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Catalytic Synthesis of AlkeneЦCarbon Monoxide Copolymers and Cooligomers. Edited by Ayusman Sen

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Books
attractively illustrated. Details too
extensive for incorporating into the
text are presented in clear tables. Antibiotics: Actions, Origins, Resistance sets a
new standard for a general work of reference on the subject of antibiotics,
and can be thoroughly recommended.
Heike Brtz-Oesterhelt
Bayer HealthCare AG
Pharmaforschungszentrum
Wuppertal (Germany)
Catalytic Synthesis of Alkene–
Carbon Monoxide Copolymers and
Cooligomers
Edited by Ayusman
Sen. Kluwer Academic/
Plenum Publishers,
New York 2003.
325 pp., hardcover
E 148.00.—ISBN
1-4020-1129-6
The finding that perfectly alternating
polyketones can be synthesized easily
under mild conditions of pressure and
temperature by using homogeneous palladium catalysts has given a strong
impulse to the field of catalysis and synthesis of new thermoplastics. The low
cost of the monomers and the good
materials properties of the polyketones
have generated academic and industrial
interest over the last two decades.
Application of this process on an industrial scale has led to commercialization
of terpolymers of carbon monoxide, ethylene, and propene as engineering thermoplastics.
Although several reviews have
appeared in the last few years concerning different aspects of the reaction,
this is the first book entirely devoted
to the subject, and is therefore a very
welcome initiative. It offers a complete
account of the catalytic reaction, written
by outstanding experts in the field. As
the title implies, the book focuses on
the catalytic polymer synthesis, with an
2880
emphasis on mechanistic considerations
and catalyst design. The reader should
be aware that the properties of the
copolymers, their reactivity, and related
aspects are not covered.
After an introductory chapter where
the main achievements and future goals
of the reaction are briefly presented,
Chapter 2 gives a detailed explanation
of the investigations that led the authors
to state the requirements for a palladium catalyst to promote this reaction.
The versatility of these catalysts, which
can be fine-tuned to give a variety of
products, ranging from high-molecularweight polyketones to simple esters,
aldehydes, or ketones is presented. The
chapter is largely devoted to reviewing
the authors' own work, and thus has
the character of a personal account.
Related to this versatility, Chapter 3
shows different ways to turn the selectivity of the reaction towards the synthesis
of low-molecular-weight co-oligomers
by controlling the parameters that influence the different steps of the reaction.
The chapter takes a fresh look at the
role of the catalyst, by analyzing results
from several mechanistic studies.
The industrial approach to the synthesis of co- and terpolymers is reviewed
in Chapter 4. The commercial development of the process required the control
of a reaction taking place in a multiphase system. Thus, in this chapter the
reader finds a discussion of the reaction
from a different viewpoint, which provides an interesting complement to the
mechanistic chapters.
Chapter 5 again deals with mechanistic considerations, focusing on the
organometallic reactions that can be
responsible for the chain transfer using
palladium catalysts. The didactic style
of this chapter is very appropriate for a
textbook, since it addresses a broader
readership.
Overall, Chapters 2, 3, and 5 overlap
to some extent. However, this is acceptable for the reader, as the mechanism of
the copolymerization reaction is
approached from very different angles.
The synthesis of regio- and stereoregular polyketones by copolymerizing
1-alkenes, mainly propene and styrene,
with carbon monoxide is discussed in
Chapters 6 and 7 of the book. Since
these polyketones possess true stereogenic centers, enantioselective catalysis
: 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
can be used to obtain optically active
polymers starting from achiral monomers. Special attention is devoted to
understanding the factors that govern
the control of regiochemistry and stereochemistry of the polyketones produced, depending on the symmetry of
the catalytic system. The authors give
an exhaustive survey of the results
reported for the synthesis of stereoregular or irregular polyketones.
Chapter 8 is again concerned with
mechanistic aspects of alkene–carbon
monoxide copolymerization reactions
in a more general sense. This rather
short chapter does not add much to the
three previous chapters devoted to the
reaction mechanism (Chapt. 2, 3, and 5).
The book is completed by Chapter 9,
which reviews theoretical research in
the field of catalytic copolymerization
of alkenes with polar monomers.
Throughout the chapter, theoretical
results are compared with independently obtained experimental data,
which is in good agreement between
theory and experiment.
It is somewhat disappointing that
nickel(ii)-catalyzed CO/alkene copolymerizations are largely neglected
throughout the book, especially since
those reactions have been very important for the historical development of
the field. Furthermore, such catalysts
have been investigated intensively as
an alternative to the costly palladium
systems. Especially in view of the
book's focus on mechanistic aspects,
and also the emphasis on commercial
applications, a detailed consideration
of the reasons for the failure of nickel(ii)-catalyzed CO/alkene copolymerization to be widely used up to now
would have been attractive.
This book offers a very good overview of the work performed in the
field of CO/alkene copolymerization,
and is of interest both for researchers
working in the area and for scientists
wishing to get a fundamental understanding of the reaction.
Amaia Bastero
Institut f5r Makromolekulare Chemie
Universit8t Freiburg
Freiburg im Breisgau (Germany)
DOI: 10.1002/anie.200385080
Angew. Chem. Int. Ed. 2004, 43, 2879 – 2880
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sen, synthesis, monoxide, cooligomers, alkeneцcarbon, catalytic, ayusman, copolymers, edited
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