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Book Review Houben-Weyl Methoden der organischen Chemie. Edited by E. Mfller

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Houben-Weyl: Methoden der organischen Chemie. Edited by
E. Muller. Georg Thieme Verlag, Stuttgart 1974. 4th, completely revised edit. Vol. 15: Synthese von Peptiden (Synthesis of Peptides). Edited by E. Winsch, written by M .
Deflner, K . - H . Deimer, E. Jaeger, P . Stelzel, P. Thamm,
G . Wendlberger, and E. Mnsch. Part 1 : XLIII, 1006 pp.,
3 figures, 86 tables, bound, DM 54Q-. Part 2: XXXVI,
806 pp., 85 figures, 67 tables, bound, D M 440.-.
The chemistry, physical chemistry, and biology of peptides
and proteins have made immense strides since du Vigneaud
published the first total synthesis of a peptide hormone, oxytocin, in 1953. As the universal building blocks of life, amino
acids stimulated chemists to the synthesis of biologically active
peptides or their partial sequences. In spite of many review
articles it has become increasingly more difficult for the peptide
chemist engaged in preparation work to have at his fingertips
the complete arsenal of the techniques of peptide chemistry.
This gap has now been filled astonishingly well by the present
reference work.
Part 1 is divided into three main sections. In the first (“Classification and Nomenclature of Peptides and their Derivatives”;
28 pages) the nomenclature of amino-acid derivatives and
the various types of peptides is explained clearly and in great
detail. The second section (“Fundamentals of Peptide Synthesis”: 18 pages) gives the principles of peptide-bond formation (mechanistic explanation of activation systems) and the
strategies for polypeptide synthesis (stepwise synthesis, condensation of fragments, universal protecting-group technique, least
possible masking of unrequired functional groups, and peptide
syntheses on solid and liquid polymeric carriers).
The most extensive main section (860 pages), on details of
methods, treats the “Blocking and Protection of the a-Amino
group” (260 pages), “Blocking and Protection of the ct-Carboxyl Group” (150 pages), and “Polyfunctional Amino Acids and
their Utilization in Peptide Syntheses” (360 pages). All the
protecting groups of a-amino and a-carboxyl groups are presented, with consideration of the literature up to 1973 (and
in part to 1974)-since the introduction of benzyloxycarbonyl
protection in 1932 there have been 60 variations of protection
as urethanes alone. The reactions are described with the aid
of clear formula schemes and, so far as they are known,
with statement of the reaction mechanisms. Critical evaluation
of the protecting groups, in particular those of proved value
for syntheses of natural products, as well as indications of
possible side reactions and, when known, how to prevent
them, together with detailed data on the stability and ease
of removal provide the peptide chemist with a wealth of
information; this is supplemented by many tables containing
analytical data for the amino-acid derivatives known so far,
as well as tables of reagents for cleavage reactions (with solvent,
time, and temperature data) and also the side reactions and
their avoidance. These tables are particularly valuable for
the polyfunctional amino acids (Lys, Arg, Glu, Asp, Ser, Thr,
Tyr, Cys, etc.); an excellent review is thus provided of the
many combination types of a,o-protecting groups; here too
the extensivedata on the stability and selective or total removal
of the individual a- and o-protecting groups illustrate the
great experience of the authors and their extremely careful
search of the original literature. Of greatest value are the
selected experimental directions for the introduction and removal of the most important protecting groups-often several
methods with a discussion of their advantages and disadvantages, depending on the amino acid used. These directions
are often expanded to include the next steps in the peptide
synthesis: synthesis of an activated ester, peptide coupling,
Angen. Chem. infernal. E d i f . 1 Vol. 14 11975)
1 No. 9
selective removal of the a-amino group, selective removal
or alteration of the ct-carboxy protecting group, and renewed
peptide coupling.
Further, short chapters deal with subsequent introduction
of the a(w)-amino group, subsequent introduction of the a-carboxyl group and the a-carboxamido group, as well as diaminodicarboxylic acids and their utilization in peptide synthesis.
Moreover, there is for the first time a clear collection of
information about pseudo-amino acids and their behavior
in peptide synthesis, including a- and @-hydroxy acids, aand @-thiol acids, a-(1-aza)- and @-(2-aza)-amino acids, t(and @-aminosulfonic acids, and a-and @-aminophosphonic
Part 2 is devoted mainly to “Formation of the Peptide
Bond” (364 pages). There is a detailed description of the
many possible methods of forming the peptide bond that
result from the presence of several functional groups in the
amino acid molecule, and of the special requirements to ensure
the necessary retention of configuration. Activation of the
carboxyl group by active esters, acid anhydrides, lactims, acetals, hydroxylamino esters, anhydrides with acids of sulfur,
phosphorus, silicon, or boron, by azides, diimides, azoles,
acylamines, thioesters, selenoesters, or acyl halides is described
and critically evaluated. Preparative examples of the preparation of activated carboxy derivatives and their use for peptide
coupling, indications of their successful application to the
synthesis of natural products, and finally detailed tables of
the corresponding amino acid derivatives offer invaluable practical aid. Other chapters deal with the “Preparation of Heterogeneous O(S)Peptide Bonds” (30 pages), “Synthesis of Polypeptides” (30 pages) by polycondensation or copolycondensation,
and “Tests for Racemization during Coupling Methods
(24 pages).
In addition to chemical reactions, in peptide synthesis the
“Testing and Representation of the purity of Synthetic Peptides” (274 pages) makes particular demands on the peptide
chemist. A wide selection of methods of analysis and preparative separation techniques has been developed for checking
the individual steps of the synthesis and for demonstrating
the constitutional and configurational homogeneity of the
intermediates and end products; these too are described, as
are the testing for optical purity and spectroscopicand enzymatic methods. Preparative methods of purification, such as
column chromatography and electrophoresis, are illustrated
by examples from the synthesis of natural products and are
supplemented by extensive tables that detail column packings,
column dimensions, eluents, and experimental conditions.
The production, graphical presentation, tables, and the
printing of both volumes are of excellent quality. Each volume
contains detailed author and subject indices and a special
subject index for experimental details, purification, and tests
of identity. It is very welcome to find the references placed
at the foot of the relevant text page, and special mention
must be made of the range and the accuracy of the citationsthere can hardly be any publication on peptide synthesis
that has not been included. Thus, these two volumes constitute
the most comprehensive and up to date review of preparative
peptide chemistry, not only providing a general source of
information but also, in particular, standing by to advise
on special questions concerning preparations. The authors
and the editor are to be congratulated without any reservations. The volumes should be by the side of every peptide
chemist, not just on a shelf in the library.
Eberhard Schroder
[NB 274 IE]
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