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Book Review Asymmetric Synthesis. By G. Procter

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BOOKS
cess of getting to grips with a new area in
the broad field of nuclear magnetic resonance, and to those wishing to look beyond the boundaries of their own, usually
fairly narrow, specialist area. The price of
this highly desirable work is likely to put
it beyond the means of most private individuals, other than true fanatics. However, libraries whose budgets are not yet
exhausted, despite present-day cuts in
funding, are strongly recommended to
buy it. All readers interested in nuclear
magnetic resonance would certainly appreciate having access to this reference
source. Finally, a suggestion for the publishers: might not a CD-ROM version
tempt private individuals to buy the work,
if the saving in production cost were
passed on to the potential buyer? Admittedly though, for this reviewer at least, the
prospect of browsing via the monitor
screen seems less attractive. By contrast,
the idea of retiring to the sofa with Volume 1 of ENMR is most inviting.
Ludger Ernst
NMR-Laboratorium der Chemischen
Institute
der Technischen Universitat Braunschweig
Braunschweig (Germany)
Industrial Organic Chemicals. By
H. A . Wittcoff and B. G . Reuben.
Wiley, New York, 1996. 531 pp., hardcover .€ 60.00.-ISBN 0-471-54036-6
This book is a completely revised and
enlarged version of Industrial Organic
Chemicals in Perspective. by the same authors, originally published in 1980. It aims
to provide a wide range of users, from students to industrial chemists, with a survey
of the technologies and products of industrial organic chemistry.
The contents are arranged in a clear and
systematic structure. The preface gives an
overview of the chapters that follow, and a
summary of available monographs, encyclopedias, and the most important industrially-orientated journals and on-line data
banks that contain relevant information.
Each chapter also has a useful and often
quite extensive section headed “Notes and
References”, which lists publications for
further reading, recent review articles. key
patents, and sources of information on related topics, and even includes occasional
anecdotes relating to the history of the
petrochemical industry. Often, however,
only the cryptic comment “see note” in the
main text tells the reader that there is a
reference to a source of further information, and one is left to search for the relevant item.
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Chapter 1 (33 pp.) discusses the importance of the chemical industry in the context of the overall economic environment,
and describes modern developments such
as economies of scale, problems of overcapacity, market saturation, research and development costs, and effects of legislation.
Here one becomes aware of one of the
book’s limitations, which also applies to
the later chapters. in that the main emphasis is on the USA chemical industry. Developments in Western Europe and Japan
only appear occasionally and, for example,
the discussion of political influences makes
no mention of European legislation on
chemicals.
Chapter 2 contains a very clear description of the production of basic petrochemicals by the distillation of crude oil and the
subsequent refining processes.
Chapters 3-11 then deal in turn with
these basic chemicals and their associated
downstream chemistry, from ethylene
through aromatics to alkanes. The various
derivatization processes and routes to endproducts are described systematically, with
special attention to polymer production.
Thus the reader is provided with a good
insight into the entire materials flow of the
industry. For example, one can follow the
series of processes leading from ethylene
via ethylene oxide and ethanolamine to
quaternary ammonium compounds. As
one is taken along the route to the endproduct the amount of industrial background information diminishes, so that often the later stages are described only by
reaction schemes with a few general comments about the process. However, one
should not be surprised at this, because
otherwise the book would have expanded
well beyond its planned size. The authors
also give examples of the uses of the endproducts, so as to give an impression of the
range of potential applications. However,
the reader will sometimes find it difficult to
gain a true picture of the importance of the
markets, as the information given is usually
only of a general nature.
As a consequence of the decision to include a very wide range of undoubtedly
interesting topics, the main industrial processes are not treated in such depth as one
finds in other standard works. The reader
from an industrial background may have
hoped to find more detailed factual information, going beyond an introductory
treatment. Also, data such as annual tonnages are not always presented in a convenient form for easy reference, and one has
to search laboriously through the text.
Chapters 12-14 deal with the chemistry
of coal, natural oils, fats, and carbohydrates. The chapter on oils and fats gives
only an incomplete picture of the industrial
Verlagsgesellsehaft mhH, 0-69451 Wemheim, 1996
processes based on these increasingly important feedstocks. Some important processes, such as physical refining, are not
mentioned at all, whereas much space i s
devoted to less important raw materials
and reactions, and some outdated areas of
application are described. In the section on
fatty alcohols the authors seem to be unaware that a process for manufacturing unsaturated fatty alcohols based on a “new
catalyst” has already been in commercial
use for several decades. Even if the authors
consider that the annual tonnages are
trivial in the context of petrochemicals, the
reader has the right to expect that a little
more care is taken after the decision to
devote a whole chapter to these products
Chapters 1 5 and 16, which complete the
book, deal with polymer production and
catalysis.
On the whole the book provides a good
overview of the industrially important aspects of organic chemistry and polymer
chemistry, giving concise and informative
descriptions of the most important chemicals and polymers, and relegating reactions
of little industrial importance to the background. However, it should be regarded
more as a textbook of applied organic synthesis than a detailed description of industrial practice.
Horst Eierdans
Henkel KGaA
Diisseldorf (Germany)
Asymmetric Synthesis. B y G . Procter.
Oxford University Press, Oxford,
1996. 237 pp., paperback E 19.50.ISBN 0-19-855725-6
Enantioselective Reactions in Organic
Chemistry. By 0. cervinka. Ellis Horwood, London, 1995. 194 pp., hardcover $ 119.95.-ISBN 0-13-276239-0
We have here two further additions to
the considerable family of books on the
subject of stereoselective synthesis. As will
be seen below, these are widely different in
all respects apart from their similarity in
length. Procter’s book originated from a
lecture course and is intended for students.
As the title indicates, the emphasis is on
synthesis. The book is concerned with various methods for preparing chiral nonracemic compounds, and describes important applications to the synthesis of natural
products and active agents. The author has
deliberately kept “stereochemical jargon”
to a minimum. Thus, instead of the usual
lengthy introduction explaining all the
terms employed in stereochemistry, the explanations are limited to the expressions
actually used in the book, and are given
0570-0833/Y6/3523-2680B 15.00+ 2510
Angew. Chem. Inr. Ed Engl. 1996, 35.NO.22
BOOKS
where they first appear. All the topics are
treated clearly and systematically.
The subject matter is arranged according to reaction types. Each chapter is selfcontained and includes a bibliography.
Chapter 1 is devoted to diastereoselective
and enantioselective addition reactions of
carbonyl compounds, and Chapter 2 describes reactions of chiral enolates with
electrophiles. The following chapters deal
in turn with asymmetric aldol reactions,
additions to carbon -carbon double
bonds, reductions and oxidations, rearrangement reactions, and enzymatic hydrolyses and esterifications.
All the important concepts of stereochemistry are covered, beginning with the
Cram and Felkin-Ahn models, then
ranging from the Zimmermann-Traxler
transition state through “chiral amplification”, enolate geometry, CBS reduction,
DIOP, BINAP. BINAL-H, alpineborane, RAMP, SAMP, the Claisen and
Wittig rearrangements, etc., to the Sharpless epoxidation and dihydroxylation reactions. The author discusses the preparation and the various applications of chiral
auxiliaries based on the oxazoline, oxazolidinone, sultdm, and q5-CpFe(PPh,)(CO)
structures. Organometallic reagents discussed include allylboranes, allylstannanes,
allylsilanes, organozinc compounds, and
boron, tin, and titanium enolates.
This first edition contains many mistakes such as incorrect structural formulas or printing errors, but most are harmless and of a kind that will be immediately
obvious to the reader who is able to follow
the discussion. As examples, on page 32
the formulas shown for (+)- and (-)-apinene are identical, on page 35 the relative configuration is given as trans instead
of anti. on page 116 compounds 6.40 and
6.39 have become interchanged in the
text, and on page 21 2 the double bond has
been omitted from a molecule that is undergoing hydrogenation. I found no errors more serious than these.
There are a few instances where important reactions relevant to the topic under
discussion have been omitted. For example, the treatment of asymmetric cyclopropanation reactions fails to mention the
well-established chiral rhodium catalysts
described by Doyle, Davies, and Pfaltz.
As many of the chiral auxiliaries appear in
more than one chapter. I suggest that the
second edition of the book should include
an appendix summarizing the different
applications of each of the auxiliaries. Also it would be desirable to break down
some of the chapters into sections so that
changes of topic would be more clearly
evident. This applies especially to Chapters 5 , 6, and 7. each of which is a giant
Angrw. Clwm. 1171.0 1 . Engl. 1996. 35. No. 22
block of nearly fifty pages without subdivisions, the three together occupying over
half the book. The subject index, containing about 500 entries, is satisfactory, and
there are about 400 literature references
extending up to 1993.
The book covers the core aspects of
modern asymmetric synthesis and can
therefore be emphatically recommended
for students and other newcomers to the
subject, especially in view of its affordable
price.
The book by Cervinka is orientated
more towards the fundamental principles
of chirality and enantioselective reactions,
with synthetic applications relegated to a
secondary role.
There are 18 chapters on topics such as
racemate cleavage, enantioselective reactions, strategies for asymmetric synthesis,
synthesis of enantiomeric compounds,
asymmetric reactions using transition
metal catalysts, asymmetric reactions using chiral auxiliaries, enantiomerically
pure building blocks, and enzyme-catalyzed reactions. This range of topics looks
excellent at first glance, but on closer examination it turns out that almost half the
chapters (Chs. 1, 2, 6, 9, 11, 13, and 14)
consist of only one o r two pages each. Often these merely refer the reader to review
articles. If this were an appropriate way of
treating the subject, the author might as
well have replaced the whole book by similar references! Chapters 8 and 18 contain
only literature references (see below).
The work as a whole has the appearance of a classification of the field of stereochemistry into subject areas, amplified
here and there by motley collections of
information. For example, enantioselective cyclopropanation reactions appear in
the section on double bond isomerizations
using transition metal complexes (p. 95),
and the reaction of an allylborane with an
aldehyde is described in the chapter
on hydroboranation reactions (p. 104).
Where topics are treated more thoroughly
the main thread of the discussion tends to
get lost. Often one finds that relatively
unimportant matters are covered in great
detail, whereas more important ones are
only mentioned briefly o r even neglected
entirely. Thus. in the discussion of chiral
ligands for transition metal catalyzed reactions, DIPAMP and DIOP are buried
within a mass of information about
numerous exotic ligands (pp. 69-83), and
in describing the use of Diels-Alder
reactions (pp. 108 ff) there is no mention of the possible formation of regioisomers.
Reading the book is made more difficult by the circumlocutory style and a tendency towards abstract and woolly lan-
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Vc.rlugsgesellschaJtmhH, 0.69451 Weinheim, 1996
guage. For example, it would be difficult
to make sense of the description of kinetic
racemate cleavage on page 55 if one did
not already know what this was all about.
The translation from Czech into English
may be responsible for these problems,
but whether that is the case is immaterial
to the reader.
The difficulties also extend into the formula diagrams. Almost all the equations
lack important information such as yields
and reaction conditions, and equilibrium
arrows are sometimes omitted (e.g., on p.
88). The problems are further aggravated
by the Roman numerals used to identify
compounds. For example, it is not particularly easy to distinguish at a glance
between compounds CXXXVII and
CXXXVIII. In general the quality of the
figures and formulas is not very good. The
more disturbing examples include Figure
12 (p. 34). which at first glance looks as
though a dozen graphics have been accidentally superimposed, Scheme 3 (p. 14),
which could hardly be described as selfexplanatory, and Figure 1 (p. 167), which
shows a “diamond lattice” that could
have been the work of Escher. Also many
molecular structures are shown wrongly:
examples are the Darvon alcohol on page
55, the nonsensical stereochemical structure of compound I1 shown on page 70,
the chiral compounds with C, symmetry
shown in Scheme 2 on page 72, the geminal dimethyl groups that are claimed on
page 87 to appear with 96% ee, the
peracid with only two oxygen atoms on
page 98, and a pentavalent carbon atom
on page 94. There are occasional examples
of incorrect terminology, as on page 18
where “homochiral” and “enantiomericalIy pure” are treated as synonymous. On
page 71 there is a mention of “diphosphines with a chiral group connecting two chiral phosphorus atoms”; in fact there are no
such compounds in the book, but in any
case a phosphorus atom, although it may
be a chiral center, is not itself chiral.
The subject index i s rather scanty, containing only about 260 entries. Chapter 8
consists solely of 205 references (up to the
year 1990) for Chapters 1 -7, and Chapter
18 similarly consists of 416 references (up
to 1994) for Chapters 9-17.
This book is only suitable for the reader
who already has a good grasp of stereochemistry, and who might discover in it a
few facts that he o r she has not previously
known. The contents of the book does not
justify its cost relative to other works on
this subject.
A . Stephen K . Hushmi
Institut fur Organische Chemie
der Universitat Frankfurt am Main
Frankfurt am Main (Germany)
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