Baeckvall J.-E. (ed.) Modern Oxidation Methods
Подождите немного. Документ загружается.
8.3.3 Biocatalytic Oxidation 306
8.3.4 Applications of Amine N-Oxidation in Coupled
Catalytic Processes 306
8.4 Concluding Remarks 308
References 309
9 Liquid Phase Oxidation Reactions Catalyzed by Polyoxometalates 315
Ronny Neumann
9.1 Introduction 315
9.2 Polyoxometalates (POMs) 316
9.3 Oxidation with Mono-Oxygen Donors 317
9.4 Oxidation with Peroxygen Compounds 323
9.5 Oxidation with Molecular Oxygen 331
9.6 Heterogenization of Homogeneous Reactions – Solid-Liquid,
Liquid-Liquid, and Alternative Reaction Systems 341
9.6.1 Solid-Liquid Reactions 341
9.6.2 Liquid-Liquid Reactions and Reactions in Alternative Media 343
9.7 Conclusion 346
References 346
10 Oxidation of Carbonyl Compounds 353
Eric V. Johnston and Jan-E. Bäckvall
10.1 Introduction 353
10.2 Oxidation of Aldehydes to Carboxylic Acids 353
10.2.1 Metal-Free Oxidation of Aldehydes to Carboxylic Acids 354
10.2.2 Metal-Catalyzed Oxidation of Aldehydes to Carboxylic Acids 355
10.3 Oxidation of Ketones 356
10.3.1 Baeyer-Villiger Reactions 356
10.3.2 Catalytic Asymmetric Baeyer-Villiger Reactions 356
10.3.2.1 Chemocatalytic Versions 357
10.3.2.2 Biocatalytic Versions 358
References 365
11 Manganese-Catalyzed Oxidation with Hydrogen Peroxide 371
Wesley R. Browne, Johannes W. de Boer, Dirk Pijper, Jelle Brinksma,
Ronald Hage, and Ben L. Feringa
11.1 Introduction 371
11.2 Bio-inspired Manganese Oxidation Catalysts 372
11.3 Manganese-Catalyzed Bleaching 375
11.4 Epoxidation and cis-Dihydroxylation of Alkenes 375
11.4.1 Manganese Salts 376
11.4.2 Porphyrin-Based Catalysis 378
11.4.3 Salen-Based Systems 381
11.4.4 Tri- and Tetra-azacycloalkane Derivatives 385
11.4.4.1 Tetra-azacycloalkane Derivatives 386
11.4.4.2 Triazacyclononane Derivatives 387
Contents IX
11.4.4.3 Manganese Complexes for Alkene Oxidation Based
on Pyridyl Ligands 403
11.5 Manganese Catalysts for the Oxidation of Alkanes, Alcohols,
and Aldehydes 406
11.5.1 Oxidation of Alkanes 406
11.5.2 Oxidation of Alcohols and Aldehydes 407
11.5.3 Sulfides, Sulfoxides, and Sulfones 408
11.6 Conclusions 411
References 412
12 Biooxidation with Cytochrome P450 Monooxygenases 421
Marco Girhard and Vlada B. Urlacher
12.1 Introduction 421
12.2 Properties of Cytochrome P450 Monooxygenases 422
12.2.1 Structure 422
12.2.2 Enzymology 423
12.2.3 Reactions Catalyzed by P450s 425
12.2.4 P450s as Industrial Biocatalysts 429
12.2.4.1 Advantages 429
12.2.4.2 Challenges in the Development of Technical P450 Applications 429
12.2.4.3 General Aspects of Industrial Application and Engineering
of P450s 430
12.3 Application and Engineering of P450s for the Pharmaceutical
Industry 430
12.3.1 Microbial Oxidations with P450s for Synthesis
of Pharmaceuticals 431
12.3.2 Application of Mammalian P450s for Drug Development 434
12.3.2.1 Enhancement of Recombinant Expression in E. coli 435
12.3.2.2 Enhancement of Activity and Selectivity and Engineering of
Novel Activities 436
12.3.2.3 Construction of Artificial Self-Sufficient Fusion Proteins 436
12.4 Application of P450s for Synthesis of Fine Chemicals 437
12.5 Engineering of P450s for Biocatalysis 438
12.5.1 Cofactor Substitution and Regeneration 438
12.5.1.1 Cofactor Substitution In Vitro 438
12.5.1.2 Cofactor Regeneration In Vitro 439
12.5.1.3 Cofactor Regeneration in Whole-Cells 439
12.5.2 Construction of Artificial Fusion Proteins 440
12.5.3 Engineering of New Substrate Specificities 440
12.5.3.1 P450
cam
from Pseudomonas putida 440
12.5.3.2 P450
BM3
from Bacillus megaterium 442
12.6 Future Trends 443
References 444
Index 451
X Contents
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, organocatalysis, or biocatalysis, enantioselective catalytic oxidation reac-
tions 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 oxida-
tions 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 oxida-
tions in organic synthesis, selective oxidation of amines and sulfides, oxidations
catalyzed by polyoxymetalates, oxidation of carbonyl compounds, and manganese-
catalyzed H
2
O
2
oxidations.
XI
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
XII Preface
List of Contributors
XIII
Hans Adolfsson
Stockholm University
Arrhenius Laboratory
Department of Organic Chemistry
SE-106 91 Stockholm
Sweden
Isabel W.C.E. Arends
Delft University of Technology
Department of Biotechnology
Laboratory for Biocatalysis and Organic
Chemistry
Julianalaan 136
2628 BL Delft
The Netherlands
Jan-Erling Bäckvall
Stockholm University
Arrhenius Laboratory
Department of Organic Chemistry
SE-106 91 Stockholm
Sweden
Matthias Beller
Leibniz-Institut für Katalyse e.V. an der
Universität Rostock
Albert-Einstein-Str. 29a
D-18059 Rostock
Germany
and
University of Rostock
Center for Life Science Automation
(CELISCA)
Friedrich-Barnewitz-Str. 8
D-18119 Rostock-Warnemünde
Germany
Albrecht Berkessel
University of Cologne
Chemistry Department
Greinstraße 4
D-50939 Cologne
Germany
Jelle Brinksma
University of Groningen
Stratingh Institute for Chemistry
Center for Systems Chemistry
Nijenborgh 4
9747 AG Groningen
The Netherlands
Wesley R. Browne
University of Groningen
Stratingh Institute for Chemistry
Center for Systems Chemistry
Nijenborgh 4
9747 AG Groningen
The Netherlands
Johannes W. de Boer
University of Groningen
Stratingh Institute for Chemistry
Center for Systems Chemistry
Nijenborgh 4
9747 AG Groningen
The Netherlands
and
Rahu Catalytics
Biopartner Center Leiden
Wassenaarseweg 72
2333 AL Leiden
The Netherlands
Ben L. Feringa
University of Groningen
Stratingh Institute for Chemistry
Center for Systems Chemistry
Nijenborgh 4
9747 AG Groningen
The Netherlands
Marco Girhard
Heinrich-Heine-Universität Düsseldorf
Institut für Biochemie
Universitätsstr. 1, Geb. 26.02
40225 Düsseldorf
Germany
Ronald Hage
Rahu Catalytics
Biopartner Center Leiden
Wassenaarseweg 72
2333 AL Leiden
The Netherlands
Yasutaka Ishii
Kansai University
Faculty of Chemistry, Materials and
Bioengineering
Department of Chemistry and Materials
Engineering
Suita, Osaka 564-8680
Japan
Eric V. Johnston
Stockholm University
Arrhenius Laboratory
Department of Organic Chemistry
SE-106 91 Stockholm
Sweden
Naruyoshi Komiya
Osaka University
Graduate School of Engineering
Science
Department of Chemistry
1-3, Machikaneyama, Toyonaka
Osaka 560-8531
Japan
Shun-Ichi Murahashi
Okayama University of Science
Department of Applied Chemistry
1-1, Ridai-cho
Okayama 700-0005
Japan
and
Osaka University
Graduate School of Engineering
Science
Department of Chemistry
1-3, Machikaneyama, Toyonaka
Osaka 560-8531
Japan
XIV List of Contributors
Ronny Neumann
Weizmann Institute of Science
Department of Organic Chemistry
Rehovot 76100
Israel
Yasushi Obora
Kansai University
Faculty of Chemistry, Materials and
Bioengineering
Department of Chemistry and Materials
Engineering
Suita, Osaka 564-8680
Japan
Dirk Pijper
University of Groningen
Stratingh Institute for Chemistry
Center for Systems Chemistry
Nijenborgh 4
9747 AG Groningen
The Netherlands
Satoshi Sakaguchi
Kansai University
Faculty of Chemistry, Materials and
Bioengineering
Department of Chemistry and Materials
Engineering
Suita, Osaka 564-8680
Japan
Kristin Schröder
Leibniz-Institut für Katalyse e.V. an der
Universität Rostock
Albert-Einstein-Str. 29a
D-18059 Rostock
Germany
Roger A. Sheldon
Delft University of Technology
Department of Biotechnology
Laboratory for Biocatalysis and Organic
Chemistry
Julianalaan 136
2628 BL Delft
The Netherlands
Yian Shi
Colorado State University
Department of Chemistry
Fort Collins, CO 80523
USA
Man Kin Tse
Leibniz-Institut für Katalyse e.V. an der
Universität Rostock
Albert-Einstein-Str. 29a
D-18059 Rostock
Germany
and
University of Rostock
Center for Life Science Automation
(CELISCA)
Friedrich-Barnewitz-Str. 8
D-18119 Rostock-Warnemünde
Germany
Vlada B. Urlacher
Heinrich-Heine-Universität Düsseldorf
Institut für Biochemie
Universitätsstr. 1, Geb. 26.02
40225 Düsseldorf
Germany
List of Contributors XV
1
Recent Developments in Metal-catalyzed Dihydroxylation
of Alkenes
Man Kin Tse, Kristin Schr
€
oder, 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-freeze 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 C¼C 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 consid-
erable advances in biomimetic non-heme complexes have been 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 OsO
4
reacts only slowly with
electron-deficient alkenes; hence, it is necessary to employ higher amounts of catalyst
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
j
1
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].
While the enantioselectivity of the reaction has largely been advanced through
extensive synthesis and screening of cinchona alkaloid ligands by the Sharpless
group, larger scale applications of this method remain problematic. The minimi-
zation of the use of expensive osmium catalyst and the efficient recycling of the metal
should be a primary focus for the development. Coming in second is 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 been developed. Historically, chlorates [9] and hydrogen peroxide [10]
were first applied as stoichiometric oxidants; however, in both cases, the dihydroxy-
lation often proceeds with low chemoselectivity. Other reoxidants for osmium(VI)
are tert-butyl hydroperoxide in the presence of Et
4
NOH [11] and a range of N-oxides
such as N-methylmorpholine N-oxide (NMO) [12] (Upjohn process), and trimethyl-
amine N-oxide. K
3
[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, K
3
[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 K
2
[OsO
2
(OH)
4
], the co-oxidant
K
3
[Fe(CN)
6
], the base K
2
CO
3
, 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 to a green 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.
Os
O
O
O
O
Os
O
O
O
O
R
2
R
1
R
1
R
2
R
1
R
2
OH
OH
H
2
O
/
ox
i
d
a
t
i
o
n
r
e
d
u
c
t
i
o
n
"Os"
+
+
catalytic
stoichiometri
c
OsO
4
Scheme 1.1 Osmylation of alkenes.
2
j
1 Recent Developments in Metal-catalyzed Dihydroxylation of Alkenes