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Book Review Reductions by the Alumino- and Borohydrides in Organic Synthesis. By J. Seyden-Penne

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reviewed here has been written by a chemist who is well
versed in the history of the subject, and who thinks of it
historically, reflecting all the many different aspects of chemistry. The particular strength of this account is that it unites
chemistry, the history of chemistry, and the history of the
chemical elements. The early stages of these are described
best and in greatest detail, whereas the treatment of prebiotic
chemistry and related research is rather brief. Thus one finds
an excellent analysis of the early stages of chemical evolution
and the contributions of chemists such as Bunsen, Kirchhoff,
Fisher, and van’t Hoff, whereas the origins of the chemical
basis of life and the corresponding work of Oparin, Haldane,
Bernal, Urey, Miller, Calvin, etc. are not discussed so thoroughly. To that extent the book does not entirely fulfill the
claim of accurately reflecting the state of knowledge at the
end of the 1980s, but despite this it can be strongly recommended.
The author gives an excellent description of the formation
of the lighter chemical elements in the “big bang”, then leads
the reader on through the formation of the heavier elements
in the stars, and describes the origin of the solar system and
of geological minerals. He treats with equal thoroughness
the interstellar medium, interstellar dust, meteorites, and
comets. The account of the chemical basis of life is divided
into the separate aspects of bioenergetics, replication, and
polymerization. The last chapter deals with the question of
chirality, where the author bases the discussion on his previous work, starting from the concept of the amplification of
weak electrical asymmetry.
Subject to the reservations mentioned above, the book can
be recommended for study by chemists, physicists, biologists, geologists, and astrophysicists who are interested in
chemical evolution. It should also be of considerable interest
to scientific historians.
Werner Ebeling
Institut fur Theoretische Physik
der Humboldt-Universitat Berlin (FRG)
Microscopy. 2nd edition. (Series : Physical Methods of
Chemistry, Vol. 4.) Edited by B. FV Rossiter and J. l?
Hamilton. Wiley, Chichester, 1991, XI, 539 pp., hardcover
L 109.00.--ISBN 0-471 -08026-8
This book describes methods of microscopy by which images can be obtained through different “illumination methods”. The volume encompasses ten contributions, each fitting well with the others, from internationally recognized
specialists. The contents are best indicated by the chapter
titles, given here in order of the contributing authors:
1, Introduction: Principles and Practice of Electron Microscopy, 3. Electron Microscopy of Defects in Crystals
(Medium Resolution), and 7. Special Electron Microscopy
Techniques, by John M. Cowley; 2. Electron Microscopy of
Biological (and Organic) Materials, and 4. High-Resolution
Imaging of Crystalline and Amorphous Materials, by David
J. Smith; 5. Electron Diffraction and Microdiffraction, by
John C. H. Spence; 6. Microanalysis by Electron Energy
Loss Spectroscopy and Energy Dispersive X-Ray Analysis,
by Peter Rez; 8. Scanning Electron Microscopy, by Ludwig
Reimer; 9. Light Microscopy, by Walter C. McCrone;
10. Determination of Particle Size, by George L. Beyer.
Two-thirds of the book is devoted to electron microscopy,
which indicates the importance of and the increasing interest
in this method. Modern developments are also to be found
in light microscopy, and the contribution about light mi1534
0 VCH
Verlugsgesellschuft mbH, W-6540 Weinheim,1952
croscopy makes it clear that this field should in no way be
forgotten. The contribution on particle size determination
provides a practical example of, among other things, the
application of light and electron microscopy (also for automated measurement methods).
With the development of electron microscopy to higher
resolution it is increasingly the differences and not the analogies between light and electron microscopy that emerge.
Electron microscopy has therefore been considered in this
book as consistently as possible from the standpoint of the
theory of coherent images, whereas light microscopy was
usually described using the concept of incoherent images.
The wave properties of electrons and the corresponding diffraction effects are set in the foreground. This volume does
not attempt to describe the field completely with results, but
sufficient reference is made to the literature for examples of
applications and further methods. The emphasis on methods
contributes to clarity because the fundamental principles are
not concealed by detail. This book shows both where the
value and the limits of each method lie and gives an impression of the necessary expenditure of time and effort. All
important ideas are explained in an easily comprehensible
form. The good general index makes the keywords, otherwise to be found scattered in specialized publications, easily
accessible. The individual contributions are so fluently written that one will not only consult them but read further with
interest.
The fact that transmission electron microscopy constitutes
the book’s main theme shows that, in this area alone, unusuallyfast and significant advances have been made in the last
few years. All types of equipment and imaging techniques
now available are introduced, for example, diffraction in a
convergent beam, possibilities for imaging and analysis with
scanning transmission microscopy, image processing, and
simulation procedures. Even the very promising method of
holography with electrons is mentioned. Some of these
working methods have only become available for normal use
by outfitting apparatus with digital technology and by employing computers. All the modern methods of contrast generation, scanning microscopy, and image processing are described in the section on light microscopy. Every chapter is
well provided with diagrams, schemes, and illustrations.
This volume, which presents a sound, up-to-date survey,
can be highly recommended to all scientists who want to be
informed about these methods, their theoretical basis, and
the necessary equipment.
Wilhelm Merten
Institut fur Anorganische und Analytische Chemie
der Universitat GieBen (FRG)
Reductions by the Alumino- and Borohydridesin Organic Synthesis. By J Seyden-Penne. VCH Publishers, New York/
VCH Verlagsgesellschaft, Weinheim/Lavoisier TEC &
DOC, Paris, 1991. XIII, 193 pp., hardcover DM 108.00.ISBN 1-56081-099-813-527-28247-5,
Alumino- and borohydrides can be used to achieve selective reductions in high yields, requiring only a simple protocol, and they have therefore rapidly become an indispensable
aid to organic synthesis. Because of the wide variety of special reagents now available, and the large number of efficient
reductions that have been described in the primary literature,
there was a pressing need for an up-to-date review. This
report on the latest situation by J. Seyden-Penne does not
claim to be complete, but by reviewing 605 publications,
0570-0833/92/1111-1534 $3.50+.25/0
Angefi,. Chem. Int. Ed. Engl. 1992, 3f. No. 1 1
most of which have appeared during the last decade
(35 during 1990), it offers an extensive reference source with
particular emphasis on the chemo-, regio-, and stereoselectivity of the reactions.
The book is divided into three parts. The first part, consisting of 13 pages, briefly describes the relevant properties
(solubility, stability, reactivity) of the most commonly used
alumino- and borohydrides, and of a few boranes. The second part (1 26 pp.) deals with reductions of the most important functional groups. This main part of the book covers the
reductive scission of CX, CO, CN, and CP single bonds, and
the reactions of the title reagents with CC, CO, and C N
double bonds, and with CC and CN triple bonds, and ends
with a chapter on the reduction of other substrates (N-, Hg-,
Pd-, S-, P-, Si-, and B-containing compounds). The third
part (12 pp.) gives a tabular survey of reductive preparations
for the most important functional groups, listing the products, educts, reagents, and relevant sections in the book.
These synoptic tables arranged according to the structure of
the product, together with the list of contents subdivided
according to the structure of the substrate and an additional
1 1 -page index organized according to reaction types, enable
the reader to readily locate particular transformations of
interest.
The examples chosen to illustrate the selectivities include
numerous synthetically relevant polyfunctional substrates,
making up a very useful compilation. The main strength of
the book undoubtedly lies in the detailed discussion of the
differential reactivities of various functional groups towards
alumino- and borohydrides, and the clear information that is
given regarding suitable chemoselective reagents for each
case. An appropriate amount of space is also devoted to
substrate- and reagent-induced stereoselective transformations, but the pleasure in reading these sections is marred for
the reasons explained below. Nowhere is there any mention
of yields; however, a few random checks in the original
papers that are cited indicate that the reactions described
give high yields.
Unfortunately, the book contains many errors that could
easily have been avoided by conscientious proofreading.
These include simple slips (for example, p. 39: “most hindered double bond” instead of “least substituted ...”, p. 99:
“trapping of the aluminum enolates obtained from alkyl
halides” instead of “ ... with alkyl halides”, p. 143: “to treat
the sulfones” instead of “... the sulfoxides”), wrongly or
incompletely drawn structures (for example, p. 26: sultone
instead of sulfate, p. 32: free alcohol instead of TMS-ether,
pp. 36 and 148: primary ozonide instead of secondary
ozonide and, accordingly, wrong products shown, p. 94:
missing imide nitrogen atom and missing CH, group in the
chiral auxiliary, p. 52: stereochemistry of the ring junction in
the decalones omitted, p. 97: relative configurations of the
3.5-dimethylcyclohexanones not shown), inappropriate descriptions (e.g. p. 29: “the reaction proceeds with configuration inversion” and p. 37: “the reaction can be regioselective”, as comments on reactions that do not show the
selectivities referred to, or p. 71 : “the reduction follows the
Felin-Anh rule”, as an explanation of the stereoselective
reduction of ketones that do not have a stereogenic center at
the CI carbon atom), and misleading representations, which
are frequent (of all places) in the important chapters on the
stereoselective reduction of ketones (for example, pp. 49, 50,
54: confusion between the major and minor products in the
reduction of C-22 ketones of the steroids series-here also
the methyl group on C-20 is sometimes missing, pp. 62-63:
interchanging of the major and minor products in the reduction of 2-acyl-l,3-oxathiones and the wrong enantiomers
A n g w . Chem. i n ( . Ed. Engl. 1992, 31, No. 11
6
shown, p. 68 : the irrelevant statement that “the two conformations C, and C, are equally populated”, where one is
dealing with different reactivities). Readers interested in the
stereoselective synthesis of steroid side chains or in applying
Eliel’s method for the enantioselective preparation of a-hydroxyaldehydes must definitely consult the original pubhcations.
To summarize, therefore, this book leaves one with a
mixed impression; a thorough revision would be necessary
before this reviewer could agree unreservedly with the recommendation by H. C. Brown in the preface that “this book
should be in the personal library of every chemist engaged in
organic synthesis”.
Peter Metz
Organisch-chemisches Institut
der Universitat Miinster (FRG)
The World of Peptides. A Brief History of Peptide Chemistry.
By 7: Wieland and M . Bodanszky. Springer, Berlin, 1991.
XJI, 298 pp., hardcover DM 198.00.--ISBN
3-54052830-X
When, in 1901 in Berlin, Emil Fischer prepared glycylglycine, the first free “peptide”, no one guessed that this
compound marked the beginning of the history of a fascinating class of substances. Peptides constitute the link between
amino-acids and proteins. The great variety of peptide structures includes compounds with remarkable biological activities. Many important hormones, antibiotics, toxins. sleep
regulators, pain regulators, immunostimulants, immunosuppressants, antitumor and anti-AIDS agents, and a variety of
other active substances, are peptides.
This “world of peptides” is described in the book by
Theodor Wieland and Miklos Bodanszky. The ten chapters
(298 pp.) are as follows: 1. Introduction. Aminoacids and a
Few Early Paradigmatic Peptides; 2. Synthesis of Peptides.
The First Epoch; 3. The Era After Emil Fischer. The Carbobenzoxy Group, Max Bergmann and his Scientific Circle;
4. A Second Breakthrough: New Methods for the Formation of the Peptide Bond; 5. A New Technology: Solid Phase
Peptide Synthesis; 6. Structure Elucidation; 7. Peptide Hormones; 8. Biologically Active Fragments of Proteins;
9. Biologically Active Peptides from Microorganisms and
Fungi; 10. Peptide Research Around the World.
Reading this highly interesting account one is aware on
every page that the authors are thoroughly at. home in this
world. Indeed, in their scientific careers they have had a part
in shaping the history of these developments, through their
fundamental contributions to experimentation and to the
literature. The first few chapters describe in detail the work
of the founders of peptide chemistry (Fischer, Curtius, Abderhalden, Leuchs, Bergmann, and others) and of the pioneers of the post-war period (Du Vigneaud, Rudinger, Merrifield, etc.). One learns more about the difficult relationship
between Fischer and Curtius, and about the temporary shift
of the center of gravity of peptide research from Germany to
the USA. Pioneering advances are related to the subsequent
developments in an admirable fashion; for example, the discovery of the Leuchs anhydrides is linked to an excellent
review of later work on the chemistry of NCA and
polyamino-acids, and that of the benzyloxycarbonyl residue
by Bergmann and Zervas is linked to an account of work on
protecting groups during the years that followed. The rapid
development of peptide chemistry after the Second World
War led to numerous innovations in methods of synthesis
VCH VerlugsgeseffschufimbH. W-6940 Weinheim, 1992
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