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Book Review New Pathways for Organic Synthesis. Practical Applications of Transition Metals. By H. M. Colqhoun J. Holton D. J. Thompson and M. V

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and R . Konig, D. Kaufmann, R. NBder, A. de Meijere. J . Chem. So?.
Chem. Commun. 1983. 771.
described in ref. [la] and proposed in this communication
then the site of attack of the electrophile would differ in
both substrates. This would, in addition to the reaction of
thiophenol, in which radical-chain processes take place,‘’l
be a further case in which regiochemistry is determined by
the localization of the HOMOS.[^'
[2] M. Christl, G. Freitag, G. Briintrup, Chem Ber. I 1 1 (1978) 2320.
[3] a) Prepared by reaction of 4,5-dibromotricyclo[4.1 .0.0’ ’lhept-3-ene with
methyllithium and subsequent reduction with Na in rert-hutyl alcohol: h)
details of the crystal structure investigation are available on request from
the Fachinforrnationszentrum Energie Physik Mathematik, D-75 14 Eggenstein-Leopoldshafen 2, on quoting the depository number CSD
51 268, the names of the authors, and the full citation of the journal.
[4] G . H. Wahl, Jr., J . Ory. Chem. 33 (1968) 2158.
[ S ] R. Gleiter, Top. Curr. Chem. 86 (1979) 197.
[6] Cf. reactions of hicyclo[ I . I.O]hutanes with non-radical electrophiles: a)
W. R. Moore, H. R. Ward, R. F. Merritt, J . Am. Chem. Soc. 83 (1961)
2019; b) K. R. Wiberg, G. Szeimies, ibid. 92 (1970) 571; c) M. ChristLAngen?. Chem. 93 (1981) 515: Angew. Chem. Int. Ed. Engl. 20 (1981) 529.
[7] N. W. Jordan, 1. W. Elliott, J . Org. Chem. 27 (1962) 1445.
[XI P. G. Gassman, G. D. Richmond, J. Am. Chem. SOC.92 (1970) 2090.
191 M. Christl, R. Lang, R. Herbert, G. Freitag. Angew. Chem. Y2 (1980) 465;
Angew. Chem. Int. Ed. Engl. 19 (1980) 451.
Received: February 25, 1985:
supplemented: April 9, 1985 [Z 1189 IE]
German version: Angew. Chem. 97 (1985) 595
CAS Registry numbers:
l a , 35618-58-7: l b , 96865-97-3: Za, 96865-98-4; Zb, 96865-99-5; 3a, 9686600.1: 3b, 96866-01-2: 4a, 16118-23-3; 6 , 287-13-8; 7, 95866-02-3; TCNE,
670-54-2: 4,5-dibromotricycl0[4.1 0.0z.’]hept-3-ene, 5291 1-87-2.
[I]a) M. Christl, E. Rrunn, F. Lanzendorfer, J. A m . C/iem. Sor. 106 (1984)
373: h) for the reaction of vinylcyclopropanes with TCNE cf. [12] in [la]
BOOK R E V I E W S
New Pathways for Organic Synthesis. Practical Applications
of Transition Metals. By H . M . Colqhoun, J . Holton, D .
J . Thompson and M . I/. Twigs. Plenum Press, New
York-London
1984. xiv, 454 pp., bound, $ 59.50.ISBN 0-306-41318-3
A retrospective glance at the Nachrichten aus Chemie,
Technik und Laboratorium for 1983 indicates, amongst
other things, how vigorously organometallic chemistry is
developing. The results from organometallic chemistry fill
16 columns while those of classical organic chemistry only
account for 9. The demand for information and teaching
material is considerable in this field. Therefore many
books have appeared in recent years dealing with organotransition metal chemistry. With few exceptions the disappointed reviewer has laid them aside. This book is one of
the exceptions.
Organic molecules or residues bonded to a transition
metal often display reactions which d o not fit into the classical organic chemical picture. Surprisingly little attention
is paid to these new reactions by organic chemists or by the
authors of organic chemistry textbooks or laboratory manuals. Starting from this point the authors, four industrial
chemists, address themselves to the practical organic
chemist and present an extensive collection of catalytic
and stoichiometric organic syntheses in which transition
metals play a part. The emphasis is-as the authors say in
the introduction-on processes which are not possible using classical methods, which are generally applicable,
which d o not require a great deal of apparatus or much financial outlay and which-where possible-do not deter
people by their toxicity. In order to ease the application of
the methods described they present in the final chapter
brief instructions for the handling of air-sensitive compounds, give instructions for the preparation of 18 important transition metal catalysts and educts and list sources
for such compounds.
Between the introduction and the final chapter the material is divided u p as follows: Formation of C C bonds (single bond, double bond) (55 p.); Synthesis of carbocyclics
(69 p.); Synthesis of heterocyclics (25 p.); Isomerization of
Angew Chrni. 1111 Ed. Enyl. 24 (1985) No. 7
8
alkenes (20 p.); Direct introduction and removal of carbonyl groups (65 p.); Reduction (73 p.); Oxidation (31 p.).
The description-product-oriented-is
in the HoubenWeyl style, i.e. brief, with formulas reduced to the most important, taking account of stereochemical aspects, giving
warning of sources of danger and interspersed with concrete experimental data (in all 147). Only occasional reference is made to theoretical and mechanical details; however, the reader can easily obtain additional information
from the carefully chosen references (in all 976).
Since the carbonyl group is the most important functional group in organic chemistry the chapter “Direct introduction and removal of carbonyl groups” is worthy of
special interest. On reading this it will become clear to
many chemists for the first time that the chemistry of organic carbonyl compounds after its great leap forward in
the 19th century has been experiencing a great renaissance
since the middle of this century. The chapter on heterocyclics offers the specialist in organotransition metals or heterocyclic chemistry surprising information and an exciting
glimpse of a new field. On the other hand criticism must be
made of the chapter “Formation of C C bounds”. The
more recent developments such as the important application of alkyltitanium compounds as alkylation agents with
high chemoselectivity, the stereoselective addition reactions of organotransition metal compounds to carbonyl
groups or the transition metal-containing reagents for carbony1 olefination are not mentioned (on the other hand,
non-oxidative alkene dimerization, cross coupling according to Kumada, the McMurry reaction, the Semmelhack method, C C linkage via n-ally1 complexes, alkyl cuprate reagents and alkene metathesis are all covered). Such
gaps, also to be found in other chapters, and the list of references show that the book was completed some time ago
(1978- 1980). However, the authors used the intervening
period to check the text and formulas carefully.
This book, which is fluently written, may be recommended: a) To the mentally and practically flexible organic chemist searching for new methods of synthesis. b)
For use with a textbook containing the theoretical and
613
practical basics of organotransition metal chemistry (Collman, Hegedus: Principles and Applications of Organotransition Metal Chemistry is recommended), to bring university organic chemistry tuition u p to date, especially in
the practical field-The book deserves to sell, to be improved by its authors by the making good of the gaps
which have been mentioned and to be continually updated
by the inclusion of new methods.
Thomas Kauffmann (NB 660 IE]
Organisch-chemisches Institut
der Universitat Munster (FRG)
Die Bleibelastung des Menschen. By G. Lehnert and D .
Szadkowski. Verlag Chemie, Weinheim 1983. vii, 96 pp.,
D M 28.00,-ISBN 3-527-26096-X
This booklet describes in 80 pages the important sources
of lead uptake (described here as lead burden) and their
regulating boundary conditions, the functional changes initiated (“stresses”) and the public health measures necessary (in essence tolerance levels). The actual effects of lead
and therapeutic questions are only touched on cursorily.
The descriptive mode of presentation makes the work suitable for use as a n introduction to the field for non-specialists and less useful for medical and toxicological experts.
Its value lies in the long list of literature references covering the occurrence and possibilities of uptake of lead from
industry, technology, foodstuffs and confections and beverages, in the home and in the air. Daily and annual variations and the possibilities of mobilizing lead in the individual are devoted particular attention. There are no references to guide the interested reader to the larger, more
comprehensive monographs on lead and the effects of
lead, although they are continually borrowed from both
for the text and the diagrams. The MAK for lead is erroneously quoted as 150 pg/m3; since 1977 the value has been
100 pg/m3.
Dietrich Henschler [NB 658 IE]
Institut fur Toxikologie und Pharmakologie
der Universitat Wiirzburg (FRG)
Selectivity- A Goal for Synthetic Efficiency. Workshop
Conferences Hoechst. Vol. 14. Edited by W . Bartmann
and B. M. Trost. Verlag Chemie, Weinheim 1984. xi, 423
pp., bound, D M 85.00.-ISBN 3-527-26142-7
Selectivity is a conditio sine qua non for efficiency in
chemical synthesis. The discovery of new, more efficient
regio-, chemo- and stereoselective methods is thus of particular importance. The advances in this field are so breathtaking that several selective syntheses are often available
now for complex structures that were previously only difficultly accessible. The Achilles heel of many selective methods and syntheses is, however, their lack of practicability.
Biological synthesis is still better than chemical for many
complicated natural products of wide application such as
penicillins, cephalosporins, steroids and macrolides. The
challenge to chemical synthesis is increased by the development of gene technology. It is greatly to be welcomed
that the papers presented by internationally acknowledged
specialists at the 14th Workshop Conference Hoechst are
now available in book form and have thus been made
614
available to a wider, interested public. The following individual topics are treated:
Stereoselectivity in the Synthesis of Cyclic Ethers (P. A .
Bartlett); Some Uses of Silicon-Nitrogen Bonds in Organic
Synthesis ( R . J . P. Corriu and J . J . E . Moreau); Designed
Complexes-Science and Applications (0.J. Cram and J.
M. Cram); Asymmetric Synthesis of Carbonyl Compounds
and Primary Amines (0.
Enders); Stereoselection by Allylboronates. The Highs and the Lows (R. W . Hoffnzann); Palytoxin (Y. Kishi); Tris(dia1kylamino)sulfonium Enolates
and Phenoxide ( R . Noyori); Regio-, Diastereo- and Enantioselective Carbon-Carbon Bond Formation-Recent
Studies and Applications in Organic Synthesis (W. Oppolzer); Selectivity and Reactivity in Oligosaccharide Synthesis
(H. Paulsen); Organotin Reagents for Selective Reactions:
Synthesis and Applications of a-Heterosubstituted Organotins ( M . Pereye, B. Elissondo und J.-P. Quintard); Chiral
Building Blocks in Natural Product Synthesis (G. Quinkert); Regioselectivity in Metal-Promoted Carbon-Carbon
Coupling Reactions (M.F. Semrnelhack); Strategies for
Controlling the Stereocheniical Course of Yeast Reductions (C. J . Sih, B. Zhou, A . S . Gopalan, W.-R.Shieh and F.
Van Middlesworth) ; Conformational Control of Chemical
Reactions ( W . C . Still) ; Radical-Mediated Cyclisation
Processes (G. Stork); Diastereoselectivity and Asymmetric
Induction in the Diels-Alder Reaction with Inverse Electron Demand (L. F. Tietze) ; New Palladium-Catalyzed
Reactions of Allylic Compounds via n-Allylpalladium
Complexes (J. Tsuji); Selectivity in Excited State Chemistry (P. A . Wender); Chiral Building Blocks in Alkaloid
Synthesis (E. Winterfeldt); Selectivity in Organic Synthesis
( H . Wynberg); On the Mechanism of Titanium-Tartrate
Catalyzed Asymmetric Epoxidation ( K . B. Sharpless, S. S .
Woodard and M . G. Finn); Selectivity in Chemical and Enzymatic Synthesis (J. E. Baldwin).
The contributions, of which several have been published
in the meantime in other places in this or even in an extended form, are in their majority very clearly and synoptically written. Comprehensive reference lists make it possible to become further engaged in the widely ranging
topics. The book is to be recommended to all who stand
somewhat at a distance from this field and wish an overview-albeit incomplete-of the present state of this most
topical field of organic chemistry. The purchase of this
book which offers valuable stimulation with its collection
of the latest results from twenty-two research groups
would also pay the preparative organic chemist working in
this field. However, the price seems rather high for a n extract-like “snapshot” of a rapidly developing field.
Hans-Joachim Gais [NB 657 IE]
Institut fur organische Chemie und
Biochemie der Technischen
Hochschule Darmstadt (FRG)
Immuno Enzyme Techniques in Cytochemistry. By W . D .
Kuhlmann. Verlag Chemie, Weinheim 1984. xiii, 162 pp.,
bound, DM 128.00.-ISBN 3-527-26078-1
Advances in fundamental biological and medical research are based to a large extent on the introduction of
new methods. Nowadays, no laboratory working in cell
biology can manage without gene manipulation and/or
immunological techniques. Scientists are always being
confronted anew with the problem of choosing and/or
Anyeu Chem Int Ed Enyl 24 (19RSi No 7
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