At the very latest, with the award of the 2001 Nobel Prize for work on asymmetric oxidation, there has been a need for a comprehensive book on such methods. Edited by J.-E. Backvall, one of the world's leaders in the field, this book fills that gap by covering the topic, from classical to green chemistry methods. He has put together a plethora of well-established authors from all over the world who cover every important aspect in high-quality contributions -- whether aerobic oxidation or transition metal-catalyzed epoxidation of alkenes. By providing an overview of this huge topic, this book represents an unparalleled aid for any chemist working in the field. Chapters include: Recent Developments in the Osmium-Catalyzed Dihydroxylation of Olefins Transition Metal-Catalyzed Epoxidation of Alkenes Organocatalytic Oxidation - Ketone-Catalyzed Asymmetric Epoxidation of Olefins Modern Oxidation of Alcohols using environmentally Benign Oxidants Aerobic Oxidations and Related Reactions Catalyzed by N-Hydroxyphthalimide Ruthenium-Catalyzed Oxidation of Alkenes, Alcohols, Amines, Amides, b-Lactams, Phenols, and Hydrocarbons Selective Oxidations of Sulfides and Amines Liquid Phase Oxidation Reactions Catalyzed by Polyoxometalates Oxidation of Carbonyl Compounds Mn-catalysed Oxidation with Hydrogen Peroxide
Preface.
List of Contributors.
1. Recent Developments in the Osmium-catalyzed Dihydroxylation of Olefins (Uta Sundermeier, Christian Döbler, and Matthias Beller).
1.1 Introduction.
1.2 Environmentally Friendly Terminal Oxidants.
1.2.1 Hydrogen Peroxide.
1.2.2 Hypochlorite.
1.2.3 Oxygen or Air.
1.3 Supported Osmium Catalyst.
1.4 Ionic Liquids.
References.
2. Transition Metal-catalyzed Epoxidation of Alkenes (Hans Adolfsson).
2.1 Introduction.
2.2 Choice of Oxidant for Selective Epoxidation.
2.3 Epoxidations of Alkenes Catalyzed by Early Transition Metals.
2.4 Molybdenum and Tungsten-catalyzed Epoxidations.
2.4.1 Homogeneous Catalysts Hydrogen Peroxide as the Terminal Oxidant.
2.4.2 Heterogeneous Catalysts.
2.5 Manganese-catalyzed Epoxidations.
2.6 Rhenium-catalyzed Epoxidations.
2.6.1 MTO as an Epoxidation Catalyst Original Findings.
2.6.2 The Influence of Heterocyclic Additives.
2.6.3 The Role of the Additive.
2.6.4 Other Oxidants.
2.6.5 Solvents/Media.
2.6.6 Solid Support.
2.6.7 Asymmetric Epoxidations Using MTO.
2.7 Iron-catalyzed Epoxidations.
2.8 Concluding Remarks.
References.
3. Organocatalytic Oxidation. Ketone-catalyzed Asymmetric Epoxidation of Olefins (Yian Shi).
3.1 Introduction.
3.2 Early Ketones.
3.3C2 Symmetric Binaphthyl-based and Related Ketones.
3.4 Ammonium Ketones.
3.5 Bicyclo[3.2.1]octan-3-ones.
3.6 Carbohydrate Based and Related Ketones.
3.7 Carbocyclic Ketones.
3.8 Ketones with an Attached Chiral Moiety.
3.9 Conclusion.
Acknowledgments.
References.
4. Modern Oxidation of Alcohols Using Environmentally Benign Oxidants (I. W. C. E. Arends and R. A. Sheldon).
4.1 Introduction.
4.2 Oxoammonium-based Oxidation of Alcohols TEMPO as Catalyst.
4.3 Metal-mediated Oxidation of Alcohols Mechanism.
4.4 Ruthenium-catalyzed Oxidations with O2.
4.5 Palladium-catalyzed Oxidations with O2.
4.6 Copper-catalyzed Oxidations with O2.
4.7 Other Metals as Catalysts for Oxidation with O2.
4.8 Catalytic Oxidation of Alcohols with Hydrogen Peroxide.
4.9 Concluding Remarks.
References.
5. Aerobic Oxidations and Related Reactions Catalyzed byN-Hydroxyphthalimide (Yasutaka Ishii and Satoshi Sakaguchi).
5.1 Introduction.
.2 NHPI-catalyzed Aerobic Oxidation.
5.2.1 Alkane Oxidations with Dioxygen.
5.2.2 Oxidation of Alkylarenes.
5.2.2.1 Oxidation of Alkylbenzenes.
5.2.2.2 Synthesis of Terephthalic Acid.
5.2.2.3 Oxidation of Methylpyridines and Methylquinolines.
5.2.2.4 Oxidation of Hydroaromatic and Benzylic Compounds.
5.2.3 Preparation of Acetylenic Ketones by Direct Oxidation of Alkynes.
5.2.4 Oxidation of Alcohols.
5.2.5 Epoxidation of Alkenes Using Dioxygen as Terminal Oxidant.
5.2.6 Baeyer-Villiger Oxidation of KA-Oil.
5.2.7 Preparation of -Caprolactam Precoursor from KA-Oil.
5.3 Functionalization of Alkanes Catalyzed by NHPI.
5.3.1 Carboxylation of Alkanes with CO and O2.
5.3.2 First Catalytic Nitration of Alkanes Using NO2.
5.3.3 Sulfoxidation of Alkanes Catalyzed by Vanadium.
5.3.4 Reaction of NO with Organic Compounds.
5.3.5 Ritter-type Reaction with Cerium Ammonium Nitrate (CAN).
5.4 CarbonCarbon Bond Forming Reactionvia Generation of Carbon Radicals Assisted by NHPI.
5.4.1 Oxyalkylation of Alkenes with Alkanes and Dioxygen.
5.4.2 Synthesis of -Hydroxy--lactones by Addition of -Hydroxy Carbon Radicals to Unsaturated Esters.
5.4.3 Hydroxyacylation of Alkenes Using 1,3-Dioxolanes and Dioxygen.
5.4.4 Hydroacylation of Alkenes Using NHPI as a Polarity-reversal Catalyst.
5.5 Conclusions.
References.
6. Ruthenium-catalyzed Oxidation of Alkenes, Alcohols, Amines, Amides, -Lactams, Phenols, and Hydrocarbons (Shun-Ichi Murahashi and Naruyoshi Komiya).
6.1 Introduction.
6.2 RuO4-promoted Oxidation.
6.3 Oxidation with Low-valent Ruthenium Catalysts and Oxidants.
6.3.1 Oxidation of Alkenes.
6.3.2 Oxidation of Alcohols.
6.3.3 Oxidation of Amines.
6.3.4 Oxidation of Amides and -Lactams.
6.3.5 Oxidation of Phenols.
6.3.6 Oxidation of Hydrocarbons.
References.
7. Selective Oxidation of Amines and Sulfides (Jan-E. Bäckvall).
7.1 Introduction.
7.2 Oxidation of Sulfides to Sulfoxides.
7.2.1 Stoichiometric Reactions.
7.2.1.1 Peracids.
7.2.1.2 Dioxiranes.
7.2.1.3 Oxone and Derivatives.
7.2.1.4 H2O2 in Fluorous Phase.
7.2.2 Chemocatalytic Reactions.
7.2.2.1 H2O2 as Terminal Oxidant.
7.2.2.2 Molecular Oxygen as Terminal Oxidant.
7.2.2.3 Alkyl Hydroperoxides as Terminal Oxidant.
7.2.2.4 Other Oxidants in Catalytic Reactions.
7.2.3 Biocatalytic Reactions.
7.2.3.1 Haloperoxidases.
7.2.3.2 Ketone Monooxygenases.
7.3 Oxidation of Tertiary Amines toN-Oxides.
7.3.1 Stoichiometric Reactions.
7.3.2 Chemocatalytic Oxidations.
7.3.3 Biocatalytic Oxidation.
7.3.4 Applications of AmineN-oxidation in Coupled Catalytic Processes.
7.4 Concluding Remarks.
References.
8. Liquid Phase Oxidation Reactions Catalyzed by Polyoxometalates (Ronny Neumann).
8.1 Introduction.
8.2 Polyoxometalates (POMs).
8.3 Oxidation with Mono-oxygen Donors.
8.4 Oxidation with Peroxygen Compounds.
8.5 Oxidation with Molecular Oxygen.
8.6 Heterogenization of Homogeneous Reaction Systems.
8.7 Conclusion.
References.
9. Oxidation of Carbonyl Compounds (Jacques Le Paih, Jean-Cédric Frison and Carsten Bolm).
9.1 Introduction.
9.2 Oxidations of Aldehydes.
9.2.1 Conversions of Aldehydes to Carboxylic Acid Derivatives by Direct Oxidations.
9.2.1.1 Metal-free Oxidants.
9.2.1.2 Metal-based Oxidants.
9.2.1.3 Halogen-based Oxidants.
9.2.1.4 Sulfur- and Selenium-based Oxidants.
9.2.1.5 Nitrogen-based Oxidants.
9.2.1.6 Miscellaneous.
9.2.2 Conversions of Aldehydes into Carboxylic Acid Derivatives by Aldehyde Specific Reactions.
9.2.2.1 Dismutations and Dehydrogenations.
9.2.2.2 Oxidative Aldehyde Rearrangements.
9.2.3 Conversions of Aldehyde Derivatives into Carboxylic Acid Derivatives.
9.2.3.1 Acetals.
9.2.3.2 Nitrogen Derivatives.
9.2.3.3 Miscellaneous Substrates.
9.2.4 Oxidative Decarboxylations of Aldehydes.
9.3 Oxidations of Ketones.
9.3.1 Ketone Cleavage Reactions.
9.3.1.1 Simple Acyclic Ketones.
9.3.1.2 Simple Cyclic Ketones.
9.3.1.3 Functionalized Ketones.
9.3.2 Oxidative Rearrangements of Ketones.
9.3.2.1 Baeyer-Villiger Reactions.
9.3.2.2 Ketone Amidations.
9.3.2.3 Miscellaneous Rearrangements.
9.3.3 Willgerodt Reactions.
9.4 Conclusions.
References.
10. Manganese-based Oxidation with Hydrogen Peroxide (Jelle Brinksma, Johannes W. de Boer, Ronald Hage, and Ben L. Feringa).
10.1 Introduction.
10.2 Biomimetic Manganese Oxidation Catalysis.
10.3 Bleaching Catalysis.
10.4 Catalytic Epoxidation.
10.4.1 Manganese Porphyrin Catalysts.
10.4.2 Manganesesalen Catalysts.
10.4.3 Mn-1,4,7-triazacyclononane Catalysts.
10.4.4 Miscellaneous Catalysts.
10.5cis-Dihydroxylation.
10.6 Alcohol Oxidation to Aldehydes.
10.7 Sulfide to Sulfoxide Oxidation.
10.8 Conclusions.
References.
Subject Index.
