Table Of Content39
Topics in Organometallic Chemistry
Editorial Board:
M. Beller l J. M. Brown l P. H. Dixneuf
A. Fu¨rstner l L. Gooßen l L. S. Hegedus
P. Hofmann l T. Ikariya l L. A. Oro l Q.-L. Zhou
Topics in Organometallic Chemistry
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Vol. 28, 2010
Organometallics and
Renewables
Volume Editors: Michael A. R. Meier
Bert M. Weckhuysen Pieter C. A. Bruijnincx
With Contributions by
L.M. de Espinosa M.A.R. Meier P.C.A. Bruijnincx
R. Jastrzebski P.J.C. Hausoul R.J.M. Klein Gebbink
B.M. Weckhuysen A. Behr A.J. Vorholt T.J. Korstanje
A. Buchard C.M. Bakewell J. Weiner C.K. Williams
Editors
Michael A. R. Meier Bert M. Weckhuysen
Institute of Organic Chemistry Pieter C. A. Bruijnincx
Karlsruhe Institute of Technology (KIT) Debye Institute of Nanomaterials Science
Karlsruhe Utrecht University
Germany Utrecht
Netherlands
ISBN 978-3-642-28287-4 ISBN 978-3-642-28288-1 (eBook)
DOI 10.1007/978-3-642-28288-1
Springer Heidelberg New York Dordrecht London
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Karlsruhe Institute of Technology (KIT) Inorganic Chemistry & Catalysis
Institute of Organic Chemistry Debye Institute of Nanomaterials Science
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Aims and Scope
The series Topics in Organometallic Chemistry presents critical overviews of
research results in organometallic chemistry. As our understanding of organometallic
structures, properties and mechanisms grows, new paths are opened for the design
of organometallic compounds and reactions tailored to the needs of such diverse
areas as organic synthesis, medical research, biology and materials science. Thus
the scope of coverage includes a broad range of topics of pure and applied
organometallic chemistry, where new breakthroughs are being made that are of
significance to a larger scientific audience.
The individual volumes of Topics in Organometallic Chemistry are thematic.
Review articles are generally invited by the volume editors.
In references Topics in Organometallic Chemistry is abbreviated Top Organomet
Chem and is cited as a journal. From volume 29 onwards this series is listed with
ISI/Web of Knowledge and in coming years it will acquire an impact factor.
vii
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Preface
Growing scarcity of fossil resources, concerns about the effects of global warming,
and the desire for a more independent, stable supply of energy and resources force
us to develop more sustainable production routes based on renewable resources.
These efforts should culminate in the development of highly integrated biorefi-
neries, which will eventually replace the conventional petrochemical ones. In order
to be able to compete economically as well as ecologically, such biorefineries
should not only produce our required energy-carriers but also focus on the produc-
tion of high value chemicals and materials, as needed by our society, to be an
integral part of such a facility. As far as the renewable production of carbon-
containing chemicals and liquid transportation fuels is concerned, biomass is in
principle the only viable and abundantly available alternative resource. This, of
course, with the provision that the biomass is produced in such a manner that it does
not compete with the food supply.
In addition to the geopolitical imperative for a transition from fossil to renewable
resources, using biomass as feedstock holds additional, specific advantages for the
chemist. Nature supplies us with an enormous structural diversity in the highly
functionalized feed that is biomass. Not only are the various components of
biomass often extensively functionalized, they often come to us stereochemically
pure. This feedstock thus provides an excellent opportunity for a more facile
production of highly valuable polymer building blocks, specialty chemicals and
pharmaceuticals. Indeed, achieving such structural complexity in the petrochemical
bottom-up approach by selectively introducing functional groups, hetero-atoms,
and stereochemical information is currently a rather cumbersome process as one
has to start from non-functionalized hydrocarbons. For the production of bulk and
commodity chemicals, on the other hand, selective defunctionalization is often
required if we want to obtain these high volume products from renewable resources.
In any case, i.e., both for selective functionalization as well as defunctionalization,
the development of new catalysts and new catalytic conversion routes will be
essential. In fact, catalysis has been identified as one of the key enabling technol-
ogies ultimately required for the realization of the “ideal biorefinery.” To achieve
ix
x Preface
this, both chemical and enzymatic catalysis will be necessary and in particular a
combination of both represents a promising yet challenging approach. Organome-
tallics, or more broadly speaking transition-metal complexes, are ideally suited as
catalyst to deal with the complex biomass feedstock in a selective manner. One can
easily envisage that the application of the general approach of systematic catalyst
optimization by rational ligand design, common in transition metal-complex catal-
ysis, to renewable substrates, such as sugars, terpenes, or fatty acid derivatives, can
give rise to many new or improved chemo-, regio-, and enantioselective conversion
routes. This volume reviews and highlights some of the recent efforts in this
direction. The five chapters are organized along the lines of reaction types rather
than class of renewable substrate. Behr and Vorholt, for instance, discuss a classical
set of olefin addition reactions, i.e., the hydroformylation and related conversions,
when applied to renewables. The exploitation of unsaturations in renewable sub-
strates such as fatty acids and terpenes by the exceptionally versatile ruthenium-
metathesis catalysts is reviewed by Montero de Espinosa and Meier. Korstanje and
Klein Gebbink review the wealth of information on the selective rhenium-catalyzed
oxidation and deoxygenation of renewables. Bruijnincx, Weckhuysen, and co-
workers discuss the renaissance of the palladium-catalyzed telomerization reaction
in light of the recent use of renewables as multifunctional substrates. Finally,
Williams and co-workers show the recent advances in using transition-metal
catalysts and initiators for the production of renewable polymers. Together, these
contributions show the potential and power of using transition-metal catalysts for
the production of renewable chemicals. One also has to note, however, that the area
of “Organometallics and Renewables” is a terrain that largely still remains to be
explored. Many other exciting contributions of research on catalysis with organo-
metallics to the blooming field of catalytic biomass conversion can therefore be
expected in the near future. We hope that this volume not only highlights the
potential of the field but also serves as a source of inspiration for the organometallic
chemist to further investigate this field rich in opportunities.
Karlsruhe, Germany Michael A. R. Meier
Utrecht, The Netherlands Pieter Bruijnincx, Bert Weckhuysen
