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Book Review Two Books on Solid Catalysts. Organic Chemistry Using Clays. By M. Balogh and P. Laszlo

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BOOKS
opment at which it is worthwhile to review
the overall picture and take stock. Such a
situation applies in the case of this book
by Ari Koskinen, in which he describes
methods for asymmetric synthesis, illustrated by examples of successes in the field
of natural products. The development of
such methods has now reached a stage
which is leading not just to individual applications but to progress in natural products syntheses on a broad front, and this
in turn is contributing positively to advances in basic principles.
In his introduction the author is concerned to impress on the reader the importance of natural products chemistry, especially by describing examples in the field
of pharmaceuticals. The enormous variety of natural products is well illustrated
by dozens of structures which, like the
schemes appearing later in the book, are
excellently drawn and well set out. The
examples range from very simple odor and
flavor substances through pheromones
and antibiotics to complex molecules such
as cyclosporin, vitamin B,,, and palytoxin. The author offers his readers (or
listeners, since the book is based on a lecture series) a highly original selection of
examples with the aim of stimulating their
interest in the subject. The brief sketch
of the history of natural products in
medicine (regrettably only four pages
long) also contributes to that aim.
This is followed by a short (26-page)
account of the basic principles of stereochemistry, explaining the concepts of chirality. topology, and asymmetric synthesis. The author evidently wished to ensure
that the reader’s understanding of the
subsequent chapters should not be hindered by a lack of knowledge of the fimdamentals of stereochemistry and nomenclature. In the limited available space he
has been able to cover only the basic essentials of conformational analysis and
the stereochemical descriptors. Nevertheless, the use of the terms h r e o and erythro
is discussed, as well as examples of nonlinear effects. Thus the book is intended
mainly for readers who already have some
familiarity with the basic ideas of stereochemistry. It is pleasing to find that
stereoelectronic effects are treated from a
modern standpoint using clearly presented orbital models.
Chapter 3 (55 pp.) describes basic
methods of asymmetric synthesis. Here
again the treatment is limited to the essentials. covering reactions of carbonyl
groups (nucleophilic addition. alkylation,
enolate chemistry, Michael addition) and
of olefins (epoxidation, hydroxylation,
hydroboration, and the Diels-Alder reaction). The introduction to the effects of
steric hindrance (“allylic strain”) on the
course of reactions and to the Cram and
Felkin- Anh models could appropriately
have been included in the first chapter.
However, these topics have been very
skillfully and effectively incorporated into
the next section on reductions and alkylations of carbonyl compounds. The basic
principles of the Felkin-Anh model are
treated too briefly; experience has shown
that students have difficulty in understanding the distinction between this and
the Cram model. I also feel that the Sharpless epoxidation and enantioselective cishydroxylations should have been covered
in more detail in view of their dominant
role as reagent-controlled reactions. The
Corey model to explain the high enantioselectivity of cis-hydroxylations should
be well within the scope of advanced students, and also provides a good teaching
opportunity for explaining the principles
of catalysis in asymmetric reactions. The
surveys giving formulas with the most important reagents, catalysts, and ligands,
together with the names of the relevant
authors, are very useful. In many cases
typical ee values that can be obtained are
also given. Here, however, it would have
been helpful to include short tables showing the range of selectivities actually
achieved.
The fourth and longest chapter
( I 26 pp.) describes examples of syntheses
of natural products in the areas of carbohydrates, amino acids and peptides, nucleosides and nucleotides, polyketides,
isoprenoids, shikimic acid, and alkaloids.
Here again, rather than assuming previous knowledge, the author explains the
structure, biosynthesis, and pharmacological importance of each class of substances. Synthetic reaction schemes with
detailed explanations of the individual
steps are generally accorded an importance equal to that of descriptions of important compounds belonging to the class
under discussion. A rigid and systematic
connection with the earlier method-orientated chapters is not attempted; instead
these are to be regarded as setting the
scene and preparing the reader. In a book
of this limited size the range of examples
cannot, of course. be very comprehensive,
but the author has skillfully presented a
very good selection. This main part of the
book can be regarded as a short introduction to modern natural products chemistry which is complete in itself.
Considering the wealth of information
presented and the many structures shown,
the incidence of errors has been kept reasonably low. Most of these are trivial;
however the omission of the free radical
dots in describing the mechanism of the
endiin antibiotics (p. 13) makes this difficult to understand. This very reasonably
priced book can be thoroughly recommended for all undergraduate and graduate students, as well as researchers and
lecturers, who wish to learn about modern
trends in natural products synthesis.
Karsfeii Krolin
Fachbereich Chemie und Chemietechnik
der Universitlt-Gesamthochschule
Paderborn (FRG)
Two Books on Solid Catalysts
Organic Chemistry Using Clays. By
M . Balogh and P.Laszlo. Springer,
Berlin, 1993. 184 pp., hardcover
DM 188.00.--ISBN 3-540-55710-5
Catalysis over clays is an attractive alternative to the well established conventional chemical methods for many chemical transformations. The applications of
clays in organic synthesis are summarized
here in 17 chapters, each illustrated with
formula schemes and supported by a comprehensive and up-to-date bibliography.
The book is intended for organic as well as
catalysis chemists.
Chapter 1 is concerned with electrophilic
aromatic substitutions. The main emphasis is on alkylations, halogenations, and
nitrations of arenes. Chapters 2 and 3 describe various types of addition and elimination reactions, respectively. Chapter 4
is devoted to oxidation of hydrocarbons
and alkyl groups, ammoxidation reactions.
dehydrogenation of aliphatic hydrocarbons. and oxidation of alcohols, thiols,
sulfides, and amines. Chapter 5 deals with
two types of aromatization reactions, including, for example, dehydrogenation of
cycloalkanes. Chapter 6 deals with the hydrogenation of carbon-carbon multiple
bonds, hydrogenation of aromatic rings,
and reduction of carbonyl and other functional groups. Chapter 7 discusses the use
of montmorillonite and bentonite clays in
the synthesis of hydrocarbons and heterocyclic compounds. Diels-Alder reactions
are known to be catalyzed by Lewis acids,
and the use of clays as catalysts for these
reactions is described in Chapter 8. The
importance of clays in isomerization reactions is illustrated in Chapter 9. Chapter 10 deals with the dimerization of alkenes, reactions of heterocycles, and oxidative couplings of arenes. Montmorillonite,
super-filtrol, and clayfen catalysts are
used for these reactions. The next chapter
is concerned with rearrangement reactions of arenes, illustrated by well chosen
examples. Chapter 12 discusses the con-
BOOKS
densation reactions of alcohols and thiols.
coupling reactions of aromatic compounds, and aldol condensations. Chapter 13 deals with the thermal and hydrolytic decomposition of a wide variety
of pesticides, which is very important
from the viewpoint of protection of the
environment; examples of the degradation of pesticides and decomposition of
organic peroxides are discussed. Chapter 14 summarizes reactions of carbonyl
compounds. the C O group being probably the most versatile functional group in
organic chemistry. The reactions described include the formation of acetals
and ketals, condensation reactions with
amines and anilines. Knoevenagel condensations, and carbonyl group deprotection. Reactions of carboxylic acids and
derivatives with alcohols, arenes, and
ethylene are described in Chapter 15.
Chapter 16 describes synthesis of amino
acids, polymerization of amino acids, reactions of nucleotides, and formation of
peptides from amino acid adenylates.
Lastly. Chapter 17 contains the miscellaneous reactions which are not discussed in
the previous chapters. The book ends with
a glossary and subject index.
Balogh and Laszlo have produced a
book that sets new standards. They inform the readers expertly, comprehensively, and without unnecessarily lengthy detail about the capabilities and range of
applications of the various clay catalysts
described. The book is nicely written and
each chapter contains a separate list of
references. It can be recommended unreservedly for the chemist working in
academia or industry who wants detailed
information about the applications of clay
catalysts in organic synthesis.
Zeolite, Clay and Heteropoly Acid
in Organic Reactions. By Y; Zzumi,
K. UrahP and M . Onaka. VCH Verlagsgesellschaft,
Weinheim/VCH
Publishers, New York, 1992.
166 pp., hardcover DM 128.00.ISBN 3-527-2901 1-7/1-56081-700-3
This book by Y. Izumi, K. Urabe and
M. Onaka describes the applications of
solid catalysts in organic reactions. It contains three chapters with 350 references,
giving a detailed survey of the state of research on this topic up to the end o f 1991.
The first chapter comprises three sections giving a brief introduction to organic
reactions on zeolites and montmorillonite
clay. Each section (except the introduction) is divided into subsections discussing
different reactions. The topics covered are
the use of acid and base sites of zeolites in
Aii,qcw. C ’ l w i i .
Iiir
Ed. Eiigl. 1994. 33. h’o. I N
the 0-alkylation of alcohols to ethers, Nmonoalkylation of aniline derivatives, ring
opening of epoxides, regioselective bromination with adsorbed bromine on zeolite,
aldol reactions, Michael addition reactions, addition of ester enolates to ynoates,
and carbon-carbon bond forming reactions.
Chapter 2 is devoted to clays which are
potential catalysts in organic synthesis.
After a short introduction to clays, this
chapter discusses the structure and composition o f clays, factors determining
their catalytic efficiency, and new catalytic aspects of synthetic clays. Other topics
covered are the selective hydroisomerization of n-hexane, selective dehydrogenation of cyclohexane, selective etherification of n-butyl alcohol, selective hydrolysis of chlorobenzene to phenol, and
metathesis reaction of propene.
Chapter 3 discusses the usefulness of
heteropoly acids in organic synthesis. This
chapter describes the fundamental chemistry of heteropoly acids, and their uses in
acid-base and redox molecular catalysis
for various types of organic reactions.
The authors have succeeded in providing the reader with a lot of information
regarding organic reactions over solid catalysts. The summary tables, reaction
schemes, and literature references make it
easier for the reader to get more deeply
involved in this wide-ranging field of research and facilitate quick access to the
original papers.
The book is a useful addition to the literature on zeolite, clay, and heteropoly
acid in organic reactions. To those who
are seriously interested in organic reactions using solid catalysts, I can recommend reading this neat and well written
book.
Ganesh Pandey
Organic Chemistry (Synthesis) Division
National Chemical Laboratory
Pune (India)
Comprehensive Handbook on Hydrosilylation. Edited by B . Marciniec.
Pergamon, Oxford, 1992. 754 pp.,
hardcover
E 150.00.-1SBN 0-08040272-0
This book edited by Bogdan Marciniec
is an extension of the Polish version of
Hydrosil.vlation, published in 1981. The
present monograph aims to provide a
complete coverage of the literature from
1965 up to the beginning o f 1990. Over
1360 literature references and 750 patents
are included. The volume is divided into
two parts. The first part is a critical survey
C VCH Verlug.sgesrll.sr.huflmhH. 0.69451 Weinheim,1994
of the scope and application of hydrosilylation reactions. The second part is a truly
extensive tabulation of published hydrosilylation reactions from 1965 to 1990.
Part I consists of six chapters which
deal with the systematic trends of the hydrosilylation reaction, focusing on catalyst, silane, and unsaturated substrate.
Chapter 1 is a very brief introduction discussing the rationale and organization of
the subject matter and its relation to other
reviews in the field. Chapter 2 is a survey
o f mechanistic aspects of the hydrosilylation reaction including free radical, acid
and base catalysis, and transition metal
catalyzed reactions. Chapter 3 deals with
the reactivity of the major classes of unsaturated organic compounds and their
utility in the synthesis of organosilicon
compounds. This chapter is organized by
compound class with separate discussions
of alkenes, dienes. alkynes, carbonyls, and
other functional groups. The effects o f
substituents on the organosilane reagents
with regard to reaction rate and regio- and
stereoselectivity are described in Chapter 4. The chapter also includes practical
applications to the synthesis of organosilicon monomers. Chapter 5 is a short discussion of the hydrosilylation reactions of
unsaturated organosilicon compounds,
which are important both as models for
activated curing processes and as routes
to the synthesis of carbosilane oligomers
and polymers. Finally, Chapter 6 covers
some practical applications o f the hydrosilylation reaction including the role of
organosilanes as coupling agents and as
reducing agents for organic substrates.
The use of hydrosilylation in polymer
modification is also discussed. The topics
covered in Part I are very generously illustrated by examples, but sometimes these
get in the way o f the guiding principles.
Also numerous typographical errors,
nomenclature lapses, and hard-to-read
figures make this section of the book difficult for browsing or casual reading.
Part IT of this volume is a nearly exhaustive compilation of hydrosilylation
reactions from 1965 to 1990, and includes
both literature and patent references. The
425pages of data are organized into
tables which list initial reagents, reaction
conditions (catalyst, temperature, time,
solvent, etc.), products with yields, and
references. The primary division of the
tables is according to trisubstituted silanes
of increasing complexity (Si, C, and H
numbers), followed by the type and complexity of unsaturated organic substrates
(C and H numbers). The table is keyed to
a separate bibliography giving the appropriate literature references. Patents are
identified not only by the patent number
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