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Book Review Transition Metals in the Synthesis of Complex Organic Molecules. By L. S. Hegedus

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BOOKS
Professor Knight of Durham University indeed takes as his scope the whole of
the history of chemistry. Not to worry, he
has the scholarship to match! However,
besides the misleading book title, which
the subtitle corrects to some extent. the
chapter titles are other irritants. Each
chapter corresponds to a historical period, and is labeled in the manner of those
books of yesteryear which had names such
as “The Age of Enlightenment”, “The
Age of Revolutions”, and so on. Here,
chapters bear names such as “A teachable
science”. “A deductive science”, etc. Of
course each such label is questionable.
Some--~”Aservice science” for presentday chemistry--raise the blood pressure.
The philosophical bases appear as a little
weak, for a book of this sort which aims at
providing an intellectual history. Chapter 7, “The experimental science”, is not
one of the best. Somehow, it fails to convey what “thinking with one’s hands” entails. “Experimental science” has two
meanings. The jaded meaning is sociological, that of professionals spending their
time in the laboratory and somehow, theorizing from their observations, producing novel knowledge. The stronger meaning is philosophical : the methodology,
which we owe to Boyle and Bacon, of
questioning matter through experiments,
the results of which raise new questions,
leading in turn to new experiments, so that
truth is approached inquisitively rather
than speculatively. Hence. some naive
statements such as “observation with
instruments is remote and theory-laden
compared with the working with testtubes and bottles, and seems somehow
unchemical” are questionable.
This is a delightful introduction to the
history of chemistry. The tone combines
simplicity, down-to earthness, some of the
flavor of speech, and erudition, worn
lightly. It resembles in these respects some
of the outstanding science programs of
the BBC. never condescending, always explanatory. David Knight succeeds in making this slim historical volume into a popularization of chemistry. His trick is to
talk to the layman as if he too were a layman. Here is just one example of such felicitous writing: “the texture of things get
into the memory: the viscosity, mobility
and viscidity of different liquids, and the
gritty, unctuous o r glassy feel of solids;
the undescribable but unforgettable smell
of things.”
One can learn a lot from Professor
Knight’s learned conversation. and I did:
Richard Watson’s description of saturnism at the end of the eighteenth century;
Lyon Playfair‘s 1852 prophetic tirade on
recycling; o r the phrase glyptic ,fownulae
to describe what we nowadays call molecular modeling.
The insularity is not totally unexpected.
Sometimes the constant hagiography of
British scientists rubs raw. But it is involuntary and unsystematic, for instance Laurent’s ideas and methodology get the rich
praise they deserve. A minor irritant is the
abysmal typesetting, swarming with typos. Conversely, the jacket design is admirable. All in all, a highly recommended
book, which any chemist would be well
advised to own.
Pierre Laszlo
Laboratoire de chimie
Ecole polytechnique
Palaiseau (France)
Transition Metals in the Synthesis of
Complex Organic Molecules. By L. S.
Hegedus. University Science Books,
Mill Valley, CA (USA), 1994. 358 pp.,
paperback E 27.95.-ISBN 0-93570228-8
The use of transition metals has revolutionized organic synthesis in various
ways. In many cases reactions that would
otherwise have been simply classified as
“impossible” can be carried out using transition metal compounds. Moreover, much
of the modern armory of the preparative
chemist, especially with regard to chemo-,
regio-, and stereoselective methods, is
based on transition metal-assisted reactions, so that synthetic chemistry without
these has now become unthinkable. This
situation has already been well recognized
by the excellent treatment in Part 111 (Apphxtions to Organic Synthesis) of the
book Principles and Applications of
Organotransition Metal Chemistry (2nd
Edition), by J. P. Collman, L. S. Hegedus,
J. R. Norton, and R. G. Finke (University
Science Books, Mill Valley, 1987). The
development of synthetically relevant
organometallic processes has continued
apace in recent years, and many new applications of transition metal-assisted reactions in the synthesis of complex organic molecules have been published, and
therefore this updated survey by L. S.
Hegedus, covering the literature up to
January 1993, is very welcome.
The main contents of the book are arranged according to the well proven system used in Chapters 13-20 of Collman,
Hegedus, Norton, and Finke. These are
preceded by two short, well structured
chapters (45 pp. in total) on formalisms,
bonding situations, and organometallic
reaction mechanisms. which equip the
reader with the essential tools for under-
standing the following chapters on synthetic applications. Chapter 3 (transition
metal hydrides) is mainly concerned with
homogeneous hydrogenation reactions,
now also including enantioselective reductions using ruthenium-BINAP catalysts.
Chapter 4, on complexes containing
metal-carbon o-bonds, has been extensively revised (with over 100 new references), and gives the reader good insights
into modern organocopper chemistry and
the Fdscinating synthetic possibilities now
opened up by palladium-catalyzed processes such as enyne cycloisomerizations,
cross-couplings, and Heck reactions. The
chapter also includes a new section on reductive cyclodimerizations of alkenes and
alkynes based mainly on zirconium chemistry. In Chapter 5 (carbonyl complexes)
the sections on coupling reactions, carbonylations, and decarbonylations correspond fairly closely to those in Collman
et al., but the chapter also includes some
more recent applications of chiral nonracemic metal acyl enolates. In contrast
Chapter 6 (carbene complexes) consists almost entirely of recent examples of the
various uses of electrophilic and nucleophilic transition metal carbene complexes in organic synthesis, with over 100 new
references. Cyclopropanations, Dotz reactions, photochemical generation and subsequent reactions of ketene complexes, as
well as metal-catalyzed decompositions of
diazo compounds followed by insertion
into C-H or X - H bonds or formation of
ylides, are all described in detail. This
chapter ends with a brief section on carbonyl-olefination using Schrock-type carbene complexes. Many new references also appear in Chapter 7 (alkene, diene, and
dienyl complexes). The use of palladium(1I) complexes to assist the attack on
alkenes by 0-,N-, and C-nucleophiles is
thoroughly discussed, including cyclization-induced rearrangements. Other topics highlighted in this chapter are the use
of iron complexes to protect alkenes and
1,3-dienes, and the regio- and stereoselective formation of carbon-carbon bonds
by nucleophilic attack on molybdenum
diene complexes, and especially on iron
dienyl complexes. Chapter 8 (alkyne complexes) discusses the use of cobalt complexes for the protection of the alkyne function, and in this connection describes new
applications of the Nicholas reaction and
subsequently takes a closer look at the
Pauson-Khand reaction. Cobalt-catalyzed cyclo-oligomerizations of alkynes
provide another major topic of this chapter, which ends with a completely new
section on zircon0 benzyne complexes.
Chapter 9 (q3-allyl complexes) begins
with the telomerization of 1 Sdienes, with
BOOKS
~
special attention to recently developed in-
trarnolecufar processes catalyzed by palladium. iron, or nickel. This is followed by
a long section concerned mainly with re-
gio- and stereoselective reactions of n-allyl palladium complexes using C-. N-, and
0-nucleophiles, their reduction to olefins,
and their elimination reactions yielding
1,3-dienes. Also covered in this chapter
and supported by a wealth of new literature references are allylic alkylations using vinyl or aryl tin compounds, palladium ene reactions and cascades based
thereon, and formal [3 + 21-cycloadditions
via trimethylenemethane intermediates.
The chapter ends with a survey of other
q3-allyl metal complexes (of Mo, W, Fe,
Co, and especially Ni). Chapter 10 (arene
complexes) gives a n up-to-date review of
the synthetic applications of arene-chromium tricarbonyl complexes, including nucleophilic substitutions of aryl halides, regio- and stereoselective additions of
.C-nucleophiles, along with possible types
of follow-on reactions, ring lithiations,
and reactions involving activation of the
benzylic position. Also the potential for
using alternative metals that have not yet
been thoroughly investigated in this context (Fe, Ru, Mn) is briefly considered at
the end of this chapter.
With this updated survey of transition
metal-assisted methods the author has
succeeded in producing an independent
and highly stimulating book, whose particular strengths lie in the carefully chosen
examples, the excellent figures, and the
succinct explanations. Apparently as a result of limiting the coverage to reactions of compounds containing transition
metal-carbon bonds, as in Collman et al.
(see p. 6), the enormously important catalytic epoxidations and dihydroxylations
are unfortunately not included. Nevertheless. this book, which is intended both as
the basis for a one-semester course for
upper-level students and as an overview
for practicing chemists, sets a new standard in the treatment of this subject matter. It is emphatically recommended for
use by advanced students and by all academic and industrial chemists concerned
with synthesis.
Peter Mets
Organisch-chemisches Institut
der Universitat Munster (FRG)
Bioinorganic Chemistry. Edited by I.
Bertini, H. B. Gray, S. J Lippard and
J. S. Valentine. University Science
Books, Mill Valley, CA (USA), 1994.
61 1 pp.. hardcover E 28.95.-ISBN
0-935702-57-1
Although this work is in fact a textbook
on bioinorganic chemistry, it does not aim
to compete in quite the same market as
other recent introductory textbooks by W.
Kaim and B. Schwederski, by J. A. Cowan, and by s. J. Lippard and J. M. Berg. It
consists of nine chapters by a total of
15 authors, covering a wide variety of topics, mostly in considerable detail. The
reader will not find here an introduction
addressing the question “What is bioinorganic chemistry?”, nor a systematic treatment of the basic principles of coordination chemistry, biochemistry, and
physical methods. Instead the book aims
to fill the gap between introductory
textbooks (such as those mentioned
above) and highly specialized review
articles. The level of the contents would
be more accurately reflected by a title
such as “Advanced Bioinorganic Chemistry”.
The chapters are of a fairly uniform
length, with the exception of Chapter 1 , a
much shorter one in which E. C. Theil and
K. N. Raymond give a clear and understandable description of the storage,
transport, and biomineralization of transition metals (including zinc). In the second chapter I. Bertini and C. Luchinat
discuss the reactions of zinc enzymes.
Taking carbonic anhydrase as an example, they illustrate the importance of
N M R spectroscopy and protein crystallography in this field. For some important
zinc enzymes the authors describe possible catalytic cycles. The chapter also includes a short section on coenzyme and
vitamin B I Z .
The wide-ranging importance of calcium in the regulation of cell functions is
recognized by devoting a separate chapter
to this topic. After a short introduction (in
which we also learn about the calcium
content of a “good” beer), S. Forsen and
J. Kordel describe the methods used to
measure the concentration and distribution of calcium in cells. This is followed by
sections on the transport and regulation
of C a 2 + ions in higher organisms and on
CaZ receptor proteins in cells. In Chapter 4 G. B. Jameson and J. A. Ibers contribute a review of both biological and
synthetic dioxygen-transporting molecules. They begin by describing the
thermodynamics of dioxygen transport
and the biomolecules hemoglobin, hemocyanin, and hemerythrin, then go on to
I
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1036
6
VCH Verlagsgesellschu/i mbH, 0-69451 Weinheim. f995
~
discuss some aspects of the chemistry of
molecular oxygen, iron, copper, and
cobalt. The chapter ends by describing the
structural characteristics of dioxygenbinding biomolecules and synthetic complexes.
Chapter 5, by J. S. Valentine, is concerned with the reactions of the 0, molecule that are of biological importance. After dealing with the chemistry and toxicity
of O,, the author discusses the relevant
enzymes, namely cytochrome c oxidase,
oxygenase, catalase, peroxidase, and
Cu,Zn superoxide dismutase. Chapter 6 is
devoted to electron transfer processes.
H. B. Gray and W. R. Ellis Jr. describe
the various electron transfer proteins
and the types of biological processes in
which electron transfer plays a part
(e.g. photosynthesis). The emphasis is
on theoretical aspects, especially with regard to long-range electron transfer in
proteins.
In Chapter 7 E. I. Stiefel and G. N.
George discuss proteins containing metal
sulfide centers. They begin with iron sulfur proteins, concentrating appropriately
on relevant (model) complexes of low
molecular mass. Hydrogenases and nitrogenases are then discussed (including the
recent crystal structure study by J. Kim
and D. C. Rees). Chapter 8, by J. K. Barton, deals with interactions and reactions of metal ions and their complexes
with nucleic acids. Topics covered include tris(phenanthro1ine) metal complexes, zinc-finger proteins, the MerR protein,
and Fe”-bleomycin.
In the last chapter S. J. Lippard discusses practical applications of bioinorganic chemistry, concentrating on the uses
of metal compounds in medical diagnostics and chemotherapy. Cisplatin is treated at length (over 50pages) as a case
study. This chapter is also of interest in
that the author broadens the discussion to
include aspects beyond basic research, for
example in drawing parallels between protagonists of new inorganic drugs and Hollywood film producers.
The inclusion of color plates and about
2000 (!) literature references add to the
appeal of this excellent book, and there
are few textual errors. It is unfortunate,
however, that the IUPAC recommendation to enclose formulas of coordination
compounds in square brackets has only
been followed consistently in Chapter 9. I
feel it is especially important in a student
textbook to stick to the accepted rules of
nomenclature.
Anyone who already has an elementary
knowledge of bioinorganic chemistry,
even if only from an introductory lecture
course. will find this book useful and
B fO.00+ .2.5/0
0570-0~Y33/95/0909-1036
Angew. Chem. Int. Ed. Engl. 1995, 34, N o . 9
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