Modern Oxidation Methods E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 757

Veröffentlichungsjahr: 2011

Beschreibung

While rust is an unwanted oxidation reaction, there are also many other useful oxidation reactions that are extremely important and number among the most commonly used reactions in the chemical industry.
This completely revised, updated second edition now includes additional sections on industrial oxidation and biochemical oxidation.
Edited by one of the world leaders in the field, high-quality contributions cover every important aspect from classical to green chemistry methods:

- Recent Developments in Metal-catalyzed Dihydroxylation of Alkenes
- Transition Metal-Catalyzed Epoxidation of Alkenes
- Organocatalytic Oxidation. Ketone-Catalyzed Asymmetric Epoxidation of Alkenes and Synthetic Applications
- Catalytic Oxidations with Hydrogen Peroxide in Fluorinated Alcohol Solvents
- Modern Oxidation of Alcohols using Environmentally Benign Oxidants
- Aerobic Oxidations and Related Reactions Catalyzed by N-Hydro xyphthalimide
- Ruthenium-Catalyzed Oxidation for Organic Synthesis
- Selective Oxidation of Amines and Sulfides
- Liquid Phase Oxidation Reactions Catalyzed by Polyoxometalates
- Oxidation of Carbonyl Compounds
- Manganese-Catalyzed Oxidation with Hydrogen Peroxide
- Biooxidation with Cytochrome P450 Monooxygenases

By providing an overview of this vast topic, the book represents an unparalleled aid for organic, catalytic and biochemists working in the field.

Leseprobe

Table of Contents

Preface

List of Contributors

1 Recent Developments in Metal-catalyzed Dihydroxylation of AlkenesMan Kin Tse, Kristin Schröder, and Matthias Beller

1.1 Introduction

1.2 Environmentally Friendly Terminal Oxidants

1.3 Supported Osmium Catalyst

1.4 Ionic Liquid

1.5 Ruthenium Catalysts

1.6 Iron Catalysts

1.7 Conclusions

References

2 Transition Metal-Catalyzed Epoxidation of AlkenesHans 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

2.5 Manganese-Catalyzed Epoxidations

2.6 Rhenium-Catalyzed Epoxidations

2.7 Iron-Catalyzed Epoxidations

2.8 Ruthenium-Catalyzed Epoxidations

2.9 Epoxidations Using Late Transition Metals

2.10 Concluding Remarks

References

3 Organocatalytic Oxidation. Ketone-Catalyzed Asymmetric Epoxidation of Alkenes and Synthetic ApplicationsYian Shi

3.1 Introduction

3.2 Catalyst Development

3.3 Synthetic Applications

3.4 Conclusion

References

4 Catalytic Oxidations with Hydrogen Peroxide in Fluorinated Alcohol Solvents Albrecht Berkessel

4.1 Introduction

4.2 Properties of Fluorinated Alcohols

4.3 Epoxidation of Alkenes in Fluorinated Alcohol Solvents

4.4 Sulfoxidation of Thioethers in Fluorinated Alcohol Solvents

4.5 Baeyer-Villiger Oxidation of Ketones in Fluorinated Alcohol Solvents

4.6 Epilog

References

5 Modern Oxidation of Alcohols using Environmentally Benign Oxidants Isabel W.C.E. Arends and Roger A. Sheldon

5.1 Introduction

5.2 Oxoammonium based Oxidation of Alcohols – TEMPO as Catalyst

5.3 Metal-Mediated Oxidation of Alcohols – Mechanism

5.4 Ruthenium-Catalyzed Oxidations with O2

5.5 Palladium-Catalyzed Oxidations with O2

5.6 Copper-Catalyzed Oxidations with O2

5.7 Other Metals as Catalysts for Oxidation with O2

5.8 Catalytic Oxidation of Alcohols with Hydrogen Peroxide

5.9 Concluding Remarks

References

6 Aerobic Oxidations and Related Reactions Catalyzed by N-Hydroxyphthalimide Yasutaka Ishii, Satoshi Sakaguchi, and Yasushi Obora

6.1 Introduction

6.2 NHPI-Catalyzed Aerobic Oxidation

6.3 Functionalization of Alkanes Catalyzed by NHPI

6.4 Carbon-Carbon Bond-Forming Reaction via Catalytic Carbon Radicals Generation Assisted by NHPI

6.5 Conclusions

References

7 Ruthenium-Catalyzed Oxidation for Organic SynthesisShun-Ichi Murahashi and Naruyoshi Komiya

7.1 Introduction

7.2 RuO4-Promoted Oxidation

7.3 Oxidation with Low-Valent Ruthenium Catalysts and Oxidants

References

8 Selective Oxidation of Amines and SulfidesJan-E. Bäckvall

8.1 Introduction

8.2 Oxidation of Sulfides to Sulfoxides

8.3 Oxidation of Tertiary Amines to N-Oxides

8.4 Concluding Remarks

References

9 Liquid Phase Oxidation Reactions Catalyzed by Polyoxometalates Ronny Neumann

9.1 Introduction

9.2 Polyoxometalates (POMs)

9.3 Oxidation with Mono-Oxygen Donors

9.4 Oxidation with Peroxygen Compounds

9.5 Oxidation with Molecular Oxygen

9.6 Heterogenization of Homogeneous Reactions – Solid-Liquid, Liquid-Liquid, and Alternative Reaction Systems

9.7 Conclusion

References

10 Oxidation of Carbonyl CompoundsEric V. Johnston and Jan-E. Bäckvall

10.1 Introduction

10.2 Oxidation of Aldehydes to Carboxylic Acids

10.3 Oxidation of Ketones

References

11 Manganese-Catalyzed Oxidation with Hydrogen Peroxide Wesley R. Browne, Johannes W. de Boer, Dirk Pijper, Jelle Brinksma,Ronald Hage, and Ben L. Feringa

11.1 Introduction

11.2 Bio-inspired Manganese Oxidation Catalysts

11.3 Manganese-Catalyzed Bleaching

11.4 Epoxidation and cis-Dihydroxylation of Alkenes

11.5 Manganese Catalysts for the Oxidation of Alkanes, Alcohols,and Aldehydes

11.6 Conclusions

References

12 Biooxidation with Cytochrome P450 Monooxygenases Marco Girhard and Vlada B. Urlacher

12.1 Introduction

12.2 Properties of Cytochrome P450 Monooxygenases

12.3 Application and Engineering of P450s for the Pharmaceutical Industry

12.4 Application of P450s for Synthesis of Fine Chemicals

12.5 Engineering of P450s for Biocatalysis

12.6 Future Trends

References

Index

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The Editor

Prof. Dr. Jan-Erling Bäckvall Stockholm University Department of Organic Chem. Arrhenius Lab. 106 91 Stockholm Schweden

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Preface

Oxidation reactions continue to play an important role in organic chemistry, and the increasing demand for selective and mild oxidation methods in modern organic synthesis has led to rich developments in the field during recent decades. Significant progress has been achieved within the area of catalytic oxidations, and this has led to a range of selective and mild processes. These reactions can be based on metal catalysis, organo catalysis, or biocatalysis, enantioselective catalytic oxidation reactions being of particular interest.

The First Edition of the multi-authored book ‘Modern Oxidation Methods’ was published in 2004 with the aim of fulfilling the need for an overview of the latest developments in the field. In particular, some general and synthetically useful oxidation methods that are frequently used by organic chemists were covered, including catalytic as well as noncatalytic oxidation reactions, the emphasis being on catalytic methods that employ environmentally friendly (‘green’) oxidants such as molecular oxygen and hydrogen peroxide. These oxidants are atom economic and lead to a minimum amount of waste.

This Second Edition has in total twelve chapters, each covering an area of contemporary interest, and now includes two additional chapters on topics that were not covered in the first book, the other chapters having been updated. One of the added chapters (Chapter 12) reviews biooxidation with cytochrome P450 mono-oxygenases, an area of increasing interest, and the other (Chapter 4) covers oxidations with hydrogen peroxide in fluorinated alcohol solvents. Topics that are reviewed in the updated chapters involve olefin oxidations and include osmium-catalyzed dihydroxylation, metal-catalyzed epoxidation, and organocatalytic epoxida-tion. In subsequent chapters, catalytic alcohol oxidation with environmentally benign oxidants and aerobic oxidations catalyzed by N-hydroxyphthalimides (NHPI), with a special focus on the oxidation of hydrocarbons via C–H activation, are reviewed. Other chapters include recent advances in ruthenium-catalyzed oxidations in organic synthesis, selective oxidation of amines and sulfides, oxidations catalyzed by polyoxymetalates, oxidation of carbonyl compounds, and manganese-catalyzed H2O2 oxidations.I

I hope that the Second Edition of ‘Modern Oxidation Methods’ will be of value to chemists involved in oxidation reactions in both academic and industrial research and that it will stimulate further development in this important field. Finally, I would like to warmly thank all the authors for their excellent contributions.

Stockholm, June 2010

Jan-E. Bäckvall

List of Contributors

Hans AdolfssonStockholm University Arrhenius LaboratoryDepartment of Organic ChemistrySE-106 91 Stockholm Sweden

Isabel W.C.E. ArendsDelft University of TechnologyDepartment of BiotechnologyLaboratory for Biocatalysis and OrganicChemistryJulianalaan 1362628 BL DelftThe Netherlands

Jan-Erling BäckvallStockholm UniversityArrhenius Laboratory Department of Organic ChemistrySE-106 91 StockholmSweden

Matthias BellerLeibniz-Institut für Katalyse e.V. an derUniversität RostockAlbert-Einstein-Str. 29aD-18059 RostockGermany

and

University of RostockCenter for Life Science Automation(CELISCA)Friedrich-Barnewitz-Str. 8D-18119 Rostock-WarnemündeGermany

Albrecht BerkesselUniversity of Cologne Chemistry Department Greinstraße 4 D-50939 CologneGermany

Jelle BrinksmaUniversity of Groningen Stratingh Institute for Chemistry Center for Systems Chemistry Nijenborgh 49747 AG Groningen The Netherlands

Wesley R. BrowneUniversity of Groningen Stratingh Institute for Chemistry Center for Systems ChemistryNijenborgh 4 9747 AG Groningen The Netherlands

Johannes W. de BoerUniversity of Groningen Stratingh Institute for Chemistry Center for Systems ChemistryNijenborgh 4 9747 AG GroningenThe Netherlands

and

Rahu CatalyticsBiopartner Center Leiden Wassenaarseweg 72 2333 AL Leiden The Netherlands

Ben L. FeringaUniversity of Groningen Stratingh Institute for Chemistry Center for Systems ChemistryNijenborgh 4 9747 AG Groningen The Netherlands

Marco GirhardHeinrich-Heine-Universität DüsseldorfInstitut für BiochemieUniversitätsstr. 1, Geb. 26.02 40225 DüsseldorfGermany

Ronald HageRahu Catalytics Biopartner Center Leiden Wassenaarseweg 72 2333 AL Leiden The Netherlands

Yasutaka IshiiKansai UniversityFaculty of Chemistry, Materials andBioengineeringDepartment of Chemistry and Materials EngineeringSuita, Osaka 564-8680Japan

Eric V. JohnstonStockholm University Arrhenius Laboratory Department of Organic Chemistry SE-106 91 Stockholm Sweden

Naruyoshi KomiyaOsaka UniversityGraduate School of Engineering ScienceDepartment of Chemistry1-3, Machikaneyama, ToyonakaOsaka 560-8531Japan

Shun-Ichi MurahashiOkayama University of Science Department of Applied Chemistry1-1, Ridai-choOkayama 700-0005 Japan

and

Osaka UniversityGraduate School of Engineering ScienceDepartment of Chemistry1-3, Machikaneyama, ToyonakaOsaka 560-8531Japan

Ronny NeumannWeizmann Institute of ScienceDepartment of Organic ChemistryRehovot 76100Israel

Yasushi OboraKansai UniversityFaculty of Chemistry, Materials and BioengineeringDepartment of Chemistry and Materials EngineeringSuita, Osaka 564-8680Japan

Dirk PijperUniversity of GroningenStratingh Institute for ChemistryCenter for Systems ChemistryNijenborgh 49747 AG GroningenThe Netherlands

Satoshi SakaguchiKansai UniversityFaculty of Chemistry, Materials and BioengineeringDepartment of Chemistry and Materials EngineeringSuita, Osaka 564-8680Japan

Kristin SchröderLeibniz-Institut für Katalyse e.V. an derUniversität RostockAlbert-Einstein-Str. 29aD-18059 RostockGermany

Roger A. SheldonDelft University of TechnologyDepartment of BiotechnologyLaboratory for Biocatalysis and Organic ChemistryJulianalaan 1362628 BL DelftThe Netherlands

Yian ShiColorado State University Department of Chemistry Fort Collins,CO 80523USA

Man Kin TseLeibniz-Institut für Katalyse e.V. an der Universität Rostock Albert-Einstein-Str. 29aD-18059 Rostock Germany

and

University of RostockCenter for Life Science Automation (CELISCA)Friedrich-Barnewitz-Str. 8D-18119 Rostock-WarnemündeGermany

Vlada B. UrlacherHeinrich-Heine-UniversitätDüsseldorf Institut für Biochemie Universitätsstr. 1, Geb. 26.02 40225 Düsseldorf Germany

1

Recent Developments in Metal-catalyzed Dihydroxylation

Man Kin Tse, Kristin Schröder, and Matthias Beller

1.1 Introduction

The oxidative functionalization of alkenes is of major importance in the chemical industry, both in organic synthesis and in the industrial production of bulk and fine chemicals [1]. Among the various oxidation products of alkenes, 1,2-diols have numerous applications. Ethylene and propylene glycols are produced annually on a multi-million tons scale as polyester monomers and anti-free ze agents [2]. A number of 1,2-diols such as 2,3-dimethyl-2,3-butanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, and 1,2- and 2,3-butanediol are important starting materials for the fine chemical industry. In addition, enantiomerically enriched 1,2-diols are employed as intermediates in the production of pharmaceuticals and agrochemicals. Nowadays 1,2-diols are mainly manufactured by a two-step sequence consisting of epoxidation of an alkene with a hydroperoxide, a peracid, or oxygen followed by hydrolysis of the resulting epoxide [3]. Compared to the epoxidation-hydrolysis process, dihydroxylation of C=C double bonds comprises a more atom-efficient and shorter route to 1,2-diols. In general dihydroxylation of alkenes is catalyzed by osmium, ruthenium, iron, or manganese oxo species. Though considerable advances in biomimetic non-heme complexes have bee n achieved in recent years, the osmium-catalyzed variant is still the most reliable and efficient method for the synthesis of cis-1,2-diols [4]. Using osmium as a catalyst with stoichiometric amounts of a secondary oxidant, various alkenes, including mono-, di-, and tri-substituted unfunctionalized as well as many functionalized alkenes, can be converted to the corresponding diols. Electrophilic OsO4 reacts only slowly with electron-deficient alkenes; hence,itisnecessaryto employ higher amounts ofcatalyst and ligand for these alkenes. Recent studies have revealed that these substrates react much more efficiently when the reaction medium is maintained in an acidic state [5]. Citric acid appears to be superior for maintaining the pH in the desired range. However, it acts also as a ligand in this reaction but does not provide any asymmetric information transfer to the alkene. In contrast, it was found in another study that nonreactive internal alkenes, especially tetra-substituted ones, react faster at a constant pH value of 12.0 [6].

Since its discovery by Sharpless and coworkers, catalytic asymmetric dihydroxyla-tion (AD) has significantly enhanced the utility of osmium-catalyzed dihydroxylation (Scheme 1.1) [7]. Numerous applications in organic synthesis have appeared in recent years [8].

Scheme 1.1 Osmylation of alkenes.

While the enantioselectivity of the reaction has largely bee n advanced through extensive synthesis and scree ning of cinchona alkaloid ligands by the Sharpless group, larger scale applications of this method remain problematic. The minimization of the useof expensive osmium catalyst and the efficient recycling of the metal should be a primary focus for the development. Cominginsecondis the replacement of the costly reoxidants, which generate overstoichiometric amounts of waste in the form of Os(VI) species.

Several reoxidation processes for osmium(VI) glycolates or other osmium(VI) species have bee n developed. Historically, chlorates [9] and hydrogen peroxide [10] were first applied as stoichiometric oxidants; however, in both cases, the dihydroxy-lation often procee ds with low chemoselectivity. Other reoxidants for osmium(VI) are tert-butyl hydroperoxide in the presence of Et4NOH [11] and a range of N-oxides such as N-methylmorpholine N-oxide (NMO) [12] (Upjohn process), and trimethyl-amine N-oxide. K3[Fe(CN)6] gave a substantial improvement in the enantioselec-tivities in asymmetric dihydroxylations when it was introduced as a reoxidant for osmium(VI) species in 1990 [13]. However, K3[Fe(CN)6] was already described as an oxidant for other Os-catalyzed oxidation reactions as early as in 1975 [14]. Today the ‘AD-mix’, a combination of the catalyst precursor K2[OsO2(OH)4], the co-oxidant K3[Fe(CN)6], the base K2CO3, and the chiral ligand, is commercially available, and the dihydroxylation reaction is easy to carry out. However, the production of over-stoichiometric amounts of waste continues to be a significant disadvantage of the reaction protocol.

This article updates an earlier version in the first edition of this book and summarizes the recent developments in the area of osmium-catalyzed dihydroxyla-tions which bring this transformation closer toa‘gree n reaction’. Special emphasis is placed on the use of new reoxidants and recycling of the osmium catalyst. Moreover, less toxic metal catalysts such as ruthenium and iron are also discussed.

1.2 Environmentally Friendly Terminal Oxidants

1.2.1 Hydrogen Peroxide

Since the publication of the Upjohn procedure in 1976, the use of N-methylmorpho-line N-oxide (NMO) based oxidants has become one of the standard methods for osmium-catalyzed dihydroxylations. However, NMO has not bee n fully appreciated in the asymmetric dihydroxylation for a long time since it was difficult to obtain high enantiomeric excess (ee ). This drawback was significantly improved by slow addition of the alkene to the aqueous tert-BuOH reaction mixture, in which 97% ee was achieved with styrene [15].

Although hydrogen peroxide was one of the first stoichiometric oxidants used in osmium-catalyzed dihydroxylation [10a], it was not employed efficiently until recently. When hydrogen peroxide is used as a reoxidant for transition metal catalysts, a very common big disadvantage is that a large excess of H2O2 is required to compensate for the major unproductive peroxide decomposition to O2.

Recently, Bäckvall and coworkers were able to improve the H2O2 reoxidation process significantly by using N-methylmorpholine together with an electron transfer mediator (ETM)as co-catalysts inthe presence of hydrogen peroxide [16]. Thus, a renaissance of both NMO and HO was brought about. The mechanism of the triply catalyzed HO oxidation is shown in