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Book Review Preparative Acetylenic Chemistry (Series Studies in Organic Chemistry Vol. 34). 2nd Edition. By L

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[5] 5 . C,,H,,O,Zr,,
M = 502.9, monoclinic, P2,In. a = X.9177 (6).
h = 7 . 7 6 7 0 ( 6 ) , c = 1 3 . 9 1 7 ( 1 ) ~ , ~ = 9 0 . 1 0 2 ( 7 ) "V. = 9 6 4 . 0 A 3 , 2 = 2 ,
= 1.73 gcm-'. ~ ( M o ) =
~ .10.76cm-I, Enraf-Nonius diffratomeheavy atom
ter. 4340 measured reflections, 3352 observed ( I z 2 o
method, hydrogen positions calculated and not refined, R = 0.047,
R , = 0.071 for 11X pdrdmterS[9b].
[6] Cf. G. Erker, U. Dorf, P. Czisch. J. L. Petersen, Orgunorneidics 5 (1986)
668; G. Erker, P. Czisch, R. Schlund, K. Angermund, C. Kriiger, Angew.
Chem. 98 (1986) 356; Angew. Chem. Inr. Ed. Engl. 25 (1986) 364: G. Erker,
K. Kropp, C. Kruger, A.-P. Chian, Chem. Ber. if5 (1982) 2447.
[7] 5 : m.p. = 220 "C (dec.); correct elemental analysis (C. H); MS (70 e V ) : m/r
500 ( M e , 18%), 470 (MQ - CH,O, loo), 390 (33). 220 (60); 'H NMR
(200 MHz, CDCl,): 6 = 5.89 (Cp), 2.42 (CH,); "C NMR (50 MHz. CDCl3): 6 = 107.8 ('J(CH) = 171 Hz, Cp), 64.0 ('J(CH) = 153 Hz, CH,); b)
6: yield 81 %, m.p. 160'C (dec.); correct elemental analysis (C. H); 'H
NMR (200 MHz, [D,]benzene): 6 = 5.81,5.45 (each s, each 10H, ZrCp,),
5.08 (s, 5H, CoCp), 4.34 (s, 2H, CH,), 2.58 (s, 2H, ZrCH,); I3C NMR
(50 MHz, [DJbenzene): 6 = 290.0 (carbene C), carbonyl C not observed,
113.0(ZrCp,), 107.8 (ZrCp,), 95.4 ('J(CH) = 143 Hz, CH,), 84.5 (CoCp).
66.4 ('J(CH) = 154Hz, ZrCH,); IR (KBr): F(C0) = 1905 crn-l; c) 7:
yield 41%, m.p. 170°C (dec.); MS (70eV): mi; 642(Me, 0.13%). 585
(Me CH,CHMe,, 28%). 220 (Cp,Zre, 66%); 'H NMR (200 MHz,
[DJbenzene): 6 = 5.57 (s, 20H. Cp), 2.39 (s, 4H, ZrCH,), 2.21 (m. 2H,
CH,CH), 1.32 (d, 12H, CH(CH,),), 0.15 (d, 4H, AICH,CH). - 3.66 (s,
l H , ZrHZr); "C NMR (50 MHz, [DJbenzene): 6 = 105.8 (Cp). 53.0
('J(CH) = 156 Hz, ZrCH,), 29.0 ('J(CH) = 123 Hz, CHCH,), 26.8
('J(CH) = 118 Hz, CHCH,), 22.1 (broad, AICH,CH).
[81 a) K. Kropp. V. Skibbe. G. Erker. C. Kriiger, J. Am. Chem. Soc. 105 (1983)
3353; b) cf. G. Erker, R. Lecht, J. L. Petersen, H. Bonnemann, Organumerullics 6 (1987) 1962.
M = 645.1, trichlinic, Pi, u = 10.217 (l),
[91 a) 7: C,,H,,AlO,Zr,,
h = 11.281 ( 2 ) , c = 13.844(2)A,x= 1 0 0 . 3 7 ( 1 ) , ~ = 9 0 . 1 2 ( 1 ) , ~106.36
(1)",V=1503.7~3,2=2,~bor=1.42gm~~,~(Mo,.)=7.33cm~'.Enraf-Nonius dlffractometer, 7145 measured reflections. 4601 observed
( I 2 u (4). R = 0.042, R, = 0.041 for 445 parameters, b) further details of
the crystal structure investigations are available on request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number
CSD-53731, the names of the authors, and the journal citation.
[lo] R. M. Waymouth, B. D. Santarsiero, R. J. Coots, M. J. Bronikowski,
R. H. Grubbs, J. Am. Chem. SOC.108 (1986) 1427.
\ /
The reactions of 5 presented here confirm and extend the
emerging consistent picture of the special behavior of metallaoxirane compounds of the early transition metals. c6, a,
Received: October 12, 1988;
revised: December 27, 1988 [Z 3004 IE)
G e m a n version : Angew. Chem. I01 (1 989) 644
CAS Registry numbers:
1. 83385-36-8; 4, 12636-72-5; 5 , 83385-20-0; 6, 119747-76-1; 7, 119747-77-2;
[(<TI, O)ZrCp,l,, 85442-82-6; CpCo(CO),,
11) E. L. Muetterties, J. Stein, Chem. Rev. 79 (1979) 479; C. K. Rofer-De
Poorter, ihid. 81 (1981) 447; see also J. F. Knifton, J. Am. Chem. SUC.I03
(1981) 3959.
[2] G. Erker, Acc. Chem. Res. 17 (1984) 103, and references cited therein;
R. E. LaPointe, P. T. Wokzdnski, J. Am. Chem. SOC.108 (1986) 3535;
P. T. Wolczanski, R. S. Threlkel, J. E. Bercaw, ibid. 101 (1979) 218; P. T.
Barger, J. E. Bercaw, Organometallics 3 (1984) 278; T. Beringhelli,
G . D'Alfonso, G. Ciani. H. Molinari, &id. 6 (1987) 194.
13) G. Fachinetti, C. Floriani, A. Roselli. S. Pucci, J. Chem. Soc. Chem. Cummun. 1978, 269: S. Gambarotta, C. Floriani, A. Chiesi-Villa, C. Guastini,
J. A m . Chem. SOC.105 (1983) 1690.
[4] G. Erker. K. Kropp, Chem. Ber. 115 (1982) 2437.
Preparative Acetylenic Chemistry (Series: Studies in Organic
Chemistry, Vol. 34). 2nd Edition. By L. Brandsma. Elsevier, Amsterdam 1988. x, 322 pp., hard cover,
HFI 220.00.-ISBN 0-444-42960-3
This book is a completely reviewed and updated version of
the original 1971 publication, and has been enlarged by more
than 100 pages. It is aimed at advanced students and preparative organic chemists.
As in other books by the same author (L. Brandsma,
H. D. Verkruijsse: Synthesis of Acetylenes, Allenes and Cumuienes, Elsevier, Amsterdam 1981 ; L. Brandsma, H. D.
Angen. Chc,m. I n i . Ed. Engl. 28 (1989) No. 5
Verkruijsse: Preparative Polar Organometallic Chemistry,
Springer, Berlin 1987), all the preparative methods contained here have been carefully tested. The reader benefits
from the author's many years of experience in acetylenic
chemistry. The recommended reaction conditions take into
account the reactivities of the starting compounds and intermediates. In practice a lack of knowledge of reactivities often
leads to reactants being unnecessarily stirred under reflux for
hours, despite the fact that the reaction is in fact completed
within a few minutes. Much time and money can be saved
when accurate information on reaction durations and reproducible laboratory recipes are available.
The topics covered in the book's twelve chapters are as
follows. Chapter 1 gives practical advice of a general nature,
and describes a number of extremely useful tricks from the
author's wealth of experience. The rest of the chapters are:
2. Metallation of Acetylenes; 3. Functionalization of Metallated Acetylenes with Alkyl Halides, cl-Haloethers, Epoxides
and Alkyl Orthoformates; 4. Ethynylation and Alkynylation
of Carbonyl Compounds; 5. Carboxylation, Alkylation and
Related Reactions; 6. Silylation, Stannylation and Phosphorylation; 7. Sulfenylations and Related Reactions; 8. Halogenation and Cyanation; 9. Introduction of the Triple Bond
by Elimination and Addition-elimination Reactions; 10.
Couplings of Acetylenes Assisted by Copper and Palladium
Compounds; 11. Base-promoted Interconversions of
Acetylenes; 12. Miscellaneous Preparations of Acetylenic
Derivatives. More than 500 acetylene derivatives, which can
ic3 VCH Verlu~sgiwllschafimhH, D-6940 Weinheim, 1989
S 02.5010
63 1
be classified into 20 different groups on the basis of their
functionality, are described in these chapters.
The concise factual style and the orderly arrangement of
the material are pleasing features. Regrettably the pages do
not have a headline identifying the chapter, and as a result
cross-referencing often involves the reader in thumbing
through the pages for a long time to find the required passage. The layout is attractive and the text contains hardly
any printing errors. Although there are only 241 literature
references this does not imply that the coverage is superficial; the smallness of the total is entirely a result of the
author’s rigorous criteria for choosing references.
To summarize, it can be said that this book, which is
structured in the style of Organic Syntheses, gives an excellent and detailed overview of important synthetic building
blocks containing C = C bonds that are simple and obtainable in good yields. When the synthetic methods are read in
conjunction with the “Introductions” which precede over
half of them and the appended “Notes” on each one, the
work is seen to be more than a mere “cook-book”. It will
certainly contribute to acetylenes assuming an even more
important role in future in the planning of synthetic routes.
The book will undoubtedly have a place in the standard
reference collection of every chemistry library.
Rolf W! Saalfrank [NB 956 IE]
Institut fur Organische Chemie
der Universitat Erlangen-Nurnberg (FRG)
Organolithium Methods. (Series: Best Synthetic Methods.)
By B. J. Wakefield. Academic Press, New York 1988. xvii,
189 pp., hard cover, $29.50.-ISBN 0-12-730940-3
The present reviewer has already remarked in this journal[*] that he regards the series title “Best Synthetic Methods” as a misleading description. Nevertheless, the volume
on “Organolithium Methods” by Wakefield is very successful as an introduction to the topic with a strong emphasis on
practical aspects. The author confines his treatment to
organolithium compounds which are not stabilized by
mesomeric effects (with the exceptions of ally1 and benzyl
derivatives of lithium). There are occasional passing references, perhaps unintentional, to the chemistry of compounds
such as lithium enolates, but to cover these fully would have
made the book too long.
The logical construction of the book together with its detailed contents list and the subject index allow one to quickly
find the relevant chapter for each topic of interest (although
the index is rather scanty). The introductory chapter is likely
to be of particular value for newcomers to the field, such as
students about to undertake their first work using organolithium compounds; it deals very briefly with constitution,
reactivity and solvent effects, and, most importantly, gives
much practical advice on matters such as the drying of solvents, use of inert atmosphere, handling of organolithium
compounds, and quantitative analysis, illustrated in some
cases by drawings of suitable apparatus.
The next chapter is devoted to the preparation of organolithium compounds, with a systematic and very instructive
presentation of the principles, which are then translated into
practical terms by giving laboratory recipes, most of which
have been tested, and clear tables. The following chapters
deal with the addition reactions of organolithium compounds to systems with multiple bonds, with the main em-
[*] Angew. Chem. Int. Ed. Engl. 27 (1988) 1567
Verlagsgesellschaft mbH. 0-6940 Weinheim, 1989
phasis, naturally, on carbonyl compounds as electrophiles.
Next follow substitution reactions with the formation of C-C
or C-heteroatom bonds, and related types of reactions. The
following chapter describes some methods whereby organolithium compounds can be used to prepare organoboron,
organosilicon and organophosphorus compounds, andthough only in outline-other organometallic species. Lastly, possibilities for using elimination reactions to form arynes, carbenes and ylides are briefly mentioned.
Every chapter includes detailed laboratory recipes and numerous examples in the form of tables. The relevant literature citations have been compiled with great thoroughness
up to 1986; even a few references to work published in 1987
are included, making the coverage pleasingly up-to-date.
As each chapter includes a brief but succinct introduction
summarizing the main features of current knowledge about
mechanisms (or sometimes the lack of it), one can obtain
from the book not only numerous practical hints and stimulating ideas, but also some basic science. Unfortunately,
though, there is no reference to the principle of polar reversal
of reactivity (umpolung), which has been and still is especially important for organolithium compounds.
The book is very attractively produced, and there are comparatively few printing errors (e.g.. the formula scheme on
page 37 has gone somewhat wrong). It is to be hoped that
this book by Wakefkld will achieve a wide circulation. It
should at least be available in all libraries. However, although it would be especially useful to students, they will
probably find it too expensive.
Hans-Ulrich Reissig [NB 952 IE]
Institut fur Organische Chemie
der Technischen Hochschule Darmstadt (FRG)
The Bioinorganic Chemistry of Nickel. Edited by J. R. Lancaster, Jr. VCH Verlagsgesellschaft, Weinheim/VCH Publishers, New York 1988. xviii, 337pp., hard cover, DM
175.00.-ISBN 3-527-26692-5/0-89573-338-2
Nickel was first discovered to play a physiological role in
a biological system in 1965, and it was first found in a metalloenzyme a decade later. It is, in retrospect, surprising that
the discovery of the importance of nickel in biology was
made so late, but the fortunate result of this delay is that for
nickel, unlike copper and iron, the tools of modern inorganic
spectroscopy were used right from the beginning of the investigations of the biochemical properties of each newly discovered metal-containing biological system. The accounts of the
elucidation of the properties of nickel-containing biological
systems therefore read like a series of ongoing scientific detective stories. This is a well-written and well-organized volume that will be useful to a large number of readers. In
addition, it is fortunate when a book such as this one describing a new field of research is written early enough that introductory material describing the methodology used, and
the accounts of the background and current status of the
field, all fit into one reasonably sized volume.
The volume consists of 14 chapters, each written by different experts in the field. The first four chapters provide the
reader with an excellent introduction to the inorganic chemistry and spectroscopy of nickel. They are each written at an
appropriate level that will enable the non-specialist to understand and to appreciate the significance of the spectroscopic
results presented in the later chapters describing specific
nickel-containing biological systems. These chapters are
“The Coordination Chemistry of Nickel: An Introductory
Survey” (C. L. Coyre and E. I. Steifel), “Nickel(II1) Chemis-
3 02.5010
Angeu. Chem. Int. Ed. Engl. 28 (1989) N o . 5
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