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Handbook of Fluorous Chemistry. Edited by John A. Gladysz Dennis P

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Angewandte
Chemie
soon become clear to the reader of this
book that, in order to use photochemical
reactions for syntheses, it is first necessary to understand the reactions. One
must read about the details of the reaction mechanisms, which are discussed
very thoroughly, and must study the
many well-chosen examples carefully,
so as to be able to decide whether a reaction described in the book can be
adapted to fit the immediate problem
of synthesis, and whether the chance of
success with a doubtful step in the synthesis is high enough to make it worthwhile. The book offers considerable
help with this. For example, it gives
advice about how to select the desired
reaction in a system where there are
competing reactions, about the effects
of changing the reactants or the reaction
medium, about when and how one can
use sensitizers to good effect, and
about possibilities for controlling regio-,
stereo-, diastereo-, or enantioselectivity.
To use this information one needs only a
basic knowledge of photochemical reactions.
One might regret the fact that, by
restricting the scope to photochemical
reactions used for synthesis in the
narrow sense of the word, the book
does not cover other recent applications
of light radiation in detail. For example,
there are processes based on the release
of trapped reagents from specially prepared precursors (“caged compounds”)
by irradiating with light. The latter are,
in fact, discussed briefly in connection
with benzylic C X bond-breaking reactions, although applications such as this
(namely, bond scission) are also not syntheses in the strict sense.
The book is strongly recommended
for everyone whose work is concerned
with synthetic methods, or who wishes
to begin by getting an overview of the
synthetic possibilities of organic photochemistry. Chemists engaged in mechanistic studies can also benefit from it,
as the well-written descriptions of applications can be a source of stimulating
ideas for further studies. As a reliable
source of detailed information, this
book should be available in every scientific library. The book should also contribute to a wider knowledge of the
practical possibilities of light-induced
reactions, thus helping to ensure that
Angew. Chem. Int. Ed. 2005, 44, 4120 – 4122
these gain a permanent place in the repertoire of synthetic methods.
Dietrich Dpp
Institut fr Organische Chemie
Universitt Duisburg-Essen (Germany)
Handbook of Fluorous Chemistry
Edited by John A.
Gladysz, Dennis P.
Curran and Istvn
Horvth. WileyVCH, Weinheim
2004. 595 pp.,
hardcover
E 169.00.—ISBN
3-527-30617-X
When three scientists who opened up an
interesting, many-faceted, and highly
promising new field of chemistry now
write a book about it, what do we
expect to get from them? Naturally, an
excellent comprehensive description of
the current state of knowledge on the
subject. That expectation is thoroughly
fulfilled by the editors of this handbook,
who are also authors of a large proportion of it.
Although the field was opened up
only some ten years ago, the chemistry
of fluorous phases has had a rapid and
far-reaching impact that is scarcely
equaled by any other advance in chemistry. It has stimulated new developments
in areas as diverse as organic synthesis,
coordination chemistry and related catalysis, enzymatic catalysis, separation
techniques, and materials science. That
impact is reflected by the long list of
review articles on individual aspects
that have been published only within
the last five years, and almost every
recent monograph on synthetic methods, catalysis, or fluorine chemistry contains a chapter on the subject. Therefore, the time was ripe for the publication of a comprehensive work covering
the field. The many interested readers
and potential users of the new technology will be especially pleased that the
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gap has now been filled in the form of
this handbook, which contains many
laboratory recipes written by experts in
the field.
After a short introductory chapter,
which gives very helpful explanations
of the terminology and main features
of fluorous-phase chemistry, Chapter 2
provides an interesting account of the
history of its discovery and the first ten
years of its development as a field of
research. The following seven chapters
give a comprehensive, almost textbookstyle, introduction to the fundamentals
of fluorous-phase chemistry, and a
survey of the current state of knowledge
in the area. The reader is provided with
a wealth of information about fluorous
solvents, strategies for recovering fluorous catalysts and reagents, the properties of perfluoroalkyl groups as linkers
or labels and their structural and electronic roles in chemical reactions, the
partition coefficients of different classes
of organic compounds and transitionmetal complexes between perfluorocarbons and organic solvents (with a 32page table), and chromatographic separations using fluorous silica gel as the
stationary phase. Lastly, examples are
described to illustrate under what circumstances it is advantageous to use
“light” fluorous molecules (molecular
masses below 900), and when one
should instead use “heavy” fluorous
molecules (masses above 1100), as well
as explaining how to plan syntheses
using fluorous phases.
In their preface, the editors describe
a long-term aim for fluorous-phase
chemistry as that of developing fluorous
versions of all the important types of
organic molecules that are used in synthesis: building blocks, reagents, and
catalysts. Chapter 10, the longest in the
book with nearly 200 pages and 19 subchapters, gives details of all the synthetic
possibilities and catalytic approaches in
this area that have been investigated
up to now. A comprehensive summary
of all these would make the review inappropriately long, so only a brief outline
is given here.
The first part of Chapter 10 deals
with a number of fluorous reagents,
including reagents for the Wittig and
Mitsunobu reactions, various tin-based
reagents for free-radical reactions, and
oxidizing reagents that can be regener-
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4121
Books
ated. That is followed by reviews on fluorous protecting groups, linkers, and
labels. The next subchapters are devoted
to the use of fluorous ligands in metalcatalyzed reactions, including various
C C bond-forming reactions such as
hydroformylations, as well as oxidations
and reductions. That is followed by
lipase-catalyzed racemate resolutions
for alcohols and esters, using fluorous
components or by carrying out the reactions in fluorous two-phase systems. The
next three subchapters deal with epoxidations of olefins and oxidations of thioethers using hydrogen peroxide or dioxiranes in perfluorinated alcohols, the
regeneration of catalysts, and the use
of microwave techniques in fluorousphase chemistry. The 19 subchapters
have all been written by different
authors, and inevitably there are a few
cases of overlapping, sometimes also
with other chapters.
Chapter 11 (130 pp.) contains 50
detailed laboratory recipes for syntheses, each accompanied by a brief discussion of the reaction type, and important
tips for performing analogous reactions.
This enables potential users, especially
those who are new to the field of fluorous-phase chemistry, to learn about
key reactions and the relevant reagents
4122
or catalysts, and to form an impression
of the amount of synthetic effort
involved and the advantages compared
with conventional methods.
Chapters 12 and 13 highlight in
detail some applications of fluorous
compounds in certain types of materials—surface-active and colloidal systems, nanoparticles, and hybrid materials—and especially in the biomedical
area (50 pp.). The final chapter of the
book, entitled “Fun and Games with
Fluorous Chemistry”, describes some
spectacular and instructive experiments
that can be used as demonstrations,
and thus offers ideas that can help
towards giving chemistry a positive
public image.
On the whole, the handbook leaves
one with a very favorable impression.
However, I have a criticism directed at
the publishers. It is true that typographical layout is largely a matter of taste,
but I find that the lack of a clear distinction between subheadings of different
hierarchical levels is unhelpful, and
also that the typeface of the text is too
small for easy reading. If the reason for
the latter is to economize on space,
then the margins could be reduced without sacrificing clarity, especially since
many of the schemes, figures, and
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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tables already extend outside the text
boundary. Furthermore, the list of contents is not very clearly set out, and it
is not clear how anyone might find it
useful to be given page numbers for
“Acknowledgements” and “References”.
The Handbook of Fluorous Chemistry is a highly relevant and important
resource for readers engaged in many
areas of chemistry, and it should be
available in every chemistry library.
For preparative chemists, it is an excellent laboratory resource for the strategic
planning of syntheses and separations,
and for materials chemists it will reveal
the wide-ranging possibilities for using
fluorous compounds. If the work could
be followed soon by an updated edition
in paperback form, it would make it
easier for experimental chemists to
keep a copy immediately to hand in
the laboratory.
Gnter Haufe
Organisch-Chemisches Institut
Universitt Mnster (Germany)
DOI: 10.1002/anie.200485236
Angew. Chem. Int. Ed. 2005, 44, 4120 – 4122
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