вход по аккаунту


Book Review Methods for the Oxidation of Organic Compounds. Alkanes Alkenes Alkynes and Arenes. By A. H

код для вставкиСкачать
tensive compilations on [Cp2ML2]complexes containing ligands whose donor atoms are elements of main Groups V,
VI and VI 1. Particular attention is given to the corresponding compounds containing metal-carbon o bonds. Three
separate chapters deal with the synthesis and reactions of
o-alkyl, o-alkenyl and o-alkynyl complexes of the type
[Cp2MR2]. Many users of this book will find the richly illustrated chapter o n the molecular structures of
[Cp2M”’R2]compounds especially useful. The treatment of
Cp2M chemistry is continued with short chapters on metallocene-silyl, -germyl, and -stannyl compounds and on hydride complexes.
There is also much valuable information o n metallocene(iv) compounds in the chapters which follow on
Cp2Zr”’ and Cp2Hf”‘ compounds and adducts of Cp2M“
groups with neutral donor ligands. Cp,M and Cp4M compounds have a chapter to themselves, as also d o complexes
of zirconium and hafnium with anionic n ligands other
than C5Hs, and metal complexes with neutral n ligands.
Two chapters on homoleptic and heteroleptic alkyl compounds complete the treatment of the inorganic chemistry
and the special characteristics of the organometallic chemistry of zirconium and hafnium compounds.
The book ends with a chapter on organo-zirconium and
organo-hafnium complexes in organic synthesis and catalysis, which unfortunately is too brief. Here, if not earlier
in the book, it becomes apparent that restricting one’s attention to the organometallic chemistry of the two heavier
Group IV transition elements. leaving out titanium, is a
marked disadvantage when comparisons with the corresponding titanium compounds need to be introduced for a
better understanding of chemical properties.
The strength of the book lies in its wealth of well-presented factual information, which is mostly arranged in the
form of clear tables, each with a list of literature references. It is definitely not a work of reference, if only because of its limited index (a subject index of eleven pages),
but it is made for reading. The book is a must for libraries.
For everyone actively concerned with the organometallic
chemistry of zirconium o r hafnium, it will be a welcome
aid for many years to come. One only hopes that a similar
review on the organometallic chemistry of titanium will
soon be available.
Gerhurd Erker [NB 802 IE]
Institut fur Organische Chemie
der Universitat Wurzburg (FRG)
Three volumes in the series “Best Synthetic Methods”:
Hydrogenation Methods. By P. N. Rylunder. Academic
Press, New York 1985. xv, 193 pp., bound, $ 48.00.ISBN 0- 12-605365-0
Methods for the Oxidation of Organic Compounds. Alkanes, Alkenes, Atkynes, and Arenes. By A. H . Huines.
Academic Press, New York 1985. xix, 388 pp., bound, $
83.00.- ISBN 0- 12-315501-0
Palladium Reagents in Organic Synthesis. By R. F. Heck.
Academic Press, New York 1985. xx, 461 pp., bound, $
99.00. -ISBN 0- 12-336140-0
For some time now the original literature in organic
chemistry has been producing a flood of new synthetic
methods and reagents, most of which are implicitly
claimed to be better than the established procedures. The
synthetic chemist has the task of making a choice, and relies more on instinct than o n rational evaluation. The seAngew. Chem. Int. Ed. Engl. 26 (1987) No. 6
ries of books under review is designed to eliminate this unsatisfactory state of affairs by a direct assault, enabling the
user to find, under such circumstances, not merely a suitable recipe, but quite simply the best one available. The
claim of this series to provide a critical evaluation obviously goes beyond the information which has long been
available from other highly regarded works such as “Organic’ Synthesis”, “Organic Reactions”, “Reagents for Organic Synthesis”, o r “Houben, Weyl and Miiller”. Consequently, one is keen to discover how successfully the
“best” method for each case has been chosen from the
hundreds of possibilities.
Rylander’s “Hydrogenation Methods” seems to have an
especially easy task in that respect, since the catalytic hydrogenation reaction discovered as long ago as 1899 is virtually an ideal example of a perfectly controlled method.
The book begins with a general description of the variations of catalyst, solvent and apparatus, which is quite long
(28 pp.) in relation to the book as a whole, but does not go
beyond non-committal statements and well established
knowledge. The second chapter (23 pp.) is devoted to hydrogenation of C C double bonds, and this again contains
little that is new; the problem of double bond migrations is
discussed in detail, but the much more troublesome one of
racemization during the hydrogenation of a-chiral olefins
is ignored. All stereochemical aspects are dismissed in a
mere four pages. From the detailed chapter on acetylenes
one concludes essentially that there is nothing better than
the good old Lindlar catalyst, and the lengthy discussion
on the hydrogenation of multiple bonds involving heteroelements (50 pp.) needs to be more selective in this age of
complex hydrides. Arene hydrogenation reactions are of
more significance in industrial practice than as laboratory
methods. The three concluding chapters contain exhaustive treatments of the hydrogenolysis reactions of carbonhalogen bonds and of heteroatom single bonds in rings
and in acyclic protecting groups (breaking of 0-benzyl and
N-benzyl bonds), and they offer much that is of interest to
all readers. Altogether Rylander’s book contains much valuable and detailed information and many useful hints, but
lacks a sufficiently clear and systematic organization of the
material. One soon gets the impression that here is an expert who has dipped into his well-filled, but no longer
completely up-to-date, card index, and has thereby produced only a few ideas which could help the reader over
his immediate difficulty.
The book by Huines, in contrast, is very clearly set out,
dealing in a lucid and exemplary way with the standard
methods for oxidizing CH, C=C, and C = C bonds. The
many examples of reactions which are collected together
in the form of tables, and the experimental details given
(both of which are absent from Rylander’s book) make this
a true laboratory handbook. Well-tried methods predominate on the whole, e.g. in the field of C H oxidations, those
given prominence are dehydrogenation with DDQ and selenium, or allylic oxidations by the Kharush-Sosnovski
method, and with selenium dioxide. Special techniques
such as “remote functionalization” of the steroid ring system by the Breslow o r Burton methods are, however, unduly stressed, whereas the equally important Vedejs reagent (Moo,-pyridine-HMPT) for the a-hydroxylation of
carbonyl compounds is not mentioned. The chapter on
C=C oxidation without bond breakage describes the synglycolysis method with iodine/silver acetate, as given by
Woodwurd, o r with osmium tetraoxide, in all the possible
variations. Detailed attention is also given to epoxidation
using peracids, or using peroxides with transition metal cat593
alysts, and also to the Sharpless reaction; no reference is
made, though, to the possibilities for diastereofacial control in the peracid epoxidation reaction. In the section on
oxidative cleavage of C = C bonds, one finds a wealth of
information on ozonolysis and the Lemieux variants. The
chapter on alkynes confines its attention to the oxidation
to 1,2-diketones, the scission of terminal acetylenic bonds
to give carboxylic acids, and the Glaser coupling. In the
final chapter the author gives a detailed discussion of such
aspects of the oxidation of arenes as hydroxylation with
peracids, peroxides or lead tetraacetate, the formation of
quinones with cerium ammonium sulfate or thallium trifluoroacetate, oxidative ring cleavage by ozone, permanganate, peracetic acid or ruthenium tetraoxide, and oxidative
phenol coupling with iron(m) salts. One quickly learns to
find one’s way around Haine’s book, helped considerably
by the terse presentation, liberal use of structural formulas,
and descriptive chapter titles.
The most up-to-date of the three volumes as regards
content is undoubtedly Heck‘s “Palladium in Organic Synthesis”. Whereas in the two volumes already described, literature citations for the last ten years tend to be the exception, they are instead the rule in this one. A comparison
with slightly older monographs on the same topic (e.g.
Tsuji : Organic Synthesis with Pailadium Compounds,
Springer 1980) does, however, show that progress during
the most recent years has not been quite so fast. The book
starts with a brief summary of methods for preparing the
most important of the catalyticalIy active palladium complexes, and deals also with the recovery of this expensive
noble metal. The subsequent chapters describe the areas of
application of palladium catalysis. Thus, for example,
Cope and Claisen rearrangements can be carried out under
very mild conditions; acetate shifts or rearrangements of
vinyl epoxides o r of a&-epoxyketones proceed readily
even in neutral media. Again, many variations of the
Wacker process have been developed. a-Olefins can be oxidized to give methyl ketones, and a,P-unsaturated esters
to give 0-keto-esters. The intramolecular version of the
Wacker oxidation leads to tetrahydrofurans, or in the case
of o-allylphenols to benzofurans, while the analogous oallylanilines undergo cyclization to indoles. An extensive
chapter (62 pp.) is devoted to substitutions which proceed
via x-allylpalladium intermediates. These allow one to introduce dialkylamines and well-stabilized carbanions of
the acetoacetic ester and malonic ester types into ally1 esters and ally1 ethers under mild conditions. An interesting
variation of this type of reaction is the Diels-Alder-like
[3 21 cycloaddition of trimethylenemethane complexes to
electron-deficient olefins, as discovered by Trost. About
half the book is concerned with variations on the theme of
the palladium-catalyzed C C bond, which leads readily to
biarylenes, 1,3-dienes or styrene derivatives. The carbonylation of unsaturated halogen derivatives gives a wide
range of carboxylic acid derivatives, while the cyclopropanation of CC double bonds with diazomethane/palladium
acetate gives a high yield only in the presence of electronwithdrawing substituents. Hydrogen transfer reactions using cyclohexene or sodium tetrahydroborate as the hydrogen donor, as described in the final chapter, offer a
mild alternative in many cases to the classical method of
catalytic hydrogenation. The usefulness of the Heck volume, like that of the Haines, benefits from the inclusion of
many tables and working rules, In some places the author
unfortunately gives way to his encyclopedic tendencies,
where it would have been more useful to confine the discussion to the most advantageous applications of palladium catalysis.
Altogether “Best Synthetic Methods” is undoubtedly a
very welcome work. Whether or not one really is given the
best method is, however, debatable. To achieve that, the
authors ought to have included many more critical comparisons with alternative methods. Some important volumes have yet to appear; one needs only to think of the
possibilities of boron, silicon, titanium or selenium reagents. Whether it is worth buying the whole series is something that one must decide for oneself; the high prices of
the individual volumes mean that one could quickly get
into large figures. It i s certainly worth having one or another single volume. Perhaps organic synthesis, influenced
by practical monographs such as this, will become reorientated again towards practical realizability and good sense,
which would be a desirable outcome. There have been
many sins in this respect in the past, when one considers
the tiny scale of the reactions described, the poor standard
of reproducibility, and the exaggerated yield figures that
are often given. Instead of setting oneself the task of preparing unduly complicated compounds, which are usually
more easily made by microbiological methods, one should
again concentrate attention more on that which is feasible
and sensible. Only in this way will it be possible to mend
the gulf between academic synthetic work and industrial
practice which is now deplored on all sides.
Johann Mulzer [NB 797 IE]
Institut fur Organische Chemie
der Freien Universitat Berlin
Registered names, trademarks, err. used in thisjournal, men when not marked as such. are not to be considered unprotected by law.
0 VCH Verlagsgesellschaft mbH. D.6940 Weinheim. 1987. - Printed in the Federal Republic of Germany by Zechnersche Buchdntckerei, Speyer/Rhetn.
At1 rights reserved (including those of translation into foreign languages). No part Of this issue may be he reproduced rn any form - by photoprint, microfilm. or any othcr means - nor tranrmitted or translated into a machine language without written permission from the publishers. Only single copies of contributions, or parts thereof, may be made lor personal use.
Valid lor users in the USA: The appearance of the w d e at the bottom of the first Page Of an article in this journal (serial) indicates the copyright owner’s wnsent that wpics of the article may be
made for personal or internal use. or for the personal or internal use of specrfic clients. This consent is given on the condition, however, that the copier pay the slated per-copy fee through the
Copyright Clearana Center. Inc., for copying beyond that permitted hy Sections 107 or 108 of the US.Copyright Law This m n x n t docs not extend to other kinds of copying, such as mpying
for general distribution. for advertising or promotional purpoys for crating new follcnive works, or for resale. For copying from back volumes of this journal see ‘Permissions to PhotoCopy.
Puhlisher’s Fce List’ of the CCC.
Editofid affiec: Pappelallce 3. M940 Weinheim, Federal Rrpublic of Germany, Telephone (06201) 602315, Telex 465516 vchwh d, Telefax (06201) 602328.
mitor: P,C6hlZ.
Associate editors: D. 1. Lorwus, A. Slimson. Editorial assirtmnl: E Srhweikorr
Publisherr: VCH Verlagsgexllschaft mbH. (Managing Directors: box Dr. Hefmul Griinewaid and Hans Dirk Kijhler), Pappelallee 3, M940 Weinheim, Federal Republic of Germany.
Correspondence concerning advertisements should be addressed to VCH Vcrlagsgesellschaft mbH. (Advertising Manager R . 1. Roth), Baschstr. 12. P.O. Box 1260/1280, D6940 Wcinhcim, Federal Republic of Germany, Telephone Wcinhcim (06201) 6024).Telex 465516 vchwh d, Tclcfax (06201) 602328.
Angew. Chem. Int. Ed. Engl. 26 (1987) No. 6
Без категории
Размер файла
286 Кб
oxidation, book, compounds, alkynes, organiz, method, alkane, alkenes, areneв, review
Пожаловаться на содержимое документа