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Book Review The Chemistry of Linear Oligopyrroles and Bile Pigments. By H. Falk

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majority of the references are to papers from earlier years.
Some random checks showed that modern developments in,
for example, enantioselective cis-hydroxylation using osmium tetraoxide, polarity reversal of the reactivity in enones
and enals, free radical addition to enones (e.g. for synthesizing C-glycosides) and modern variants of the Khand-Pauson, Sakurai and Nazarov reactions are all included. It is
true that in several of these areas there have been further
rapid advances since the volume appeared, but the reader
will nevertheless find here a good introduction to these topics. This reviewer was disappointed to note that some important contributions to enones chemistry from the carbohydrates field were not included. The neglect of this aspect is
regrettable in view of the use now being made of renewable
raw materials for synthesizing enantiomerically pure natural
substances.
There is now an increasing level of interest in the safety
and toxicity aspects of chemical substances and reagents,
and editors of comprehensive handbooks will probably need
to give more thought to this in the future. In the present
volume such information is only rarely included, e. g. the
warning about the possible explosive risk with some molybdenum oxodiperoxy complexes (p. 548).
Now some comments regarding the formulas. The convenient small page format used in “Patai” has advantages for
the user, but occasionally, for typographical reasons, it necessitates moving a formula scheme on to the next page. The
formulas are generally clear and well set out (except for the
fact that the stereo-arrows are too thick, especially in the
representation of cyclopentene on p. 255).
The idea of constructing the handbook as a collection of
self-contained monographs means that it is particularly important to have comprehensive author and subject indexes.
It would perhaps have been useful to make the subject index
even a little more comprehensive, at the expense of some
duplication. To give just one example, the Sakurai reaction
cannot be found in the index under this name; it is (very
correctly) indexed as the Hosomi-Sakurai reaction.
No library which already contains parts of the Patai series
can afford to be without this volume. Because of the importance of the functional groups that it deals with, it will also
be a useful and worthwhile addition to the private collections
of preparative organic chemists.
Karsten Krohn [NB 1059 IE]
Institut fur Organische Chemie
der Technischen Universitat Braunschweig (FRG)
The Chemistry of Linear Oligopyrroles and Bile Pigments. By
H. Falk. Springer, Vienna 1989. xii, 261 pp., hardcover,
DM 270,00.--ISBN 3-221-82112-0
There is hardly another class of compounds in organic
chemistry that has held more fascination for investigators of
successive generations than the pyrrole pigments. Since the
pioneering work of Hans Fischer and his school, pyrrole
derivatives in the widest sense have for several decades been
the subject of studies by many renowned laboratories
throughout the world. One recalls, for example, such celebrated studies as that which led to the determination of the
C . Hodgkin),
structure of the vitamin B,, coenzyme (D.
those on the total syntheses of chlorophyll a ( R . B. Woodward) and of cyanocobalamine ( A . Eschenmoser and R. B.
Woodward),the biosynthesis of the corrinoids ( A . Battersby,
A . I. Scott and others), the development of models for oxygen fixation (J. P. Collman, J. E. Baldwin and others), and
AnKen. Chwi. Ini Ed. Enni. 29 (1990) No. 9
many more. However, whereas the chemistry and biology of
the macrocyclic pyrrole pigments and the chemistry of
pyrrole and its derivatives have been reviewed more than
once during the past fifteen years, since the publication of the
classic work by R. Lemberg and J. W Legge (“Hematin
Compounds and Bile Pigments”) and of the mainly medically orientated book by 7: B. With (“Bile Pigments”, 1968)
there has been no comparable monograph covering the bile
pigments and the related linear oligopyrroles. This is probably due to the fact that bile pigments occur as breakdown
products of the biologically important porphyrin chromophores, and consequently in the past it is their clinical
significance that has been emphasized. Although Lemberg
discovered as long ago as 1933 that the substances responsible for the colors of cyanobacteria and red algae belong to
the class of bile pigments, the renaissance in the chemistry of
these compounds did not occur until the early 195Os, following the pioneering work of H. Fischer and his school, when
a chromophore of the bile pigment type was also shown to be
present in phytochrome, the photoreceptor which controls
plant morphogenesis. Since then there have been some important milestones in the new era of bile pigment chemistry,
such as the elucidation of the structures of the chromophores
mentioned above (J. J. Katz, H. Rapoport, W Riidiger, H. u!
Siegelman and others) and of a bioluminescent bile-type pigment found in marine organisms ( Y . Kishi et al., 1988), and
particularly the recently published X-ray structural analysis
of the photoreceptor proteins of cyanobacteria ( R . Huber et
a]., 1986), and these successes have stimulated a continued
growth in activity in this area.
The book “The Chemistry of Linear Oligopyrroles and
Bile Pigments”, by H. Fulk, thus closes the existing gap in the
literature at an opportune moment, and it does this admirably. The eight chapters of this 534-page work deal exhaustively with the physical and chemical properties of the
various members of this class of compounds. After a short
introductory chapter, the troublesome question of the
nomenclature of linear oligopyrroles is critically discussed in
Chapter 2, and suggestions for a rational system of nomenclature are offered. Since moves to resolve this problem at an
international level are still in their beginnings, the reader is
strongly recommended to read this chapter right at the start.
The account in Chapter 3 of the occurrence, formation and
importance of linear tetrapyrroles in nature is rather brief
(20 pp.), although it is true that further information on these
topics is given in the chapters that follow (for example, the
latest papers on the enzymic synthesis of tetrapyrroles are
cited on p. 352, and the structures of the bile pigments present in butterfly wings are given on pp. 203-205, 231, 318
etc.). The reader whose main interest concerns the clinical
aspects of bile pigments is referred to several relevant recent
monographs. Chapter 4 collects together some very instructive information about the historical development of pyrrole
chemistry; the connection between this and the human intellect is illustrated by drawings from the papyrus Ebers of the
17th century B.C., and by the oboe passages of Mozart’s
Magic Flute (which is even cited in the index).
Chapter 5 covers more than half the book (293 pp.), and
deals with the structure and stereochemistry of pyrroles (including MO methods). The majority of the work described
here comes from the author’s own scientific papers, and the
reader thus has the benefit of getting the required information directly from the present leading chemist in this area of
research. Non-specialists will also appreciate the short general description in Section 5.1.3 of the physical methods used
for the structural analysis of pyrroles, and the references to
relevant literature. Chapter 6 describes the synthetic meth-
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ods used for preparing linear oligopyrroles with two to six
units in the chain, using the “synthone approach”, and these
are illustrated by appropriate examples. Chapter 7 deals with
the physical (mainly spectroscopic) properties of oligopyrroles. Although there is some overlapping here with the
contents of Chapter 5, the reader is unlikely to consider this
as a disadvantage. Finally, in Chapter 8, the reactivity of
oligopyrroles and bile pigments is discussed under the different types of reactions (photochemical rearrangements, the
formation of metal chelates, substitution and addition reactions, etc.). The bibliography and the author and subject
indexes, which have been very carefully compiled, reinforce
the excellent impression obtained from this book. The figures, which have been prepared using an Apple-Macintosh
computer program, are excellent and essentially error-free.
In the few exceptions to this (Figs. 3.17,5.96,6.197-198) the
attentive reader should have no difficulty in correcting the
mischief of the “printer’s devil”. Altogether this is an excellent book, which will be indispensable to every chemist
working in this field, and to those wishing to become involved.
Albert Gossauer [NB 1028 IE]
Department of Organic Chemistry
University of Fribourg (Switzerland)
Carbon-13 NMR of Flavonoids. (Series: Studies in Organic
Chemistry, Vol. 39). Edited by P. K . Agrawal. Elsevier,
Amsterdam 1989. 564 pp., hardcover, DFI 350.00.-ISBN 0-444-87449-6
Flavonoids occur widely in plants as pigments and other
constituents, and are very important not only in food technology, pharmacology and chemotherapy, but also as key
substances in the chemotaxonomy of plants. Because of their
wide variety of structures their identification and structural
elucidation requires unambiguous spectroscopic methods.
To the earlier monograph and data compilation The
Flavonoids, edited by J. B. Harbone and T J Mabry and published in 1975, is now added this volume by P. K . Agrawal
and coauthors on the 13C NMR data, which supplements
and updates the earlier work.
The introduction briefly describes and compares the most
important spectroscopic methods that have been used to
determine flavonoid structures (IR, UV, MS, ‘H NMR),
then leads into the subject of the book by revising the structures of a few well-known flavonoids on the basis of their
3C NMR spectra. A useful guide is provided by tables listing typical ‘H and 13CNMR chemical shift ranges and coupling constants. Chapter 2 deals very briefly with the most
important one- and two-dimensional NMR techniques, including decoupling procedures and correlation spectroscopy
and with chemical aids for assigning 3CNMR signals (shift
reagents, labeling methods, derivatizations). Even the offresonance decoupling method, now completely superseded
by more sensitive and unambiguous methods for determining CH multiplicities (notably DEPT), is revived yet again.
Chapters 3 to 9 (altogether 414 pp.) constitute the largest
and most useful part of the book, in which over 800 literature
references are reviewed. These chapters provide a survey, in
the form of tables accompanied by a concise commentary, of
3C chemical shifts for flavonoids and anthocyanidines
(Chapter 3), isoflavonoids, coumarins, pterocarpanoids and
rotenoids (Chapter 4), neoflavonoids, auronoides and homoisoflavonoids (Chapter 5), flavonoid-glycosides (Chapter
6), chalconoides (Chapter 7), and flavanoids and flavanoid-
’
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glycosides (Chapter 9). The final chapter of the book gives
useful advice on using 3C chemical shift data to distinguish
between the different classes of flavonoids, and to recognize
functional groups and determine their position. Regrettably,
though, the chapter omits to explain that, by analyzing contour diagrams from two-dimensional correlation experiments such as CH-COSY and CH-COLOC, a complete and
precise structure elucidation can be obtained even with only
a small amount of substance.
The literature up to 1987 is covered. Unfortunately the
clarity of the presentation is marred by the fact that the
formulas (usually without numbering of the carbon nuclei)
are widely separated from the data tables, necessitating constant leafing back and forth. A more user-friendly arrangement would have been to give the chemical shift values directly alongside the carbon nuclei in the formulas, a form of
presentation that could have been achieved by using commercially available text-graphics software. This would also
have enabled the 6(’H) values to be clearly shown as complementary data, especially as it is nowadays possible to rapidly
determine 6(13C) and 6(’H) values in a single correlation
experiment (CH-COSY). It would also have been useful to
include details of the use of 3JcHvalues for determining substitution patterns (pp. 509f).
The subject and compound indexes have been badly printed in a 9-point matrix format. In the compound index it
would have been better to use the Chemical Abstracts method of classification (basic skeleton and substituents). Lastly,
the formulas have evidently been reproduced from the authors’ hand-drawings; the use of such technically inferior
methods is inappropriate in such a highly priced book. Nevertheless, the book is a useful work of reference for all those
concerned with identifying flavonoids and elucidating their
structures.
Eberhard Breitmaier [NB 1066 IE]
Institut fur Organische Chemie und Biochemie
der Universitat Bonn (FRG)
’
Chemistry of Tin. Edited by P. J. Harrison. BIackie, Glasgow 1989. xi, 461 pp., hardcover, s 75.0(tISBN 0-21692496-0.
Organotin Chemistry. (Series: Journal of Organometallic
Chemistry Library, Vol. 21). By I. Omae. Elsevier, Amsterdam 1989, viii, 356 pp., hardcover, DFI 270.00.ISBN 0-444-87456-9
Organotin Compounds in Organic Synthesis. Edited by Y.
Yamamoto. Tetrahedron Symposia-in-Print 36, Vol. 45,
No. 4, pp. 909-1230. Pergamon, Oxford 1989.-ISBN
0040-4020
“Tin for organic synthesis” is the best way of describing
the rapid developments that have occurred in organotin
chemistry. These developments were initiated by acknowledged masters of the art of dealing with complex organic
molecules and their subtle stereochemistry, chemists such as
E. .I
Corey, D. H . R. Barton, G. Stork and J. K . Stille. The
irony of this development is that most of the basic organotin
reactions now used had been known in the literature for
twenty years or more, though without having been exploited
to such an extent. The rift that had developed between
“pure” organic chemistry and organometallic chemistry,
and had almost become a tradition-although such a rift did
not yet exist in the days of Victor Grignard, Karl Ziegler and
Georg Wittig--was only closed again when the great “back
to synthesis” movement began.
057Q-O833]90Io9o9-lo72$3.50+ .25/0
Angen. Chem. Inr. Ed. Engl. 29 (1990) No. 9
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