synthesis of ?-Selenocarbonyl Compounds from BSA and.- 6.11.1 Vinyl Sulfides and Vinyl Selenides.- 6.11.2 Allyl Alcohols.- 6.12 Synthesis of Allyl Alcohols from Allyl Silanes.- 7. Reactions Involving Benzeneseleninyl Halides.- 7.1 Oxidation of Aldoximes to Nitriles.- 7.2 Oxidation of Amines.- 7.3 Dehydrogenation of Carbonyl Compounds to Enones.- 8. Reactions Involving Perseleninic Acids.- 8.1 Oxidation of Olefins to Epoxides.- 8.2 Baeyer-Villiger Type Oxidation of Ketones to Esters and Lactones.- 8.3 Oxidation of Selenides to Selenoxides and Selenones and of Sulfides to Sulfoxides or Sulfones.- 9. Selenium Dioxide Oxidations.- 9.1 Reactivity of SeO2 with Alkenes.- 9.1.1 Oxidation of Alkenes with SeO2 or SeO2/t-BuO2H.- 9.1.1.1 Scope of Limitation.- 9.1.1.2 Regiochemistry.- 9.1.1.3 Stereochemical Considerations.- 9.1.1.4 Mechanistic Considerations.- 9.1.1.5 Use of the Reaction for the Synthesis of Complex Molecules and as a Key Step in the Total Synthesis of Natural Products.- 9.1.2 Diol Formation from Alkenes and SeO2/H2O2 or SeO2/H2SO4.- 9.1.3 Oxidation of Functionalized Olefins With SeO2.- 9.2 Reactivity of SeO2 Towards Acetylenic Hydrocarbons.- 9.3 Reactivity of SeO2 with Carbonyl Compounds.- 9.3.1 Reactions Involving SeO2.- 9.3.1.1 Scope and Limitation.- 9.3.1.2 Oxidation of Carbonyl Compounds to a-Dicarbonyl Compounds.- 9.3.1.3 Dehydrogenation of Carbonyl Compounds.- 9.3.1.4 Acetalisation of Carbonyl Compounds Catalyzed by SeO2.- 9.3.2 Oxidation of Carbonyl Compounds with SeO2/H2O2-Synthesis of Carboxylic Acids from Aldehydes and Ketones.- 9.3.2.1 Reaction of SeO2/H2O2 with Ketones.- 9.3.2.2 Reaction of SeO2/H2O2 with Aldehydes.- 9.4 Oxidation of the Alkyl Chain of Aromatic and Heteroaromatic Compounds.- 9.4.1 Synthesis of Aryl Carbonyl Compounds.- 9.4.2 Aromatisation of Cyclic and Heterocyclic Compounds.- 9.5 Oxidation of Benzylic and Allylic Alcohols.- 9.6 Oxidation of Hydrazones, Imines, Oximes and Semicarbazones.- 9.7 Conversion of Thio- and Selenocarbonyl Compounds to Carbonyl Compounds.- 9.8 Reactions of Nitroalkanes: Synthesis of N-hydroxy Carboxamides and Nitriles.- 9.9 Synthesis of Olefins from Phosphorus Ylides and Diazoalkanes.- 9.10 Reaction of SeO2 with Phosphines, Arsines, Stibines and Related Compounds.- 9.11 Reaction with Hydrazines.- 9.12 Reaction with Organometallics.- 10. Reactions of Imidoselenium Compounds.- 10.1 With Alkenes and Alkynes: Synthesis of Allylic and Propargylic Amines.- 10.2 With Dienes: Synthesis of Cis Diaminoalkanes.- 11. Reactions Involving Selenium Oxychloride and Selenium Tetrahalides.- 11.1 Reactivity of Selenium Oxychloride.- 11.2 Reactivity of Selenium Tetrafluoride.- 11.2.1 Synthesis of Geminal Difluoroalkanes from Aldehydes and Ketones..- 11.2.2 Synthesis of Alkylfluorides from Alcohols.- 11.3 Reactivity of Selenium Tetrachloride.- References.