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Organolithiums Selectivity for Synthesis. By Jonathan Clayden

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Organolithiums: Selectivity for
By Jonathan Clayden. Elsevier Science/Pergamon,
Amsterdam 2003.
384 pp., softcover
E 45.00.—ISBN
Organolithium chemistry has developed
rapidly since the groundbreaking studies
by the groups of Ziegler, Wittig, and
Gilman. Accordingly, the last few decades have witnessed considerable activities that broaden the scope of application of organolithium compounds in
synthesis. Key issues have been all
aspects of selectivity, such as chemoselectivity, regioselectivity, and stereoselectivity. It is mainly the selectivity
issues that are featured in the book by
Clayden, whereas historical, structural,
and mechanistic aspects are touched
upon only briefly to give a background
for the discussions of selectivity.
As the title implies, this book is not a
comprehensive treatment of organolithium chemistry as such. It rather
concentrates on information needed
for the application of organolithium
reagents in organic synthesis. Considerable attention is given to the choice of
the proper organolithium reagent, solvent, reaction conditions, and additives.
Mechanistic implications are discussed
mainly to the extent necessary to justify
the choice of reaction conditions, etc.
This book is therefore written for the
practitioner, but it can serve equally well
for graduate students who are interested
in an introduction to organolithium
chemistry and its importance for synthesis.
The book highlights the developments of the last three decades and gives
useful guidelines for the preparation of
organolithium reagents by various
routes, and for attaining high selectivities in reactions using organolithium
reagents. After a short introduction (ca.
10 pp. ), Chapter 2 (ca. 90 pp.) covers
methods for deprotonating organic compounds using lithium bases. Considerable attention is given to substitutentinduced ortho- and lateral lithiation of
aromatic and heteroaromatic compounds. Chapter 3 (ca. 40 pp.) is devoted
to the preparation of organolithium
reagents by halogen/lithium exchange
and related reactions. Chapter 4 (ca. 15
pp.) deals with the formation of organolithium compounds by reduction with
metallic lithium. Chapter 5 (ca. 70 pp.)
addresses the stereochemical aspects of
organolithium compounds, their configurational stability, and the methods for
enantioselective formation of organolithium reagents. Chapter 6 (ca. 30 pp.)
discusses the stereochemistry of the
reactions of organolithium compounds
with electrophiles. Here reactivity issues
such as kinetic resolution are discussed
in detail. Chapter 7 (ca. 60 pp.) gives a
detailed account of carbolithiation
(mainly intramolecular) of C = C
double bonds. Chapter 8 (ca. 20 pp.)
describes rearrangements of organolithium compounds that are important
for synthesis, such as the Brook and
Wittig rearrangements. Finally, Chapter
9 (ca. 10 pp.) concludes the book with
nine didactically well-chosen examples
of the application of organolithium
reagents in synthesis, illustrating the
increase in synthetic efficiency that can
be gained by the judicious use of selective organolithium reagents.
Overall, the author has mastered
quite well the challenging task of discussing organolithium compounds from
the standpoint of selectivity in synthesis,
but his neglect of certain topics leaves
room for improvement in a future
edition of the book. For instance, the
addition of organolithium reagents to
the carbonyl group of organic reaction
partners is not covered at all, despite the
fact that there are fundamental selectivity issues in carbonyl addition reactions
6 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
(such as competition between enolization and addition, or stereoselectivity
aspects) that would be of concern to
every chemist engaged in synthesis.
Secondly, there are only a few examples
of reactions of allylic organolithium
compounds, with attendant selectivity
issues such as regioselectivity, and they
are spread over various chapters. A
systematic treatment in a separate chapter would have been much to the benefit
of the readers. Positive mention should
be given to Chapter 6 dealing with the
stereochemistry of the reactions of
chiral organolithium compounds. This
chapter gives an insightful treatment of
this complex topic. Also the table summarizing information on the configurational stability of various chiral organolithium compounds is likely to be copied
many times!
Technically this book is well produced. Clear formula schemes and the
numbering of the formulas make for
easy reading. Any book of this size has
errors; so does this one. But fortunately
most of the errors are easily spotted and
therefore of no consequence. All in all,
this book is a good buy, as it offers a lot
of useful and easily located information.
Reinhard W. Hoffmann
Fachbereich Chemie
Universit+t Marburg (Germany)
DOI: 10.1002/anie.200385017
Multilayer Thin Films
Edited by Gero
Decher and Josep B.
Schlenoff. WileyVCH, Weinheim
2003. 524 pp.,
E 179.00.—ISBN
Since the “rediscovery” by G. Decher
and co-authors in 1990 of the layer-bylayer (LbL) method for depositing a film
of an oppositely charged polyelectrolyte
on a charged surface (which had already
been described in articles by Iler in
Angew. Chem. Int. Ed. 2003, 42, 4426 – 4428
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clayden, jonathan, synthesis, selectivity, organolithiums
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