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Ruthenium in Organic Synthesis. Edited by Shun-Ichi Murahashi

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Ruthenium in Organic Synthesis
Edited by Shun-Ichi
Murahashi. WileyVCH, Weinheim
2004. 383 pp.,
E 129.00.—ISBN
The use of transition-metals in
organic synthesis has increased dramatically in the last two decades. Transition
metal catalysts provide new opportunities for performing highly selective reactions that are not achievable by traditional synthetic methods. Many compounds or molecular frameworks that
were impossible to make two decades
ago can now be synthesized efficiently
by the use of transition-metal catalysts.
According to a search in SciFinder,
among the many different transitionmetal catalysts, the metal complexes of
palladium, nickel, cobalt, rhodium, and
ruthenium are the top five transition
metals that are most frequently used to
catalyze organic reactions. The development of ruthenium-catalyzed reactions
has become an emerging field during
the last decade. With the wide range of
oxidation states (from 2 to + 8) and
several different coordination geometries, ruthenium catalysts can form a
variety of intermediates, such as p-allylruthenium, ruthenium-carbene, and
ruthenacycle species. Although certain
ruthenium-catalyzed reactions have
been reviewed separately, there is at
present no comprehensive book available that describes the recent developments in the field of ruthenium catalysis.
Angew. Chem. Int. Ed. 2005, 44, 6269 – 6270
It is, therefore, most timely and welcome
that Shun-Ichi Murahashi has compiled
the book Ruthenium in Organic Synthesis. It consists of 14 chapters in which 23
leading experts cover all the most
important aspects of current research
in ruthenium catalysis.
Following a concise introduction by
the editor, S.-I. Murahashi, in Chapter 1,
M. Kitamura and R. Noyori discuss
hydrogenation and transfer hydrogenation reactions in Chapter 2. As one
expects, the chapter is mainly devoted
to asymmetric hydrogenation of various
functional groups, including unfunctionalized and functionalized olefins,
ketones and aldehydes, and imines.
Chapter 3, by S.-I. Murahashi and N.
Komiya, is concerned with oxidation
reactions catalyzed by ruthenium complexes. Two classes of oxidation processes are described: dehydrogenative
oxidations by low-valent ruthenium
complexes, and oxygenation with highvalent ruthenium-oxo and rutheniumhydroperoxo species.
The next two chapters are concerned
with carbon–carbon bond-forming reactions. Y. Yamamoto and K. Itoh discuss
carbon–carbon bond formation via ruthenacycle intermediates (Chapter 4), and
T. Kondo and T. Mitsudo describe
carbon–carbon bond formation via pallylruthenium intermediates (Chapter 5).
Chapter 6, by R. H. Grubbs and
T. M. Trnka, is devoted to rutheniumcatalyzed olefin metathesis. Following
a brief description of olefin metathesis,
catalyst developments, and mechanistic
considerations, this chapter focuses on
ring-closing metathesis and cross metathesis reactions.
The contribution by H. Nishiyama in
Chapter 7 deals with ruthenium-catalyzed cyclopropanation reactions, covering both normal and asymmetric catalytic cyclopropanation.
In Chapter 8, C. Fischmeister, C.
Bruneau, and P. H. Dixneuf report on
progress in the area of nucleophilic additions to alkynes and reactions via vinylidene intermediates. They describe
ruthenium-catalyzed nucleophilic additions of oxygen-containing nucleophiles
such as water, alcohols, carboxylic
acids, carbamates, and carbonates, and
of nitrogen- and phosphorus-containing
nucleophiles, to alkynes. Developments
in hydrosilylation and addition to C–H
bonds are also reported.
In Chapter 9, F. Kakiuchi and N.
Chatani turn to the subject of ruthenium-catalyzed reactions by activation
of C–H and C–halogen bonds. By using
various ruthenium catalysts, sp, sp2, and
sp3 C–H bonds, as well as carbon–halogen bonds, can be activated, leading to
useful transformations.
R. F. R Jazzar and E. P. K>ndig give
a comprehensive review in Chapter 10
on ruthenium Lewis acid catalyzed reactions. Various processes catalyzed or
promoted by ruthenium-based Lewis
acids are described, for example: ringopening of epoxides, Mukaiyama and
Sakurai reactions, stereoselective sulfoxidation, and various cycloaddition
reactions, including Diels–Alder reactions, 1,3-dipolar cycloadditions, and
hetero-ene reactions.
Chapter 11, by T. Mitsudo and T.
Kondo, describes ruthenium-catalyzed
reactions with CO and CO2. The authors
show how these C1 building blocks (CO
and CO2) can be converted into highvalue organic compounds using ruthenium catalysis.
In Chapter 12, H. Suzuki and T.
Takao report on isomerization of
organic substrates catalyzed by ruthenium complexes. Isomerizations of
alkenyl alcohols, propargyl alcohols,
alkenes, enynes, and dienes are described. Mechanistic information about
these processes that is presented by the
authors gives a very good picture of
how the reactions proceed.
Chapter 13, by H. Nagashima, is
concerned with ruthenium-promoted
radical reactions. After giving a historical background of the development of
this area of research, the author
describes several radical processes promoted by ruthenium complexes, including intramolecular Kharasch addition,
addition of sulfonyl chlorides to alkenes,
and addition of organic halides or sulfonyl chlorides in polymer synthesis.
In Chapter 14, S. Komiya and M.
Hirano describe ruthenium-catalyzed
bond cleavage reactions. There is some
overlap of the material in this chapter
with the chapter by F. Kakiuchi and N.
Chatani (Chapter 9), but the examples
used are clearly quite different.
The book presents an interesting
overview of a fascinating area of
) 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
research. The chapters are of high quality in terms of their content, and are well
written, although attentive readers will
find several typographical and grammatical errors. With regard to literature citations, there are approximately 1350 references, of which over 80 % belong to
the years 1995–2003. In conclusion, this
book has definite value and is strongly
recommended, both for experienced
organic chemists who wish to learn
about recent developments in the field
of ruthenium catalysis, and for other
readers who would like to understand
some fundamental chemistry of ruthenium catalysis.
William Tam
Department of Chemistry
University of Guelph, Ontario (Canada)
DOI: 10.1002/anie.200485282
) 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6269 – 6270
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synthesis, organiz, shunt, murahashi, edited, ichi, ruthenium
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