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Organosilanes in Radical Chemistry. Principles Methods and Applications

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Organosilanes in Radical
Chemistry
Principles, Methods and Applications.
By Chryssostomos
Chatgilialoglu. John
Wiley & Sons, New
York 2004. 227 pp.,
hardcover
$ 90.00.—ISBN
0-471-49870-X
Organosilanes in Radical Chemistry is a
mine of information. The main literature coverage is for the 1990s, although
in some cases references to earlier
work and to results published in 2003
are included. The author has had a
very important influence on the use of
silyl radicals, and here he has managed,
within the compass of a little over 200
pages, not only to review his subject
but to include extensive background
material of general importance to radical chemistry. The text and diagrams
are set out in a neat and pleasing
manner, and the whole work is enjoyable to read and also easy to understand.
The author"s evident mastery of the field
pervades the entire volume.
The table of contents and the index,
when used together, allow fairly ready
access to the subjects covered. The first
three chapters deal with: 1. the forma-
4124
tion and structure of silyl radicals
(including crystal structures, spectral
measurements, and theoretical calculations), 2. bond dissociation energies,
and 3. hydrogen donor ability of silicon
hydrides towards carbon-, oxygen-,
nitrogen-, and sulfur-centered radicals.
There follows an extensive chapter on
the use of silanes, especially tris(trimethylsilyl)silane, for reductive removal
of halogens, chalcogens, and hydroxy
groups (the latter by the Barton–
McCombie reaction) from organic compounds. Useful tables of rate data are
included, together with an interesting
selection of examples. The performance
of other silicon hydrides and of the
recently introduced silylated 1,4-cyclohexadienes as sources of silyl radicals is
discussed. A chapter is devoted to the
process of hydrosilation of multiple
bonds, especially in alkenes, alkynes,
carbonyl groups, other carbon–heteroatom multiple bonds, and the Brook
rearrangement. Ring closures onto
cumulenes and heterocumulenes are
also reviewed. The cyclization of silicon-centered radicals receives a chapter
of its own, which also covers the related
processes of homolytic transfer of silyl
groups and intramolecular substitution
at silicon. Of particular interest to synthetic chemists is the survey in Chapter 7 of methods for making carbon–
carbon bonds by using processes mediated by silyl radicals. The author gives
an excellent choice of examples, which
illustrate firstly intermolecular reac-
3 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
tions, and then cyclizations leading to
carbocycles or to heterocycles. There
are also sections on the formation of
carbon–heteroatom bonds, rearrangements, and cascades of sequential radical processes. The discussion emphasizes
very effectively the impressive structural complexity that can easily be
assembled by radical methods based on
silicon. Of course, similar transformations can usually be achieved with stannanes, but their use can generate problems associated with the toxicity of
some organotin compounds and the
environmental damage they can cause.
In all the chapters dealing with synthetic
radical chemistry, the extensive provision of rate data greatly enhances the
reader"s appreciation of the reactions.
The book concludes with a survey of
polysilane chemistry—mainly poly(hydrosilane)s, silylated fullerenes, and silicon surfaces.
Chatgilialoglu"s treatment is definitely a major contribution to the
review literature on the important subject of radical chemistry, and his book
will be of significant value to organic
chemists—both to those with synthetic
and mechanistic interests and to polymer chemists.
Derrick L. J. Clive
Chemistry Department
University of Alberta, Edmonton (Canada)
DOI: 10.1002/anie.200385175
Angew. Chem. Int. Ed. 2004, 43, 4123 – 4124
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