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Book Review Carbocylic Cage Compounds Chemistry and Applications. (Series Methods in Stereochemical Analysis. Series editor A. P. Marchand.) Edited by E. Osawa and O. Yomitsu

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have read and greatly admire.” I can certainly endorse
that view.
Georg IlgenjiYtz
Institut fur Physikalische Chemie
der Universitlt Koln (FRG)
Carbocyclic Cage Compounds: Chemistry and Applications.
(Series: Methods in Stereochemical Analysis. Series
editor: A . P. Marchand.) Edited by E. Osawa and 0. Yonem i m . VCH Verlagsgesellschaft, Weinheim/VCH Publishers, New York, 1992. XIV, 409 pp., hardcover D M 168.00.
- ISBN 3-527-27 933-4/0-89 573-728-0.
This is the third major work on carbopolycyclic compounds
to appear within the last four years. Whereas Haufe and
Mann (Chemistry of Alicyclic Compounds, 1989; see Angew.
Chem. 1991, 103, 111 ; Angew. Cliem. Int. Ed. Engl. 1991, 30,
1191) approach the subject in a systematic way, the multiauthor volume edited by Olah (Cage Hydrocarbons, 1990) and
the book reviewed here are unstructured collections of review
articles in a style similar to that of Chemicnl Reviews. The
latter journal did in Fact include an issue in 1989 containing
17 reviews on the same subject area. Despite this there is little
overlapping of the contents, which gives an indication of the
wide-ranging nature and high level of activity in polycycles
We learn from the preface that this book arose from a series
of symposia on cage compounds that took place in Japan
in the 1980s, extending to the beginning of the 1990s.
As one might expect from this, the articles vary considerably
in their breadth of subject matter, length, readability,
up-to-dateness, and so on. Nevertheless, most of the
older contributions appear to have been revised to bring
them up to date, so that in general the articles take
into account work published up to 1989, with a few
references to publications in 1990 and 1991. A lamentable
exception is Chapter 11 in which, out of about I10
references, the most recent are one from 1981, two
from 1982, and one from 1983.
The subtitle should be regarded with caution. Anyone who
expects to find applications of cage compounds in fields other
than chemistry will be disappointed. Apart from a mention
in the preface, applications are only seriously addressed
in the last chapter (solar energy storage). It is a sad commentary on the present situation regarding support
for basic research that it is felt necessary and realistic to
justify it by citing potential applications of doubtful
validity; here, for example, research on cubane is justified
by dubious references to possibilities for explosives o r
Most of the book’s contents are concerned with down-toearth organic chemistry. In Chapter 1 A. P. Marchand gives
a very readable review of the use of cage compounds as intermediates in organic synthesis, and as rigid structures within
which reactive intermediates that could not exist otherwise
may be prepared, observed, or identified from the stable products that result from them. The reaction schemes are clear
and well annotated, a virtue not shared by some of the other
Chapter 2 (K. Naemura) deals with cage compounds that
are highly symmetrical but nevertheless chiral (an example is
D,-trishomocubane). Many of the schemes show several
structural formulas together, identified only by numbers,
which necessitates much turning of pages and spoils the clarity of the presentation.
Angeiv. Clicni. h t . Ed. EngI. 1993. 32. N o . 4
Chapter 3 (H. W. Kroto and D. R. M. Walton) is a short
one on “Postfullerene Organic Chemistry”. and is rather out
of place here in several respects. Firstly, the aromatic C,,
soccerball structure (according to the preface a “fantastic
superstar”, which rather misleadingly appears in several
copies, sadly shrunken, on the front cover) is fundamentally
different from the small saturated molecules treated in the
rest of the book. Secondly, this article consists not so much
of research results as of speculations about possible synthetic
routes to individual fullerenes (at the time when this chapter
was written the flood of publications on C,, chemistry was
only just beginning).
Chapter 4 (F. Matsuda and H. Shirahama) on “Natural
Products Chemistry in Three Dimensions” discusses the observation that unsaturated macrocycles often adopt a preferred conformation in which the plane of a double bond is
perpendicular to the plane of the macrocycle, with important
consequences for the reactivity. Chapters 5 (propellanes, Y.
Tobe). 6 (cyclophanes derived from vinyl arenes, J. Nishimura), 7 (prismanes, G. Mehta and S. Pddma - very lucid and
worth reading), 8 (cubanes, H. Higuchi and I. Ueda), and 9
(bishomocubanes, W. L. Dilling) review recent developments
in the chemistry of these compound classes, with the emphasis in each case on the work of the authors.
In Chapter 10 C. Ganter describes in detail the elegant
methods and results of his cartography of “Adamantaneland”. Chapter 11 (J. Fournier and B. Waegell) discusses the
reflex and anti-reflex effects, which are concerned with the
influence of axial substituents at the 3- and 5-positions on the
conformations of cyclohexanones. In Chapter 12 T. Miyashi,
Y Yamashita, and T. Mukai give a concise description of
photochemical methods for synthesizing cage compounds,
and the photochemical reactions that these undergo in the
presence of electron transfer catalysts. Lastly, Chapter 13
(K. Hirao, A. Yamashita, and 0. Yonemitsu) discusses the
problems that still remain to be overcome in trying to apply
a simple reaction (norbornadienesquadricyclane) on a
technical scale.
The overall impression from these articles is of thoroughly
sound contributions to the field. The rather nonsensical statement “Asymmetry is a necessary but insufficient criterion for
a chiral molecule to have a nonsuperposable enantiomer”
(p. 62) is, fortunately, not typical. When dimethyldioxirane
is wrongly described as “dimethyldioxolane” (p. 241) and
Meldrum’s acid (isopropylidene malonate) as a “glutaric acid
derivative” (p. 280), one might well excuse these as no more
than minor slips. Unfortunately there are also some annoying
errors in the formula diagrams. For example, in pagodane
(p. 36) two bonds are missing from the “waist” of the molecule, the stick projection of the C,, football on page 98 is not
successful, and in the alleged conformational equilibrium
shown at the top of page324 the two formulas actually
represent a pair of constitutional isomers. The repeated appearance of certain topics, such as 2 + 2-photocycloaddition
and the Favorsky ring contraction, was probably unavoidable. I would have preferred a more definite continuity of
theme in several of the articles, and even throughout the
The technical quality (typography, binding, etc.) is good,
and the number of printing errors is acceptably small. Libraries and specialists in the field should buy the book, but
most other chemists are unlikely to wish to d o so, in view of
its specialized nature and the fact that parts of it are no
longer completely up-to-date.
Christoph Riicker
Institut fur Organische Chemie und Biochemie
der Universitlt Freiburg (FRG)
t,‘. VCH Y e r l u ~ . s ~ e . ~ ~ ~ lmhH,
l . s ~ l i uW-6940
Weinheim, I993
OS70-0833i93j0404-0~2SX 10.00+ .25,’0
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