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Book Review Modern Acetylene Chemistry. Edited by P. J. Stang and F. Diederich

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BOOKS
Diazo Chemistry 11. Aliphatic, Inorganic and Organometallic Compounds. By H . Zollinger. VCH Verlagsgesellschaft, Weinheim, 1995. 522
pp., hardcover DM 198.00.-ISBN
3-527-29222-5
Part I1 of this splendid monograph by
Heinrich Zollinger covers aliphatic, inorganic, and organometallic diazo compounds, and, as the author explains in the
introduction, its publication alongside
Part I (aromatic and heteroaromatic diazo
compounds) now brings together the long
separated “sisters and cousins”. It can be
said at the outset that these two volumes
certainly belong together, and the combined work i s undoubtedly one of the best
ever surveys of the many and remarkably
varied aspects of diazo compounds.
The structure of Part I1 closely follows
that of Part I ; the author avoids unnecessary repetition of the general discussions
in Part I while also not assuming too much
prior knowledge. The 11 chapters treat every aspect of the chemistry of the compounds defined in the title, with comprehensive coverage of the literature up to the
fall of 1994, supplemented by extensive
footnotes referring to more recent work.
Chapter 1 (10 pp.) briefly outlines the
history of developments in aliphatic diazo
compounds and explains the recommended system of nomenclature. Chapter 2 (84
pp.) contains a very thorough and precise
description of existing methods for preparing such compounds together with discussions of alternative possibilities. The
author first explains the general principles
of the preparative methods, then describes
each individual method in turn with many
examples. The methods based on diazo
transfer reactions are treated especially
thoroughly.
In Chapter 3 (25 pp.) inorganic diazo
compounds are treated in greater detail,
with special emphasis on metal complexes
with N, ligands and diazo derivatives of
boron hydrides. This chapter also includes a concise and informative survey of
the chemistry of nitrogen fixation.
Chapter 4 (23 pp.) and Chapter 5 (45
pp.) are concerned with mechanistic and
kinetic aspects of “aliphatic” diazotization reactions. Topics discussed include
the nitrosylation of alkyl amines, the
mechanisms involved in the diazoalkane
synthesis, the carcinogenicity of N-nitrosamines, and the structure of aliphatic
diazo compounds. On the latter topic
there is a useful critical discussion of the
large amount of spectroscopic data and
theoretical results on this class of compounds, which is not available elsewhere
in such a concise form.
2154
$3
As one expects, much space is devoted
to the reactions of aliphatic diazo and diazoniuni compounds. Chapter 6 (49 pp.)
deals with reactions in which the N, fragment remains intact. Here the author
devotes special attention to 1,3-dipolar
cycloadditions, and gives convincing evidence of the great potential value of such
reactions for organic synthesis. Chapter 7
(64 pp.) discusses the often complicated
situations that occur in dediazotization
reactions involving diazonium intermediates. The mechanistic aspects of deamination and its synthetic applications are explained in precise detail.
The large and important group of dediazotization reactions that proceed via carbenes and carbenoids are treated in Chapter 8 (77 pp.). In discussing every aspect of
the reactions of diazo compounds of carbenes the author again presents an amazing wealth of information. As well as the
classical applications in organic synthesis
(including the Wolff rearrangement and
the Arndt-Eistert synthesis) the chapter
covers recent developments such as the
addition of diazo compounds to fullerenes
and applications in enantioselective syntheses. The part of the book concerned
with reactions is completed by Chapter 9
(37 pp.), which collects together various
other reactions of aliphatic diazo compounds, such as electrophilic and nucleophilic substitutions at the a-carbon atom,
electron transfer processes, and redox
reactions.
In Chapter 10 (34 pp.) the author discusses the complexation of diazonium and
diazo compounds with main-group and
transition metals. Here one is again impressed by the comprehensive nature of
this monograph. Chapter 11 is an epilog
in which the author rounds off the twovolume work on diazo compounds with
a broad survey of the historical development, extending from the original discovery by Peter Griess to the organometallic diazo compounds. The book is
completed by a list of literature citations
and a very comprehensive index, which
facilitates using the work as a reference
source.
In common with the first part (Diazo
Chemistry I) this second volume too is a
must for all chemists with an interest in
diazo compounds, and their personal
libraries should include both volumes.
Moreover, the excellent presentation of
the contents and the high standard of
writing make both books a pleasure to
read.
Thomas Zieglrr
Institut fur Organische Chemie und
Isotopenforschung
der Universitat Stuttgart (Germany)
VCH Vrrlu~gesellsr.i~uf~
mhH, 0-69451 Weinhrim, 1996
Modern Acetylene Chemistry. Edited
by P. J. Stang and F: Diederich. VCH
Verlagsgesellschaft, Weinheim, 1995.
506 pp., hardcover DM 168.00.ISBN 3-527-29084-2
This book fills a gap that has existed for
about twenty years. Everyone who has
observed and experienced the renaissance
of acetylene chemistry during the past
10-15 years has
been aware of the
lack of a compreModem
hensive source of
Ace@1ene
information on the
Chemistry
subject.
The editors of the
book,
both
of
whom have themselves made important contributions
to acetylene chemistry, have succeeded in persuading nearly
every prominent researcher in the field to
contribute an article, with the result that
practically all modern aspects of compounds containing triple bonds are discussed. In the introductory chapter D. A.
Plattner, V. Li, and K. N. Houk describe
the latest developments in the theoretical
treatment of acetylenes, diacetylenes,
polyacetylenes, and linear and cyclic C,
species with n-values from 2 to 18. Other
articles report on cyano- and halogen-substituted acetylenes (Ch. 2, H. Hopf and B.
Witulski), alkynyl-iodonium salts (Ch. 3,
P. J. Stang), and phosphaalkynes (Ch. 6,
M. Regitz, A. Hoffmann, and U.
Bergstrlsser). The synthesis and reactive
properties of the alkynyl-iodonium salts
are treated very comprehensively, whereas in Chapters 2 and 6, after describing the
synthesis of the compounds and their general reactive properties, attention IS concentrated on a few special areas, such
as the reaction of cyanoacetylenes with
cyclophane derivatives, the use of
iodoacetylenes in natural products syntheses, and the reactions of phosphaacetylenes yielding phosphorus-carbon cage compounds. Chapter 4, by
G. G. Melikyan and K. M. Nicholas, is a
general survey of the synthesis and reactions of metal-alkyne-n-complexes. The
binuclear dicobalt-hexacarbonyl-alkyne
complexes and the corresponding propargylium complexes that are described here
also appear again in other chapters as synthetic building blocks. For example, the
former are used in the Pauson-Khand
reaction for synthesizing cyclopentenones
from alkynes, alkenes, and carbon
monoxide, as described in thorough detail
by J. A. Casalnuovo and N. E. Schore in
Chapter 5. The first part of this chapter
057~t-~X33j9n~35IX-2/54
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AnZen. Chcm. Inr. Ed. E n d . 1996, 35, N o . I X
BOOKS
deals with the reactions of alkynes with
Fischer carbene complexes (including the
Dotz reaction), which yield naphtholes,
indenes,
cyclobutenones,
cyclopentenones. and other compounds. Chapter 7
contains a detailed survey of the “new”
enediyne antibiotics, whose effectiveness
depends on the Bergman cycloaromatization reaction. The diradicals formed in
this reaction abstract hydrogen atoms
from specific sites in the DNA. This leads
to the break-up of the D N A single strand,
or even of the double strand, and finally to
the death of the cell. K. C. Nicolaou and
A. L. Smith. discuss the structures and
modes of action of the compound classes
known up to now, and describe several
total syntheses and some extensive studies
aimed at preparing synthetic analogs. In
Chapter 8 R. Gleiter and R. Merger report on the synthesis of strained cyclic
alkynes and polyynes and discuss how the
strain in these compounds affects their
spectroscopic properties and reactivities.
Of special interest here are the transannular reactions and the formation of superphanes by complexed cyclobutadienes.
Chapter 1 0 on “Polyacetylenes” (E. J.
Ginsburg. C. B. Gorman, R. H. Grubbs)
and Chapter 11 on “Acetylenic Compounds as Building Blocks for High-Spin
Molecules and Molecular Assemblies”
(H. Iwamura. K. Matsuda) are of special
interest to materials scientists.
The remaining three chapters treat various types of triple-bonded compounds in
a systematic sequence that strikes one as
almost playful. L. T. Scott and M. J.
Cooney describe the synthesis of macrocyclic polyynes in which the acetylene and
butadiyne units are separated by isopropylidene or cyclopropylidene groups.
Other compounds of this general type
have different bridging groups: sulfide,
tert-butylphosphinediyl, or dimethylsilanediyl. In Chapter 12 J. K. Young and
J. S. Moore describe their strategy for
preparing dendrimers and macrocycles of
phenylacetylene. In these each acetylene
unit is flanked by two benzene rings,
which in turn are linked at the mefa and
para or at the meta and meta’ positions to
continue the acetylene chain. For reasons
of solubility the dendrimers have 3,3’-di-tbutylphenyl groups at the ends of the
branches. In the ring compounds the continuation of the chain can also take place
from the ortho positions of the flanking
phenyl groups. In the last chapter F.
Diederich begins by describing his three
syntheses aimed at approaching as nearly
as possible to the compounds cyclo-C,,,
cyclo-C,,, and cyclo-C,, . This is followed
by his syntheses of tetraethynylethenes, in
which the four acetylenic end-groups are
either protected by silyl groups or have
their protection selectively removed. It Is
thus possible by a Glaser-Hay coupling
reaction to prepare perethynylated dehydroannulenes, expanded radialenes, and
oligomeric diyne chains.
As can be seen from this selection of
topics, which is far from exhaustive, the
book covers practically all aspects of current developments in acetylene chemistry
(although this reviewer would have liked
to see a contribution from K. P. C. Vollhardt also included). Twelve of the chapters fit fairly well into the overall scheme
of the book- --the only exception is the article on the enediyne antibiotics. Notwithstanding the great interest that this class
of compounds holds for chemists and
medical scientists, one must question
whether the many approaches to their
synthesis, even including, for example,
that of the sugar fragment in some
enediyne antibiotics, really belongs in a
book on acetylenes. Despite the large
number of authors the individual articles
are very consistent in style, presumably
because of clear guidance by the editors.
In each chapter a brief introduction is followed in turn by information on synthesis, properties, and reactions. The chapter
ends with additional comments (usually
descriptions of a number of experiments),
followed by an extensive collection of references, which also affords access to earlier work on other aspects of acetylene
chemistry that are not covered in the main
text.
The book is handsomely produced with
a cover design showing - in a model - an
enediyne antibiotic molecule entering a
fold in the D N A strand, alongside a formula scheme for the Bergman cycloaromatization. There are very few printing errors that annoy one (example: in Table 8-3
the transannular distance is given as
2.09 8, instead of 2.909 A). However, the
author index needs to be thoroughly revised, as it lists only authors who are mentioned in the text, with the result that, for
example, Nicolaou appears three times
(including, exceptionally, the page number of his contribution to the work),
whereas Regitz appears only once and
Gleiter not at all.
However, this minor criticism certainly
does not detract from the value of the
book. It should be on every acetylene
chemist’s bookshelf, and will be an indispensable source for preparing lectures in
advanced chemistry courses.
Gcrhard Himbert
Fachbereich Chemie
der Universitat Kaiserslautern (Germany)
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