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Book Review The Success Story of Organometallic Chemistry! Applied Homogeneous Catalysis with Organometallic Compounds. A Comprehensive Handbook. (Volumes 1 and 2). Edited by B. Cornils and W. A. Herrmann

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BOOKS
The Success Story of Organometallic Chemistry!
Applied Homogeneous Catalysis with
Organometallic Compounds. A Comprehensive Handbook. (Volumes 1 and
2). Edited by B. Cornils and W! A .
Herrmann. VCH Verlagsgesellschaft,
Weinheim, 1996. Vol. 1, 571 pp.; Vol.
2,675 pp.; hardcover, two-volume set
DM 748.00.-ISBN 3-527-29286-1
This handbook could be considered as
the fourth component of a tetralogy on
transition metal chemistry. The first three
are: the classic Principles and Applications
of Organotransition
Metal Chernistry,
by J. P. Collman,
L. S. Hegedus, J. R.
Norton, and R.G.
Finke (University
Science Books, Mill
Valley, 1987). the
second edition of
Comprehensive
Organometallic
Chemistry, edited
by the late G. Wilkinson, F. G. A. Stone,
and E. W. Abel (Pergamon Press, Oxford,
1996), and Organometallics in Synthesis.
A Manual, edited by M. Schlosser (Wiley,
Chichester, 1994).The book under review
fills the gaps left by the now outdated
Collman’s treatment of catalytic organometallic processes and the impressive 14volume Encyclopedia of Organometallic
Chemistry, which contains very little on
homogeneous catalysis.
As pointed out by the editors, homogeneous catalysis is the success story of
organometallic chemistry. The collaboration of an industrial research scientist and
a university chemist provides an authoritative editorship for a comprehensive presentation of homogeneous catalysis in
<
This section contains book reviews and a list of
new books received by theeditor. Book reviews are
written by invitation from the editor. Suggestions
for books 10 be reviewed and for book reviewers
are welcome. Publishers should send brochures
or (better) booka to the Redaktion Angewandte
Chemie, Post?dch 10 11 61, D-69451 Weinheim,
Federal Republic of Germany. The editor reserves
the right ofselecting which books will be reviewed.
Uninvited books not chosen for review will not be
returned.
~~
L
Angm
(%cwii.
I n ! . Ed. Engl. 1997. 36, N o . 13/14
both basic and industrial aspects. The editors have assembled a team of 97 wellknown authors from academia (48) and
industry (49) who work in this field. The
book comprises only four chapters, the
central ones dealing with proven catalytic
processes (“Applied Homogeneous Catalysis”, Chapter 2,542 pp.) and exploratory
research (“Recent Developments in HOmogeneous Catalysis”, Chapter 3, 590
PP.1.
In the introduction the editors give a
brief account of the history of homogeneous catalysis and make the usual comparisons with heterogeneous catalysis.
They stress the importance of cyclical
changes in the relative popularity of the
two types of catalysis as a result of progress in basic discoveries and process technologies, and changes in market requirements and feedstock availabilities, effects
which are further developed in Chapter 2.
They also sketch the attempts to create a
symbiosis between the two types of catalysis, either a t the molecular level (organometallic surface science) o r at the macroscopic level (n-phase processes), aspects
which inspire some parts of Chapter 3.
In Chapter 2 all the basic transformations using transition metal species are arranged according to either reaction types
(hydrogenation, oxidation, hydrosilylation, hydroamination, asymmetric synthesis) or reactants (carbon monoxide and
synthesis gas, unsaturated compounds,
hydrogen cyanide, hydrocarbons).
Reactions with carbon monoxide (184
pp.) are discussed in detail by C. D.
Frohning and Ch. W. Kohlpaintner (hydroformylation) and by a panel consisting
mostly of industrial experts (synthesis of
lower acids, carbonylation of benzyl and
aryl moieties, amidocarbonylation, and
oxidative carbonylation) . This section
provides an updated and concise survey of
a domain where homogeneous catalysis
has had some of its main successes. The
discussions of reaction kinetics and mechanisms, commercial applications, and recent developments give the reader good
insights into biphasic hydroformylation
and methanol carbonylation to acetic acid,
acetic anhydride, and methyl carbonate.
Reactions of unsaturated hydrocarbons are described by a panel of 16 con-
0 VCH Verlagsgeseilsthuft mhH, 0.69451
Weinheim, 1997
tributors (including L. Bohm, Y. Chauvin,
E. Drent, W. Kaminsky, R. Taube, and G.
Wilke) who cover most of the field in
154 pages. Dimerization, codimerization,
oligomerization,
cyclooligomerization,
polymerization of alkenes, of alkynes, and
of 1,3-dienes and the corresponding crossreactions are discussed, including industrial applications. This review of the “-ization” reactions is completed by an
excellent survey of the alternating copolymerization of alkenes and carbon monoxide and a description of telomerization of
olefins, although this is limited to the
manufacture of I-octanol. Finally,
metathesis is reviewed, although too
briefly and with little information on ringopening polymerization.
The treatment of oxidations is mainly
concernd with conversion of olefins to
carbonyl compounds and with acetoxylations and other reactions promoted or
catalyzed by palladium (37 pp., R . Jira),
with details of the Wacker-Hoechst processes and a brief contribution on formation of aliphatic carboxylic acids via aldehyde oxidation (6 pp.). as well as
reactions with aryl- and alkyl-substituted
aromatic compounds (35 pp., R. W. Fischer and F. Rohrscheid). A short review
(13 pp., R. A. Sheldon) on the synthesis of
oxiranes with emphasis on developments
for organic synthesis, especially for chiral
compounds, completes this section (91
pp.), which is important because of the
high selectivities towards oxygenates
achieved in commercial homogeneous
catalytic processes.
The shorter contributions to Chapter 2
focus primarily on recent advances in
practical homogeneous catalysis. The
most instructive of these is the one by R.
Noyori and S. Hashiguchi, which illustrates the use of chiral molecular catalysts
for the synthesis of bioactive molecules.
Examples of the use of monodentate P, or
more commonly bidentate N-N, N - 0 ,
P-P, P-N, and P - 0 ligdnds for the
preparation of terpenes (Takasago), profens, pyrethroids, prostaglandins, secondary alcohols, amino alcohols, amino
acids (Monsanto- Searle), and carbapenems (Takasago) are covered in 19 pages.
The section on reactions with hydrogen
cyanide also provides examples of asym0570-0~33/97j36t3-1547X 17.5Ot 50;’O
1547
BOOKS
metric hydrocyanation of olefins (K.
Huthmacher and S. Krill, 20 pp.). The
contribution on hydrosilylation and related reactions of silicon compounds (B.
Marcicniec, 20 pp.) emphasizes the recent
advances in dehydrogenative coupling of
hydrosilanes and disproportionation of
silicon-containing olefins. Finally, the
lack of efficient catalysts for olefin hydroamination as reported by R. Taube
(14 pp.) clearly demonstrates that homogeneous catalysis is still facing many challenges.
In Chapter 3, Volume 2, some of these
challenges are discussed in the three parts
devoted to development of methods (195
pp.), special catalysts and processes (224
pp.) , and special products (173 pp.) .
One may consider three main areas in
the first section: catalyst recovery, understanding and modeling of catalytic activity, and catalytic C-C coupling reactions.
Several contributions deal with the major
drawback of homogeneous catalysis:
catalyst recovery. Immobilization by
aqueous catalysts (B. Cornils and W. A.
Herrmann, 26 pp.), heterogenization by
other immiscible phases (I. T. Horvath, 5
pp.), and immobilization using supports
(P. Panster and S. Wieland, 19 pp.) are
discussed in terms of advantages and disadvantages for industrial applications, the
best example cited being the Ruhrchemie-Rh6ne- Poulenc two-phase hydroformylation of propene. Ligand-stabilized clusters and colloids (G. Schmid,
8 pp.) and re-immobilized catalysts (H.
Bahrmann, 10 pp.) are suggested as other
approaches; these introduce new technological problems for which membrane
separation offers a possible solution. The
understanding and modeling of catalytic
activity is covered in surveys of catalytic
engineering aspects (M. Baerns and P.
Claus, 15 pp.) and molecular modeling
(R. Klein and R. Schmid, 18 pp.). An introduction to parahydrogen labeling as a
new analytical method in homogeneous
catalysis (J. Bargon, 12 pp.) is also described, as an example of the development
of special in-situ techniques for mechanistic studies. Finally, introductions to
organometallic surface science (J.-M. Basset and G. P. Nicolai, 12 pp.), to FischerTropsch synthesis (W. A. Herrmann, 16
pp.), and to multicomponent or multifunctional catalysts (D. Hesse, 13 pp.)
may indicate new routes to be explored,
especially at the frontier between homogeneous and heterogeneous catalysis. Catalytic C-C coupling reactions are examined from three major aspects which
already provide useful applications in organic synthesis. The Heck reaction and its
variants (Blaser, Jeffery, Bozell, Milstein,
1548
intramolecular . . .) are concisely summarized (W A. Herrmann, 21 pp.), together
with recent improvements using palladacycles and heterocyclic-carbene complexes of palladium. A brief report on arylaryl coupling, Grignard cross-coupling,
and phenol coupling is also provided
(W. A. Herrmann, 6 pp.). Finally, recent
developments in catalytic cyclopropanation (A. F. Noels and A. Demonceau, 15
pp.) mainly concern enantioselective catalysts based on copper and rhodium.
The second section of Chapter 3 covers
several aspects that are not easy to classify. Some undoubtedly correspond to
methods or catalysts, others to reactants
or processes. In the first group are: phasetransfer catalysis and related systems (Y.
Goldberg and H. Alper, 22 p.) describing
mainly oxidation, carbonylation, and
Heck-type reactions under phase-transfer
conditions; membrane reactors (U.
Kragl, C. Dreisbach, and Ch. Wandrey,
12 pp.), where membranes act as catalysts
or physical barriers for bulky components
such as colloids, dendrimeric structures,
etc.; homogeneous electrocatalysis (D.
Astruc, 14 pp.) and photocatalysis (A.
Heumann and M. Chanon, 15 pp.), where
electrons or photons very often participate only in the formation of the catalytic
species from the precursors. In the second
group dealing with catalysts, the review
on biocatalysis and enzyme-analogous
processes (K. Drauz, H. Waldmann, and
B. Sauerbrei, 34 pp.), in addition to a survey of the uses of hydrolases, dehydrogenases, aldolases, and transferases, offers
examples of commercial applications
which can be compared with abiotic catalysts. A summary of the potential uses of
template or host-guest relationships (F.
Vogtle, R. Hoss, and M. Handel, 22 pp.)
completes this contribution by introducing new concepts for homogeneous catalysis, with supramolecular control of the
interactions between the catalytically active site and the reactants. The use of rare
earth compounds (R. Anwander, 27 pp.)
and metallocenes (F. Kiiber, 10 pp.) concludes this second group: the authors
demonstrate that both Group 4 chiral
metallocenes and organolanthanides have
unique stereoelectronic properties for efficient reactions forming carbon-carbon
bonds (oligomerization and polymerization, Diels-Alder reactions, aldolization,
etc.) and carbon- heteroelement bonds
(hydrosilylation, hydroamination, epoxidation, etc.). In the third group, specific
reactants are considered, using aldehydes
and keto compounds for olefin formation
(W. A. Herrmann, 9 and 5 pp. respectively). The analogy between the Wittig reaction and the olefination of aldehydes with
8 VCH Verlagsgesellschaft mhH, 0-69451 Weinhelm, 1997
0570-083319713613-iS48 S 17 50t SO10
diazo compounds mediated by molybdenum and rhenium compounds is first discussed; the catalytic McMurry coupling is
considered as an additional example of
how to go from a stoichiometric process
to a catalytic one by appropriate choice of
the components involved in the mediating
system. Finally, in the fourth group,
specific catalytic processes such as homologation, isomerization, the water-gas
shift reaction, and hydrodesulfuration
processes are considered. Homologation
of methanol (H. Bahrmann, 13 pp.), with
comments on technical applications, completes the treatment of carbonylations
(Chapter 2). The contribution on doublebond isomerization of olefins (W. A. Herrmann, 12 pp.), with special attention to
reaction mechanisms, introduces recent
applications such as asymmetric isomerization. The water-gas shift reaction
(W. A. Herrmann, 7 pp.) is briefly described in view of its involvement in several carbonylation processes and its interest
for the catalytic synthesis of isocyanates
and urethanes. Hydrogenation and hydrogenolysis of thiophenic compounds
(C. Bianchini and A. Meli, 11 pp.) are described in the context of attempts to design a homogeneous process for hydrodesulfuration, a reaction of great
importance in petroleum refining.
The third section of Chapter 3 is also a
collection of short reviews on topics similar to those of the preceding part; they
roughly correspond to specific processes,
reactions, and molecules. In the first
group one finds enantioselective synthesis
and reactions in homogeneous systems.
The very thorough contribution by H.-U.
Blaser, B. Pugin, and F. Spindler (33 pp.)
complements the approach of R. Noyori
and S. Hashiguchi by considering the
technical application of homogeneous
enantioselective catalysts for additions to
C=C, C=O, and C = N groups. Some examples of step-growth and chain-growth
polymerizations are given by B. M. Novak (10 pp.), with special attention to
ROMP processes. A brief account of
biomembrane hydrogenations with water-soluble hydrogenation catalysts (L.
Vigh and F. JoO, 7 pp.) provides a good
example of exotic applications of homogeneous catalysts.
In the second group, other areas of application are described, with specific reactions leading to special products. These
reactions are related to carbon monoxide
chemistry, coupling of unsaturated compounds, oxidations, and C-H bond activation. Reductive carbonylation of nitro
compounds (R. Sundermann and H. J.
Scholl, 9 pp.) is presented, with a pessimistic assessment of prospects for indusAngew Chem In1 Ed Engl 1997,36, N o 13/14
BOOKS
--
trial production. The Pauson-Khand
synthesis of cyclopentenones (V. Rautenstrauch, 10 pp.) also seems to be of doubtful value for commercial applications.
The review on hydrovinylation (P. W. Jolly and G . Wilke, 25 pp.) details the catalysts, substrates, and mechanisms for this
reaction, whose asymmetric counterpart
would be relevant for the synthesis of
bioactive molecules. Also coming from
Miilheim/Ruhr is an exhaustive survey of
the cyclooligomerization of alkynes (H.
Bonnemann and W. Brijoux, 17 pp.), describing the formation of five- and sixmembered heterocycles and six- and
eight-membered carbocycles. The synthesis of diols via catalytic dihydroxylation
(M. Beller and K. B. Sharpless, 16 pp.) is
discussed mainly in its asymmetric version, which is of possible industrial interest for the preparation of intermediates
for pharmacologically active compounds.
Finally, activation of C-H bonds is discussed in two reports. New approaches to
C-H activation of alkanes (A. Sen, 12
pp.) draw attention to the effectiveness of
electrophilic pathways in promoting activation and functionalization of the least
reactive members of the hydrocarbon
family. On the other hand, intramolecular
C - H carbenoid insertion offers new possibilities for the catalytic synthesis of
cyclic hydrocarbons from diazoal kanes
(W. A. Herrmann, 7 pp.), the challenge
now being to achieve enantioselective cyclizations.
In the third group, specific molecules
are considered. The use of carbon dioxide
as a C , building block (E. Dinjus and R.
Fornika, 25 pp.) is discussed, with special
attention to the use of supercritical conditions which are essential for the efficient
production of formic acid and dimethylformamide. The description of a new catalytic synthesis of methacrylates from
propyne (E. Drent et al., 13 pp.) represents an additional example of proper design of a catalyst for highly efficient
methoxycarbonylation reactions. Molecular design is also the basis of a discussion
on the preparation of acrolein and acrylonitrile (W. A. Herrmann, 8 pp.).
Chapter 4. “Epilogue”, focusses on the
numerous scientific and industrial problems which remain to be solved, and
which have been made clear to the reader
in many of the conclusions reached in the
genertil and specific reviews included in
Chapters 2 and 3. The message is that
there is a need for better integration of
theoretical chemistry, chemical kinetics,
and chemical engineering, and for
stronger relationships between groups
working on homogeneous and heterogeneous catalysis.
A n g m Chrm lrir Ed EngI 1997. 36, No 13/14
Anyone who already has some knowledge of molecular transition metal chemistry will find this book extremely useful
in providing a thorough account of the
state of the art in homogeneous catalysis,
both in its accomplishments (Chapter 2)
and current trends (Chapter 3). The organization of Chapter 3 is rather open to
criticism, as it does not have a clear structure. Nevertheless, this chapter provides a
series of essays which complement the
topics developed in Chapter 2 and open
new perspectives. The reader wishing to
study topics in greater depth has access to
over 5000 literature references, with some
from 1996 (and 1997!). Very few errors
could be found, the most noticeable one
being the citation of Reppe’s work on hydroxycarbonylation (p. 146), which was
published in Liebigs Annalen der Chemie,
not in Annales de Chimie (a computergenerated error?). This reviewer was also
pleased to find on page 199 a new spelling
of his name! Some drawings are incomplete, for example structure 2 on page 961.
Lastly, there is a detailed index which will
help in searching the literature on the basis of molecules, reactions, or processes.
To summarize, this handbook is well
justified in view of the immense growth of
interest in homogeneous catalysis since
the “roaring sixties”, and the continuing
role of the subject in highlighting new fundamental problems and in presenting
chemical technology with new challenges.
Despite its price, it should be available in
every laboratory concerned with the future of catalysis and, certainly, of organic
chemistry.
Igor Tkarchenko
Institut de Recherches sur la Catalyse
CNRS
Villeurbanne Cedex (France)
Comprehensive Organic Functional
Group Transformations. Volumes
1-7. Editors-in-chief: A . R. Katvitzky, 0. Meth-Cohn and C. W
Rees. Pergamon/Elsevier, Oxford,
1995. approx. 7800 pp., hardcover
$4437.25.-ISBN 0-08-040604-1
As stated in the first sentence of the introduction, the objective of this monumental work is to cover the enormous
fieid of organic synthesis by describing
methods for introducing or modifying
functional groups. For this huge task the
editors have chosen a structural form
(said to have been conceived over a glass
or two of wine in a London club) that is
simple, convenient, and easily memorized
by the user. In this system the experimental information is arranged according to
Q VCH Verlaggesellschafi mhH. 0-69451 Wemherm, 1997
the number of attached heteroatoms, the
formal valency (“coordination”) of the
carbon atom under consideration, the position in the Periodic Table of the heteroatom(s) directly bonded to that carbon
atom, and the principle of the latest entry.
Accordingly, the six main text volumes
are as follows: Volume 1. Carbon atoms
with no attached heteroatom; Volume 2.
Carbon atoms with one heteroatom attached by a single bond; Volume 3. Carbon atoms with one heteroatom attached
by a multiple bond; Volume 4. Carbon
atoms with two singly bonded heteroatoms; Volume 5: Carbon atoms with
two attached heteroatoms, at least one being multiply bonded; Volume 6. Carbon
atoms with three and four attached heteroatoms. Volume 7 consists of an author
index and a subject index for all the above
volumes.
A work of this nature and size cannot
be reviewed in the same way as, for example, a monograph o r textbook. It can
only be evaluated after working with it on
practical tasks. Therefore we have concentrated here on the two volumes, namely Volumes 2 and 5, that we have already
used. Our presumption that similar conclusions would apply to the other four
seems well justified in view of the scientific
reputations and competence of the individual authors.
In accordance with the above scheme of
organization, Volume 2 begins with alkyl
derivatives, followed by a second part on
aryl and vinyl compounds, and finally a
third part on functionalized alkynes (the
unsubstituted alkynes are covered in
Vol. 1).
The first 30 pages contain a concise, but
complete, survey of methods for synthesizing alkyl halides. Alcohols and ethers
are then treated similarly, including methods. for asymmetric syntheses. This is followed by three very long chapters on the
synthesis of sulfur, selenium, and tellurium compounds, and a further one on
alkyl derivatives containing nitrogen or
other elements of Group 5. Part 1 ends
with the synthesis of alkyl-boron and
alkyl-silicon compounds and an excellent
chapter of 50 pages on the synthesis of
organometallic alkyl compounds. This includes useful tables of Grignard reagents
and titanium alkyls with methods for
preparing them, so that the reader can
quickly review the various possibilities.
Part 2 begins with the synthesis of vinyl
and aryl halides, followed by enols, phenols, thiols, and their ethers. The important aryl- and vinyl-substituted compounds w-th nitrogen o r phosphorus as
heteroatoms are then treated at length
(130 pp.). A chapter on the synthesis of
0570-0833197/3613-1549S 17 TO+ 5010
1549
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