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Transition Metals for Organic Synthesis. Building Blocks and Fine Chemicals. Edited by Matthias Beller and Carsten Bolm

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Angewandte
Books
Chemie
Transition Metals for Organic
Synthesis
Building Blocks
and Fine Chemicals. Edited by
Matthias Beller and
Carsten Bolm.
Wiley-VCH, Weinheim 2004.
1314 pp., hardcover
E 389.00.—ISBN
3-527-30613-7
This second, revised, edition of the book
by Matthias Beller and Carsten Bolm on
the use of transition metals in organic
synthesis is an excellent collection of
review articles written by 116 leading
experts. It extends the earlier (1998) edition and gives an overview of the current
state of research, by including a number
of new and exciting contributions to the
field during the past six years. These are
highlighted, for example, in the reviews
by Muiz (“Asymmetric Dihydroxylation
and
Aminohydroxylation—
Recent Developments”), Fu (“Transition-Metal-Catalyzed Hydroboration of
Olefins”), Wasserscheid (“Transition
Metal Catalysis using Ionic Liquids”),
da Costa and Gladysz (“TransitionMetal-Based Fluorous Catalysts”), Lee
and Hlasta (“Microwave-Assisted Catalysis”), Cintas (“Applications of Ultrasound”), and Franci and Leitner
(“Carbon
Dioxide
as
Reaction
Medium for Transition Metal Catalysis”). The revision of the book to take
into account the rapid progress in the
area is indeed timely, from both an academic and an industrial viewpoint.
The main importance of this book
stems from the fact that transition
metals possess a high ability to catalyze
Angew. Chem. Int. Ed. 2005, 44, 3337 – 3339
and mediate a wide variety of organic
reactions, such as C C bond-forming
reactions, hydrogenation, dehydrogenation, isomerization, oxidation, asymmetric synthesis, and hydrosilylation. However, that versatility also makes it difficult to cover the application of transition metals in synthesis comprehensively.
Nevertheless,
by
inviting
contributions from some of the more
renowned and younger leading scientists
in the area, the editors have succeeded
in covering the recent developments
and giving an overview of nearly all
the important reactions for organic synthesis and fine chemicals production
within just 1314 pages.
The contents of this two-volume edition are arranged in six main chapters
(three in each volume), which contain
61 individual review articles on specific
topics, giving a vivid description of the
area of chemistry that is evident from
the titles of the reviews. References at
the end of each review article provide
the reader with easy access to more
detailed information if required. The
comprehensive list of contents allows
one to locate topics of interest quickly.
The examples of catalytic reactions
described in the text are illustrated by
carefully prepared drawings and
schemes.
The arrangement of the subject
matter within the chapters is clear and
systematic, and most chapters provide
exhaustive references up to 2002, and
partially up to the end of 2003. On the
other hand, it must be mentioned that
a few authors who appeared in the first
edition have not updated their contributions. However, that is not a serious
shortcoming of this edition, since those
topics have been updated by excellent
additional chapters written by other scientists.
Volume 1 begins with an impressive
overview by Trost, covering the basic
aspects of organic synthesis with transition metals. The article emphasizes the
opportunities to solve problems of
chemoselectivity,
regioselectivity,
diastereoselectivity, and enantioselectivity, by inventing new reactions catalyzed by transition metals. The first
chapter continues with an article in
which Keim outlines concepts for the
use of transition metals in industrial
fine chemicals synthesis, emphasizing
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the importance of links between academia and industry in this field.
Chapter 2 of Volume 1 consists of 18
review articles devoted to transitionmetal-catalyzed reactions, concluding
with extended contributions on C C,
C N, and C O bond-forming reactions.
Beller and co-authors report on recent
trends in the fields of hydroformylation
and amidocarbonylation. A wide variety
of important topics, including hydrocarboxylation, hydroesterification, and
cyclopropanation (as in the contributions by Alper and Pfaltz) are covered
in more depth.
Several authors also describe important recent developments with palladium-catalyzed reactions, such as the
arylation of amines and alcohols, allylic
substitutions, and Suzuki and Heck reactions, which undoubtedly have great
industrial potential. However, it is surprising that such an important reaction
as the well-known Stille C C coupling
is not included, despite the fact that it
is now well-established in its “traditional” form, and finds many applications in preparative chemistry. A possible explanation for this omission is that
the Stille reaction cannot be easily
adapted for industrial applications. The
last three reviews of Chapter 2 are concerned with the catalytic activities of
lanthanides, bismuth reagents, and
related catalysts in organic synthesis.
Chapter 3 focuses on titanium-,
chromium-, manganese-, zinc-, and
iron-mediated reactions, outlined in 13
reviews. Readers may be amazed to
learn about the wide variety of metals
that can be applied for mediation and/
or catalysis of different transformations.
It is clear from several of the articles
(those by Frstner, Dtz, Alexakis,
Schmaltz, and Jacobi et al.) that enormous advances in the field of transition-metal-mediated reactions have
been achieved in the last few years.
Emphasis is placed upon key developments, which are illustrated with attractive and useful examples. One that
stands out especially is the titaniummediated McMurry reaction, which has
found many applications for the synthesis of natural and non-natural products,
and is therefore highly topical in this
context.
Volume 2 of the book is devoted to
detailed discussions of reductions, oxi-
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3337
Books
dations, and the role of different reaction media in transition-metal-catalyzed
reactions. It begins in Chapter 1 with
five excellent reviews on homogeneous
and heterogeneous hydrogenation, by
Noyori (Nobel Prize laureate, 2001)
and other outstanding authors.
The articles in Chapter 2 of this
volume deal in depth with catalytic oxidations, beginning with a short overview
by Sheldon and Arends of the basics of
oxidation reactions, which emphasizes
the recent progress achieved in oxidation catalysis by describing selected
examples, including catalytic enantioselective oxidations. The chapters on
“Asymmetric Dihydroxylation” and
“Asymmetric Aminohydroxylation” by
Sharpless (one of the 2001 Nobel Prize
laureates in chemistry) and co-authors
give a comprehensive overview of asymmetric conversion of olefins into synthetically very useful diols and aminoalcohols.
The articles in Chapter 3 review
exciting new topics such as transitionmetal catalysis using ionic liquids, catalysis in the liquid phase under high pressure, applications of microwave radiation
and ultrasound for organic synthesis, and
photocatalysis using transition metals.
Thus, the book covers a very broad
range of reactions and describes the
application of transition metals for
organic synthesis and fine chemicals
production, offering readers a concise
and highly informative treatment of
important selected aspects.
This book can be recommended for
all scientists working in the area of catalysis, whether in industrial research and
development or in universities. The
book is less suited as a textbook for
undergraduate students, since not all
the mechanistic concepts are explained
in enough detail to provide sufficient
insights for the less-well-informed
reader. However, it should be of great
interest to students in advanced courses
and to postdoctoral researchers who
have commenced working in this field.
Svetlana B. Tsogoeva
Institut fr Organische und
Biomolekulare Chemie
Universitt Gttingen (Germany)
DOI: 10.1002/anie.200485249
3338
Dead Ends and Detours
Direct Ways to
Successful Total
Synthesis. By
Miguel A. Sierra and
Mara C. de la Torre.
Wiley-VCH, Weinheim 2004.
276 pp., softcover
$ 79.95.—ISBN
3-527-30644-7
The excitement of journeys in total synthesis stems from their unpredictability;
this sentiment is perhaps best encapsulated by some thoughts penned by Professor Albert Eschenmoser: “The complexity in the behavior of organic molecules is such that the first execution of
any chemical synthesis based on a
design is always a venture into the
uncertain, an experiment run to find
out whether and under what conditions
the elements of design do indeed correspond to reality.” Despite recent advances, practitioners of synthesis are still
humbled by the unpredictable reactivity
of complex molecules. The fact that
endeavors in total synthesis seldom
transpire as planned is perhaps not
advertised enough. Accordingly, it is
especially gratifying to find this subject
expounded upon in great detail by
Sierra and de la Torre in their new text.
Dead Ends and Detours provides the
reader with a well-organized glimpse
into some of the trials and tribulations
encountered in approximately 35 magnificent total syntheses. The format and
content is very similar to a review published a few years ago by the same
authors (Angew. Chem. Int. Ed. 2000,
39, 1538–1559); it contains 15 syntheses
in addition to those presented originally
(also those from the review are dramatically expanded here). Over the course
of eight chapters, in which the examples
are grouped according to the type of
unexpected hurdle encountered, the
authors describe measures by which
they were overcome. These range from
small changes of strategy (such as the
fine-tuning of reaction conditions) to
complete strategic overhauls that were
necessitated by having relied on misleading model systems or by the inexplicable reactive behavior of a common
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
functional group. In several instances,
the authors actually carried out computational studies (MM2) to determine
the root of the problem. The computed
result was often in line with that which
was expected rather than that which
was actually observed, which attests to
the empirical reality of synthetic work.
The hurdles faced are often astonishing,
such as the case of an olefin that refused,
for no apparent reason, to be hydrogenated (octalactin, Chapter 4), or an
equally mysterious case of two atropisomers that differed dramatically in
reactivity (damavaricin D, Chapter 3).
Several cases are also presented where,
in hindsight, there is a rationale for the
cause of the failure, yet those reasons
did not seem compelling enough to
rule out a particular approach at the
start. For example, a major change of
plans in a beautiful synthesis of milbemycin (Chapter 5) was prompted by
the detrimental elimination of a sulfoxide group (after an unforeseen epimerization event) instead of the elegant [2,3]
rearrangement that was expected.
Each chapter presents a number of
syntheses (from three to seven), and
describes the key steps in each case.
The discussion of each molecule is
organized into sections: target relevance, synthetic plan, predictable problems, actual synthesis, and evaluation.
This logical format allows the reader to
rapidly ascertain the essence of each
synthetic endeavor and the problems
encountered therein. For the benefit of
new students, key synthetic methods
and concepts are often highlighted in
boxes at the end of each synthesis.
From a more critical viewpoint, the
book contains several spelling, grammatical, and typographical errors, but
is nevertheless well-written and free of
any major factual errors that would misinform readers. One might consider the
subtitle of the book as misleading,
since the book offers no clues on
“direct ways to successful total synthesis.” Indeed, it is the dead ends, detours,
and serendipitous discoveries (the “indirectness”) associated with synthesis that
fuel much of its charm, appeal, and vitality. To be sure, when embarking on the
synthesis of a new structural type, one
must often rely on intuition, since
there are no generally valid “direct
ways.” As Professor Samuel DanishefAngew. Chem. Int. Ed. 2005, 44, 3337 – 3339
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