вход по аккаунту


Modern Organonickel Chemistry. Edited by Yoshinao Tamaru

код для вставкиСкачать
Modern Organonickel Chemistry
Edited by Yoshinao
Tamaru. WileyVCH, Weinheim
2005. 327 pp.,
E 139.00.—ISBN
Complexes of Group X elements that
are available and convenient to work
with have been used in various kinds of
organic synthetic reactions. Nickel was
the first Group X metal to become
available cheaply, and up to the 1980s
its complexes were preferred over those
of palladium and platinum for applications in various organic syntheses, both
as reagents and as catalysts. In the 1990s,
nickel was superseded by palladium and
lost the leading place for use in organic
syntheses. Whereas the rapid progress of
organopalladium chemistry from 1990
on has produced many monographs,
there have been few monographs on
organonickel chemistry during the past
three decades, despite the fact that
original publications on the use of
nickel catalysts for organic synthesis
have continued to appear. The book
Modern Organonickel Chemistry, edited
by Yoshinao Tamaru, serves to emphasize the availability of various nickelcatalyzed reactions developed in the last
decade, and compares the relative
merits of nickel and palladium.
Chapter 1, described by Yoshinao
Tamaru as an introductory guide to
organonickel chemistry, sets readers
the task of learning about the fundamentals of organometallic chemistry,
Angew. Chem. Int. Ed. 2006, 45, 2657 – 2659
basic concepts in coordination chemistry, and elementary organometallic
In Chapter 2, by T. Takahashi and K.
Kanno, cross-coupling reactions of
organic electrophiles with organometallic compounds are categorized according to the organic electrophiles: alkyl,
alkenyl, allyl, and aryl electrophiles.
In Chapter 3, Y. Kobayashi discusses
three types of reactions—1) addition
reactions to alkenes: hydrovinylation,
hydrocyanation, hydrometalation, carbometalation, and Heck-type reactions;
2) reactions of p-allylnickel complexes,
insertion reactions of alkynes, and allylACHTUNGREation of nucleophiles or electrophiles;
3) reactions of nickel enolates. It would
have been better to deal with the first
and second of these, (1) and (2), in
separate chapters. The third part (3)
could have been included in Chapter 2
from a standpoint of oxidative addition.
Chapter 4, by S. Ikeda, deals with
addition reactions to alkynes: hydrogenation, hydrometalation, bismetalation,
hydrocyanation, hydroacylation, carbometalation, and sequential reactions by
multicomponent coupling.
Chapter 5, by M. Kimura and Y.
Tamaru, focuses on functionalizations of
1,3-dienes and allenes and their applications to organic synthesis: dimerization and polymerization, allylic and
homoallylic alkylation of carbonyl compounds, and 1,2- or 1,4-addition reactions.
Chapter 6, by S. Saito, focuses on
cyclooligomerization and cycloisomerization of alkenes and alkynes: cyclooligomerization of strained alkenes such
as cyclopropenes, methylenecyclopropanes, and norbornadiene; cyclotrimerization and cyclotetramerization of
alkynes; cyclooligomerization of 1,3dienes and allenes (cumulenes); and
cycloisomerization of 1,5-dienes, 1,6dienes, 1-en-6-yns, 1,2,7-trienes, and
Chapter 7, by M. Mori and M. Takimoto, deals with carboxylations of unsaturated compounds such as 1,3-dienes,
alkynes, alkenes, and allenes, and the
construction of carbon frameworks by
carboxylation reactions.
Chapter 8, by Y. Tamaru, deals with
carbonylation and decarbonylation
reactions, processes that may not yet
be sufficiently mature for applications in
organic synthesis. Under decarbonylation, two applications are described: the
succinic anhydrides, and the decarbonylation of cyclic anhydrides followed by
cross-coupling with organometallic
reagents. The discussion of carbonylation reactions includes electrochemical
carbonylation, terminal carbonylation in
cascade reactions, and preparation of
carboxylic acids under phase-transfer
Chapter 9, by R. Shintani and T.
Hayashi, collects together nickel-catalyzed asymmetric synthetic reactions
using various chiral ligands. They
include the cross-coupling reactions as
described in Chapter 2, the allylic substitutions by hard carbon nucleophiles
and hydride nucleophiles as described in
Chapter 3, the hydrocyanation and
hydrovinylation of 1-alkenes as described in Chapter 3, nucleophilic additions
of organometallic reagents to aldehydes
and enones, and addition reactions promoted by the activation of carbonyl
Chapter 10, by T. Osawa, takes up
the subject of heterogeneous catalysis.
Heterogeneous nickel catalysts and catalytic reactions are treated from the
viewpoint of organic synthetic chemistry. The author begins by describing the
general characteristics of heterogeneous
catalysts and catalytic reactions. He
compares heterogeneous and homogeneous catalysts and their reactions, and
discusses heterogeneous catalysis in liquids. Next, heterogeneous catalytic reactions for the petroleum refining industry
and the fine chemicals industry are
discussed, followed by diastereo- and
enantiospecific hydrogenations. Finally,
tartaric acid modified catalysts and
catalytic asymmetric hydrogenations of
ketones are reviewed.
This book provides knowledge and
information of high quality, both in the
chapter introductions and in the descriptions of recent developments in organonickel chemistry. The arrangement of
the chapter topics is good, and there are
no overlaps. The references and the
keyword index are of help to readers.
The book can be recommended for
organic chemists, both in universities
and in industrial research and development. It is less suitable as a textbook for
undergraduate students. On the other
' 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
hand, students in advanced courses will
benefit from studying the metal-catalyzed reactions that are discussed in
Modern Organonickel Chemistry, and
the book will certainly give them a good
introduction to the world of metalcatalyzed organic synthetic chemistry.
Yoshiro Masuyama
Department of Chemistry
Sophia University (Japan)
DOI: 10.1002/anie.200585289
The World’s Greatest Fix
A History of Nitrogen and Agriculture. By G. J. Leigh.
Oxford University
Press, Oxford
2004. 254 pp.,
£ 29.95.—ISBN
“This book tells the story of how
humans have used their ingenuity
throughout our history to maintain soil
fertility and avoid famine through productive agriculture” is the opening sentence of this book with its intriguing title
by G. Jeff Leigh. That first sentence
promises a lot. It also hints at who
might be attracted to reading this monograph, and that is anyone who is interested in history, anyone who is interested in science, and also anyone who is
interested in the environment. The title
also provides the focus for the book,
which is nitrogen. One would infer from
the title that nitrogen and agriculture are
somehow connected. That connection is
emphasized early in the book, starting
with Chapter 1.
Of the seven chapters that make up
this monograph, the first is the primer
for the book, setting up what the author
is trying to do, and what the reader
needs to know about chemistry (in a
section aptly titled “All the nitrogen
chemistry you need to know”), about
biology, and about industrial chemistry.
The second and third chapters give a
history of agriculture, which ranges from
the beginning of civilization, with some
intriguing connections to the various
cultures around the world, to the end
of the 19th century. Apparently, the
success of the longer-lived empires in
Egypt, in Central America, in China,
and in Europe (the Romans) all correlate with some recognition of basic
farming techniques such as crop rotations and the use of manure as a
fertilizer. The description of the fall of
the Mayan culture, as a direct consequence of the peopleDs lack of sophistication in the agricultural realm, is compelling. It is interesting to read how two
successful cultures, those of the Chinese
and the Romans, had both written “how
to” manuals that described methods to
be better farmers. A more focused
account of the history of agriculture in
England is given in Chapter 3. Some of
the early attempts to apply scientific
methods to plant growth are described;
the classic tree-growing experiment of
van Helmont is recounted, and various
interpretations are described. The word
“nitre” has a long history, and the author
unravels its first use, its many misinterpretations, and its final and correct
identification. The discussion of the use
of guano as a fertilizer and the resulting
nitrate wars is fascinating from the
viewpoints of discovery, the politics,
and the rapid depletion of this rich
source of nitrogen. An overarching
theme is the fact that many distinguished scholars had predicted the
downfall of western civilization (i.e.,
wheat eaters), on the basis of the rate
of population increase in relation to the
ability to feed these people in the future.
The predictions by Malthus and the
Club of Rome provided both incentive
and controversy, so much so that MalthusDs original publication underwent
many editions, the final one of which
was apparently at odds with the original.
The fourth chapter is a tour de force
on nitrogen, its discovery, and some of
the controversies that surrounded this
simple, abundant small molecule.
Names such as Lavoisier, Cavendish,
Rutherford (Daniel not Ernest), Davy,
von Liebig, and many others populate
this important chapter. It is here that
Leigh interleaves the theories about
nitrogen in the air and nitrogen in the
' 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
soil. During the 19th century, many
eminent scientists did not believe that
nitrogen from the atmosphere could be
converted into ammonia, to be used by
plants. The account of how this was
eventually proven to be possible is
fascinating, and it goes to the very
heart of scientific investigation and
persistence. The breakthrough experiments by Hellriegel and Wilfarth in
Prussia, which showed that pea plants
could fix nitrogen only when they were
exposed to nonsterile soil, opened up
the whole area of biological nitrogen
fixation. The discovery of a connection
with the root nodules and some infectious agent, a bacterium that infected
the soil, was a major leap forward in this
Chapter 5 moves on to a discussion
of the various industrial processes that
involve nitrogen, including the Norwegian arc process, the cyanamide process,
and the Haber–Bosch process. But these
are not just accounts of the chemistry
and conditions—the discussion here
goes further by trying to understand
something about the people who were
attempting to make these processes
work. The highs and lows of Fritz
HaberDs career are recounted here, but
not as a focal point, rather for the sake
of completeness. More important and
fascinating to read is the account of why
countries were racing to find alternative
sources of nitrate (for explosives), and
how they accomplished this. The fact
that Haber and Bosch were the eventual
winners is well known, but what might
not be so evident is how, after the First
World War, other countries tried to get
the secrets of this technology out of the
BASF staff, apparently without success.
Chapter 6 moves back to discuss the
mystery of biological nitrogen fixation,
and includes the sequence of reports and
discoveries that led to our present
understanding of the nitrogenase
enzyme. It is only since 1960 that a
reliable and reproducible method for
extracting the enzyme has become available. This important discovery by the
DuPont company has certainly accelerated knowledge in this area. But what
was still unknown, and remains so to this
day, is how the enzyme accomplishes the
conversion of dinitrogen into ammonia
under ambient conditions. Leigh discusses very recent work that outlines the
Angew. Chem. Int. Ed. 2006, 45, 2657 – 2659
Без категории
Размер файла
188 Кб
chemistry, tamara, organonickel, yoshinao, modern, edited
Пожаловаться на содержимое документа