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Book Review Organic Synthesis via Organometallics. Edited by K. H. Dtz and R. W. Hoffmann

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indication that a cyclopropyl cation such as 14a, b, or a
correspondingly bridged cation survives without ring opening. In the I3C NMR spectrum (125 MHz) of the dibromide
15b at temperatures above + 50°C two signals are observed
for methylene carbon atoms; at lower temperatures
( 5-25 “C) four sharp signals are observed. Accordingly,
two conformers of 15b are present in equilibrium whose
interconversion is characterized by a rotation barrier
(AG* z 14.1 kcalmol-’, estimated from the coalescence
temperature) unusually high for bicyclopropyl derivatives.[221
Received: July 3, 1991 [Z 4769 IE]
German version: Angew. Chem. 103 (1991) 1544
(11 a) P. LePerchec, J.-M. Conia, Tetrahedron Lett. 1970, 1587; b) L. Fitjer,
J.-M. Conia, Angew. Chem. 85 (1973) 347; Angew. Chem. Inr. Ed. Engl. 12
(1973) 332; c) A. H. Schmitt, U. Schirmer, J.-M. Conia, Chem. Ber. 109
(1976) 2588; d) W. Weber, A. de Meijere, Synth. Commun. 16 (1986) 837.
121 a) R. C. Lord, C. J. Wurrey, Spectrochim. Acta, Part A30(1974) 915; b) F.
Gerson, A. de Meijere, X.-Z. Qin, J. Am. Chem. SOC.f11 (1989) 1135.
[3] R. Gleiter, R. Haider, J.-M. Conia, J.-P. Barnier, A. de Meijere, W. Weber,
J. Chem. SOC.Chem. Commun. 1979, 130.
(41 M. Traetteberg, A. Simon, E.-M. Peters, A. de Meijere, 1 Mol. Struct. 118
(1984) 333.
[5] a) W. Weber, U. Behrens, A. de Meijere, Chem. Ber. 114 (1981) 1196; b) D.
Kaufmann, A. de Meijere, ibid. 117 (1984) 3134; c) A. Hofland, H. Steinberg, T. J. de Boer, Red. Trav. Chim. Pays-Bas 104 (1985) 350; d)A. de
Meijere, H. Wenck, F. Seyed-Mahdavi, H. G. Viehe, V. Gallez, I. Erden,
Tetrahedron 42 (1986) 1291; e) A. de Meijere, I. Erden, W. Weber, D.
Kaufmann, J. Org. Chem. 53 (1988) 152.
(61 F. Seyed-Mahdavi, R. Machinek, R. Gleiter, A. Flatow, M. Spiekermann,
A. de Meijere, unpublished results; F. Seyed-Mahdavi, Diplomarbeit, Universitat Hamburg 1982.
[7] L. Fitjer, Chem. Ber. 115 (1982) 1035, 1047.
(81 With a value of IE,, = 8.50 eV, the x-ionization energy o f 4 is about 0.1 eV
lower than that of 2 (IE”,,= 8.60 eV [6]).
[9] H. Wenck, A. de Meijere, F. Gerson, R. Gleiter, Angew. Chem. 98 (1986)
343; Angew. Chem. Int. Ed. Engl. 25 (1986) 335.
[lo] All the new compounds were completely characterized by spectroscopic
methods (‘H NMR, IR, Raman, MS), elemental analyses, and/or crystal
structure analyses.
[Ill L. Fitjer, J.-M. Conia, Angew. Chem. 85 (1973) 349; Angew. Chem. Inr. Ed.
Engl. 12 (1973) 334.
[12] W. Kirmse, H. Schiitte. Chem. Ber. 109 (1968) 1674.
1131 Systematic name: heptaspiro[]heptadecane.For
such hydrocarbons consisting exclusively of spiro-coupled cyclopropane
rings the trivial name [nltriangulanes has been proposed: N. S . Zefirov,
S . I. Kozhushkov, T. S. Kusnetsova, 0. V. Kokoreva, K. A. Lukin, B. I.
Ugrak, S . S . Tratch, J. Am. Chem. SOC.112 (1990) 7702. 10 is accordingly
an [8]triangulane with C,, symmetry [14].
1141 The preparation of the perspirocyclopropanated spiropentane, a
[6]triangulane with D,, symmetry, from 4 and diazocyclopropane generated in situ is reported in connection with a general strategy for the synthesis
of branched [n]triangulanes. Cf. N. S. Zefirov, S . I. Kozhushkov, B. I.
Ugrak, K. A. Lukin, 0. V. Kokoreva, D. S . Yufit, Y. T. Struchkov, S.
Zollner, R. Boese, A. de Meijere, J. Org. Chem. 58 (1992) in press.
[I 51 N-Cyclopropyl-N-nitrosoureawas obtained by nitrosation of cyclopropylurea analogously to the procedure for N-nitroso-N-(frans-2-methylcyclopropy1)urea: W. Kirmse, H. Urbach, Chem. Ber. 105 (1972) 8.
[I61 Cf. J. Furukawa, N. Kuwabata, J. Nishimura, Telrahedron 24 (1968) 53.
The [6]triangulane 13 was prepared independently by another route and
thus completely characterized. Cf. 114).
Determination of the crystal structures of 5 and 10: diffractometer Nicolet
R 3m/V, 2.(MoK,,), graphite monochromator, w-scan, 3” < 20 < 45”, direct
methods (SHELXTL-PLUS). 5 : crystal dimensions: 0.24 x 0.14 x
0.03 mm’, space group P2,/c, 2 = 2, T = 210 K, cell dimensions
a = 696.3(2), b = 1013.4(3), c = 819.1(2) pm, = 102.27(2)”, 612 independent intensities.481 observed (Fo 2 4a(F)), 68 parameters for the structure refinement with hydrogen atoms as rigid groups, R = 0.037,
R , = 0.038. 10: crystal dimensions: 0.20 x 0.12 x 0.09 mm’, space group
P2,/c,Z = 8, T = 190 K, cell dimensions a = 1135.5(4), b = SS8.0(4).
c = 2751.5(10) pm, p = 100.36(3)”, 3577 independent intensities, 1803 observed (Fo > 4u(F)), 308 parameters for the structure refinement with hydrogen as rigid groups, R = 0.058, R, = 0.052. Lower measuring temperatures led, in the case of 5 and 10, to a deterioration in the quality of the
crystals due to reversible phase transformations. Further details of the
crystal structure investigations are available on request from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH, W-7514 Eggenstein-Leopoldshafen 2 (FRG), on
quoting the depository numbers CSD-320287 (for 5) and CSD-320286(for
lo), the names of the authors, and the journal citation.
Similar differences in the bond lengths were observed for spiropentane (cf.
R. Boese, D. Blaeser, K. Gomann, U. H. Brinker, 1 Am. Chem. SOC.
(1989) 1501). [3]rotane (cf. R. Boese, T. Miebach, A. de Meijere, J. Am.
Chem. Soc. 113 (1991) 1743), and for the perspirocyclopropanated
spiropentane (cf. [14]).
Cf. M. Eckert-Maksic, S . Zollner, L. Maksimovic, W. Gothling, R. Machinek, R. Boese, A. de Meijere, Chem. Ber. 124 (1991) 1591, and references cited therein.
L. Fitjer, unpublished results; private communication to A. de Meijere,
May 1991.
R. Stolevik, P. Bakken, J. Mol. Struct. 197 (1989) 137.
Organic Synthesis via Organometallics.Edited by K . H. Dotz
and R. W Hofmann. Vieweg, Braunschweig 1991. viii,
323 pp., hardcover DM 92.00.-ISBN 3-528-08 947-4
This volume contains 17 papers presented at the third
symposium on research topics sponsored by the Volkswagen-Stiftung, which was held in Marburg in July 1990. It
is a wide-ranging and readable survey of recent applications
of organometallic reagents and reactions in organic synthesis. The organizers have once again put together an attractive program of lectures, containing a balanced mixture
of “classical” topics and new developments in the field of
organometallic chemistry.
Verlagsgesellschafr mbH, W-6940 Weinheim, 1991
0570-0833/91jlll1-1520 $3.50+ ,2510
Angew. Chem. Int. Ed. Engl. 30 (1991) N o . 11
R . H . Grubbs reports on the use of titanacyclic compounds
and alkylidene complexes in “Living Ring-Opening
Metathesis Polymerization” (ROMP) and the application of
this method to the preparation of block copolymers and
highly conjugated polymers, of which the extreme example is
polyacetylene. W Keim et al. give a wide-ranging review of
the enantioselective telomerization of 1,3-dienes using palladium and nickel catalysts, including discussions of analytical
and mechanistic aspects. A short article by H . H . Brintzinger
on chiral ansa-metallocenes, in which the stereoselectivity of
r-olefin polymerizations is explained by mechanistic arguments, is then followed by H . Fischer’s contribution on benzylidene complexes as C, sources, which is a somewhat
longer report describing their stereoselective conversion to
give cyclopropane derivatives and heterocycles. In a very
interesting and highly imaginative article D. Astruc summarizes the work of his group on “Organo-Iron Complexes in
Aromatic Synthesis”. This describes how simple cationic
complexes of hexamethylbenzene with iron are used, in a
single-pot reaction, to prepare “tentacle” molecules, and
how the benzyl sites are then activated by electron transfer
reactions to yield a wide variety of new complexes, many of
which are multinuclear. Especially worth mentioning here is
a compilation of literature references on the activation of
arenes by transition metals. The article by D . Walther et al.
describes the activation of CO, using nickel(0) complexes
and alkenes or alkynes to give nickela-cyclic carboxylates,
which can also be prepared by reacting a bipyridyl-stabilized
diethylnickel species with cyclic anhydrides. Especially interesting here are the cyclizations with alkynes leading to the
formation of the preparatively very useful 2-pyrones with
selectivities of more than 90 % ; the trimerization reaction of
the alkyne is almost completely suppressed. A description of
the use of steroid systems in cross-coupling reactions with
nickelacarboxylates and a section on the carboxylation of
C-H bonds and of imines as “reversible CO, carriers” serve
to emphasize the close relationship between organometallic
and bioorganic CO, chemistry. The next article by J. K.
Kochi on “Charge-Transfer Activation of Organometallic
Reactions” is quite long, and is of fundamental importance
to an understanding of many of the reactions of organometallic chemistry. However, the relevance to organic synthesis here is rather tenuous.
The review by H.-J. Knolker on the use of dienyliron complexes in synthesizing natural products is very well worth
reading and full of information. It is pleasing to find that a
large number of the author’s published papers, which have
appeared within a remarkably short period, are here summarized. The emphasis is again on iron in the article by P .
Eilbracht et al. ;these authors have converted cyclohexadiene
derivatives, via their complexes with Fe(CO), with insertion
of CO. into a wide variety of carbocycles, some of which are
quite complicated, and have investigated the mechanisms of
the reaction steps. G. R. Stephenson et al. are concerned with
the control of regiospecificity in alkylation reactions using
cyclohexadienyliron complexes, and the very careful and
thorough study reported here shows that there are close
relationships to alkaloid syntheses. C. P . Casey et al. summarize their recent investigations on new reactions of
organorhenium compounds, which are very interesting from
a mechanistic standpoint; they also discuss the importance
of heterobimetallic systems. J. Okudu et al. describe the ligand (3-butenyl)tetramethylcyclopentadienyl; as a ligand
with an olefinic side-chain this is capable of reversibly blocking one of the coordination sites of the metal atom in the
corresponding cyclopentadienyl complexes. The chemical
behavior with cobalt is particularly interesting here, since the
Angew. Chem. In!. Ed. Engl. 30 (1991) No. 11
[2 + 2 + 21-cycloadduct was formed from two alkyne molecules and the double bond of the ligand, which, however, is
irreversibly attached to the ligand. The contribution by C.
Bolm is concerned with the use of optically active bipyridines
in enantioselective synthesis; the author has alkylated aldehydes and u,fl-unsaturated ketones with varying degrees of
enantioselectivity in the presence of these chiral ligands using
palladium or nickel catalysts. In the article by K Schurig the
main preparative interest is centered on enantioselective
methods for preparing simple oxiranes. The author also discusses aspects of prochiral and chiral recognition using complexation gas chromatography. In the article by D . Hoppe we
are reminded that “organometallics” are not confined to
transition metal compounds: N,N-dialkylcarbamoyloxy
groups not only facilitate lithiation at the adjacent sites but
also, as a result of intramolecular complexation, increase the
configurational stability of the ion pairs that are formed,
which has very important consequences for enantioselective
syntheses. An industrial research team led by A . Hafner describes a fruitful combination of transition metal chemistry
with carbohydrate chemistry: by forming chiral complexes
of carbohydrates with titanium, zirconium and hafnium, the
authors were able to prepare a number of enantiomerically
pure reactive alkylating agents. In a large number of reactions this good idea yielded enantiomeric excesses and
diastereoselectivities that were in most cases very high. Last
but not least in this collection of articles, R. Noyori et al.
present a very lucid contribution on “Multiplication and
Amplification of Chirality”. Catalytic concentrations of
enantiomerically pure 3-exo-(dimethylamino)isoborneoI
(DAIB) cause alkylzinc compounds to react with aldehydes
giving secondary alcohols with ee values up to 99%. Even
when the DAIB present in catalytic amounts has an ee value
of only 14%, a product with an ee value of 98 % is obtained.
The 17 articles have been reproduced directly, which
means that the publishers have had almost no typesetting or
correction work to do. The authors too have done their work
thoroughly, and there are very few errors; in the case of the
German authors one occasionally comes across idioms carried over from the German language. It would have been
desirable in the reaction schemes to give details of yields and
reaction conditions wherever possible. The book can be recommended to everyone interested in organometallic chemistry and organometallic methods of synthesis; it is suitable,
rather in the manner ofan advanced seminar, as an introduction to the areas of work described. A cheaper paperback
edition would have been desirable.
Holger Butenschh [NB 1177 IE]
Max-Planck-Institut fur Kohlenforschung
Mulheim a. d. Ruhr (FRG)
Materials Science and Technology (A Comprehensive Treatment). Volume 5: Phase Transformations in Materials. Edited by P . Haasen. VCH Verlagsgesellschaft, Weinheim/
VCH Publishers, New York 1991. xiii, 648 pp., hardcover
DM 430.00.-ISBN 3-527-268 18-9/0-89573-693-4
This series is planned to consist of 18 volumes altogether;
by the end of this year a further six volumes will have been
published in addition to Volume 5 which is reviewed here.
One can expect this to be an exciting series when completeand the same also goes for the price. The editors ( R . W Cahn,
P . Haasen and E. J. Kramer), on behalf of the authors (of
whom there are more than 200), introduce the series as follows: “The new series is intended to mark the coming-of-age
lJerlagsgesellschaft m b H , W-6940 Weinheim, 1991
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