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Book Review Organoselenium Chemistry. Edited by D. Liotta

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BOOK R E V I E W S
Organoselenium and Organotellurium Chemistry in
an Up-Current
Organic compounds containing selenium and tellurium
have been known since the middle of last century, but because they have been found to be mostly evil-smelling and
toxic, and often obtainable in pure form only with difficulty, they have been relegated to the small print of the textbooks. Only during the last two decades have organoselenium compounds, like modern organometallic transition
metal reagents, established themselves as important tools
in organic synthesis. Modern organoselenium chemistry
began around 1973/1974, at the same time as the publication of two basic monographs by Klayman and Giinther
(Wiley, 1973) and Zingaro and Cooper (Van Nostrand
Reinhold, 1974), and also of the standard work on organotellurium chemistry by Irgolic (Gordon and Breach, 1974).
The volumes reviewed here, namely
Selenium Reagents and Intermediates in Organic Synthesis.
By C. Paulmier. Pergamon Press, Oxford 1986. xiii, 463
pp., paperback, $ 30.00.- ISBN 0-08-032485-1
The Chemistry of Organic Selenium and Tellurium Compounds, Vol. 1. Edited by S. Patai and Z . Rappoport. Wiley, Chichester 1986. xiv, 939 pp., bound, L 150.00.ISBN 0-471-90425-2
Organoselenium Chemistry. Edited by D. Liotta. Wiley,
Chichester 1987. ix, 422 pp., bound, $ 62.25.--ISBN 047 1-88867-2
are evidence of the much increased interest in organoselenium and organotellurium reagents that has arisen during
the past 15 years. The main reason for this is summarized
by Sir Derek Barton in his preface to Paulmier’s book: although organoselenium reagents are in general more costly
and more toxic than the corresponding sulfur compounds,
they react under much milder conditions. For example, selenolate ions are better nucleophiles, and can be more easily introduced by substitution reactions ; selenenyl chlorides are easier to handle and react more effectively with
enolates. Mild reaction conditions are especially important
in reactions of unsaturated molecules with various functional groups, e.g. in natural products chemistry. Some
organoselenium reagents also fulfil the needs which
arise nowadays with regard to chemo-, regio- and
stereoselectivity.
The decrease in bonding strength in the series S-Se-Te
leads to reduced stability in certain selenium and tellurium
compounds, e.g. those with small rings, or molecules with
C=Se or C=Te bonds. However, it is exactly this behavior
which is often useful in organic synthesis, as shown, for
example, by the ease of the RSe/Li exchange in selenoacetals, or in epoxide ring opening followed by spontaneous
loss of selenium or tellurium.
The book by Pauimier is aimed at preparative organic
chemists. The book, written in a fluent style, begins with a
short outline describing classes of compounds, commercially available selenium reagents, and the inorganic selenium reagents of greatest importance for organic chemists.
The preparation and reactions of organoselenium functional groups are described in Chapters 11 to VI. I espe444
cially like the treatment of their reactive properties, e.g. the
sections on syn elimination (p. 132 onwards), and on the
2,3-sigmatropic rearrangements of allylic selenium oxides
(p. 143 onwards). Equally useful are the systematically organized chapters on addition reactions (VII), addition
reactions with cyclization (VIII), oxidation reactions (XII),
and reduction reactions (XIII), the latter including special
reactions using elemental selenium, alkali metal selenolates and COSe. The chemistry of selenium substituted carbocations is outlined briefly, and Chapter IX is devoted to
carbanions ; the main features of selenocarbonyl chemistry
are also clearly presented.
As the title of the book indicates, Paulmier is mainly
concerned with synthetic aspects, and limits the discussions about structure, bonding and spectroscopic data to
what is essential. This leads to a pleasingly concise treatment, which after covering the serious business of the book
still leaves room for a more relaxed chapter (XIV) on special structures, natural products and biologically active
compounds. In this chapter Paulmier also describes examples of syntheses to illustrate the methodology of organoselenium chemistry.
Literature references, which are mainly to work published in the period 1974-1984, are included with each
chapter, and there are useful author and key word indexes.
Although the book has been prepared by photoreproduction of the original typescript, the text (supported by clear
structural formula diagrams and reaction schemes) is easy
to read-it is well worth buying!
Volume 1 of the two-volume work “The Chemistry of Organic Selenium and Tellurium Compounds”, edited by Patai and Rappoport, is not in competition with Paulmier’s
book, as it is totally different in concept. Following the
general pattern of this series “The Chemistry of Functional
Groups”, the 18 chapters by recognized experts deal with
the topics in greater depth. This has resulted in a comprehensive compilation of material in which some of the individual chapters are monographs in themselves. Following
the guidelines laid down by the editors, most of the authors have concentrated on the latest developments rather
than aiming at completeness. However, two particularly
comprehensive articles are the one of nearly 100 pages on
structural chemistry by I . Hargittai and B. Rozsondal,
which may serve as a Se/Te sequel to Hargittai’s book on
the structures of volatile sulfur compounds, and that of
more than 170 pages on complexes with Se and Te ligands,
by H . J . Gysling, which is superbly compiled, and is a mine
of information for inorganic chemists. Other highlights are
contributions on N M R and ESR spectroscopy, mass spectrometry, analysis, heterocycles, and directing and activating effects. The articles on functional groups with Se and
Te in various oxidation states ( N . Sonada and A . Ogawa)
and on derivatives of Se and Te with valencies of four or
more ( J . Bergmann, L. Engman, and J . Sidin) include synthetic applications, but the complete treatment of synthetic
methods and applications is not due to appear until the
publication of Volume 2“’. The two volumes together will
certainly constitute an indispensable, but unfortunately
[*I
Volume 2 appeared late in 1987:
The Chemistry of Organic Selenium and Tellurium Compounds. Vol 2.
Edited by S. Para;. Wiley, Chichester 1987. xiv, 864 pp.. bound,
L 140.00.--ISBN 0-471-91020-1
Angew. Chem. In!.
Ed. Engl. 27 (1988) No. 3
very expensive, handbook on organoselenium and organotellurium chemistry. It is to be welcomed, since this subject
has not been covered in “Comprehensive Organometallic
Chemistry”. It is an advantage to have selenium and tellurium chemistry treated together, with frequent comparisons of structure and reactivity in the S-Se-Te
series.
This helps the reader to understand the basic trends and
relationships in Main Group VI, and contributes to the
systematization of our knowledge.
Liotta’s “Organoselenium Chemistry”, which is likewise
published by Wiley, consists of nine review articles, dealing with the electrophilic, nucleophilic and free radical
reactions of organoselenium compounds, their oxidation
reactions, and the chemistry of selenium-containing carbanions and organic conductors. These specialized aspects
of selenium chemistry are very well described (e.g. in the
article by H. J . Reich on selenoacetals, carbanions and sigmatropic rearrangements). However, the book as a whole
is by no means an alternative to Volume I of the Patai series, especially as the excellent contributions by 7’.G . Back
o n electrophilic and free radical reactions, and by F. S.
Guziec on selenocarbonyls, in the book edited by Liotta,
are to be followed by articles from the same authors in
Vo I u m e 2 of Pa tai/Rappoport[*].
Wov- Walrher du Mont [NB 857 IE]
Fachbereich Chemie
der Universitat Oldenburg (FRG)
In most of the book the chemistry is easy to follow. In
some chapters, however, the material is not as logically organized as it could be, and this leads to a somewhat disjointed presentation. I n some places the equations are not
adequately explained and consequently are not readily understood. In many cases, results from the literature are
given without comment or a critical evaluation of the results; occasionally the equation for an unusual reaction is
presented without comment or speculation as to the mechanism. To include this kind of commentary, however, is a
formidable task, so it is understandable that the authors
chose not to d o so. In other chapters, the chemistry becomes repetitive such that it possibly would have been better to include tables rather than going through example
after example, each with an equation and verbal explanation.
There are relatively few mistakes and inconsistencies,
most of which will be apparent to organic chemists.
Overall, I highly recommend this book both for those
involved in organotin chemistry and in general organic
chemistry. It not only serves as an excellent text for introducing organotin chemistry, but also is an excellent reference source. It is the only book of its kind available.
John K . Stifle [NB 856 IE]
Department of Chemistry
Colorado State University
Fort Collins, C O 80523 (USA)
Tin in Organic Synthesis. By M. Pereyre, J.-P. Quintard.
and A . Rahm. Butterworths, London 1986. 342 pp.,
bound, =f50.00.--ISBN 0-408-01435-0
This book, containing 17 chapters, is divided into four
parts: Part I is an introduction, containing two chapters.
Part I1 concerns the reduction of various functional groups
with tin hydrides, each of five chapters treating a different
functional group. Part 111 covers the synthetic applications, including chapters on the cleavage of tin-carbon
bonds by various reagents, transmetallation reactions
(primarily for the synthesis of organolithium reagents)
and the coupling reactions of organotin reagents in the
formation of carbon-carbon bonds. Part IV covers syntheses involving tin-heteroatom bonds in seven chapters. The references are collected at the end of each
part (rather than at the end of each chapter). There is
an excellent compilation of references on organotin
chemistry. Unfortunately the references cover only
through 1984 (with a few 1985 references) so there is
a two year gap between writing and publication at a
time when the field was undergoing an explosive development. A few noteworthy books and references on the synthesis of tin compounds have not been listed in the references for Part I. With these exceptions, the references are
quite inclusive.
All areas of tin reagents in organic synthesis have good
coverage, with the possible exception of the synthesis of
certain organostannanes in Part I. For example, the reaction of tin amides with monosubstituted acetylenes to yield
tin acetylides and the mild, palladium catalyzed reaction
of hexaalkylditins with vinyl and aryl halides to yield vinyl- and arylstannanes are omitted. Perhaps too much coverage was given to desulfurization reactions of xanthates
with tin hydrides an: on the benzylation, acylation and alkylation of sugars. The discussion of radical cyclization
reactions in Chapter 3 could have been made more coherent and presented more clearly by utilizing the framework
of Baldwin’s rules.
Fine Chemicals for the Electronics industry. By P. Bumfield.
The Royal Society of Chemistry, London 1986. v, 247
pp., bound, L 27.50.- ISBN 0-85 186-636-0
This book contains 14 papers presented at a specialist
symposium in April 1986, and provides a good insight into
the manufacture of chemicals for high-technology applications. Although each of the papers relates to a specialist
topic, the combined effect provides an excellent and nearly
up-to-date picture of this fascinating branch of materials
science. In addition to the more conventional materials
such as luminescent substances, the topics covered include
newer ones such as optical fibers, ceramics and semiconductors, including materials used in solar energy conversion. It is pleasing that the materials discussed include not
only inorganic, but also organometallic and organic substances. The interaction between manufacturing technology and the requirements to be met for different applications (including those concerning purity) comes out very
clearly. It would have been helpful to have a little more
information under the topic “Sampling and Analysis”, including the techniques and their limitations, e.g. limits of
detection. The chemistry involved in the applications is explained more effectively than the chemical manufacturing
processes, owing to the more informative diagrams provided in the former case.
Nearly every contribution illustrates the complexity of
the materials problems nowadays encountered in the area
of advanced technology. I n almost every case one is concerned with high value products which are used only in
relatively small quantities. Some discussion of the international competitive situation, and of the availability of raw
materials, would have been useful, but would have gone
beyond the scope of the report.
A clear impression emerges that much of this high-technology business still relies to a very large extent on providing tailormade systems designed on an empirical basis for
specific applications. Many such areas are still at a development stage, and one cannot yet predict the final out-
Angew Chem Int Ed Engl 2711988) No. 3
445
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