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Graphical Abstract Angew. Chem. Int. Ed. 362003

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Contents
The following articles are available online (in Wiley InterScience). You can find them at
www.angewandte.org, under Full Text, Early View.
P. Comba,* A. Hauser, M. Kerscher, H. Pritzkow:
Bond-Stretch Isomerism: Trapped Isomeric Structures of Hexacoordinate Copper(ii) Bispidine Chromophores along a Jahn?
Teller Active Vibrational Coordinate
DOI: 10.1002/anie.200351900
Published online: September 8, 2003
M. P. Sibi,* J. Zimmerman, T. Rheault:
Enantioselective Conjugate Radical Addition to b-Acyloxy Acrylate Acceptors: An Approach to Acetate Aldol-Type Products
DOI: 10.1002/anie.200352096
Published online: September 8, 2003
H. Xu, W. A. Goedel*:
Mesoscopic Rings by Controlled Wetting of Particle Imprinted
Templates
DOI: 10.1002/anie.200351428
Published online: September 8, 2003
R. J. Amir, N. Pessah, M. Shamis, D. Shabat*:
Self-Immolative Dendrimers
DOI: 10.1002/anie.200351962
Published online: September 8, 2003
Articles judged by the referees or the editor as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editorial office in final form. As long as there is no page number available these articles should be
cited in the following manner:
Author(s) Angew. Chem. Int. Ed., online publication date, DOI.
News
Royal Society of Chemistry Awards 4282
Books
Makromolekle
4283
Wandering in the Gardens of the
Mind
4284
Meilensteine der Wissenschaft
4284
Hans-Georg Elias
reviewed by H. W. Schnecko
John Prebble, Bruce Weber
reviewed by R. J. P. Williams
Peter Tallack
reviewed by H. Hopf
Predictable with the color rules? The NIR
dye 1 has a novel, mesoionic structure
that exhibits a ?super acceptor? function
and an absorption far in the near infrared
within a remarkably small chromophore.
Highlights
NIR Dyes
H. Langhals*
4286 ? 4288
An Unexpectedly Simple NIR Dye for
1.1 mm with a Central Mesoionic Structure
4272
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 4272 ? 4278
Angewandte
Chemie
Minireviews
O
Ph
Ph
OtBu
O
Ph
PTC
RX
N
N
OtBu
Ph
R
Optically appealing: Catalytic asymmetric
methods should allow the synthesis of
large amounts of optically active a- and bamino acids using only small amounts of
optically active catalysts (see picture;
O
Synthesis of Amino Acids
H2N
OH
J.-A. Ma*
R
PTC = phase-transfer catalyst). This contribution highlights some of the recent
developments in this area involving chiral
organometallic catalysts and metal-free
organic catalysts.
4290 ? 4299
Recent Developments in the Catalytic
Asymmetric Synthesis of a- and b-Amino
Acids
Reviews
Grignard Reagents in Synthesis
P. Knochel,* W. Dohle, N. Gommermann,
F. F. Kneisel, F. Kopp, T. Korn,
I. Sapountzis, V. A. Vu
4302 ? 4320
New perspectives in organic synthesis
have been opened by the halogen?
magnesium exchange reaction. It appears
that many more functional groups than
previously thought are compatible with
magnesium organometallic reagents
under the mild conditions required for
halogen?magnesium exchange. The central role of Grignard reagents and recent
developments in the application of
organomagnesium reagents are
described.
Highly Functionalized Organomagnesium
Reagents Prepared through Halogen?
Metal Exchange
Communications
The tendency for silver-rich compounds to
form higher agglomerates of silver atoms
or ions is well known. The synthesis of
Ag13OsO6 represents the first compound
in the Ag/Os/O system. Besides [OsO6]4
octahedra, the compound contains icosahedrally shaped Ag134+ clusters (see
picture), which are observed for the first
time in solid silver oxides.
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Angew. Chem. Int. Ed. 2003, 42, 4272 ? 4278
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
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www.angewandte.org
Subvalent Ternary Silver Oxide
S. Ahlert, W. Klein, O. Jepsen,
O. Gunnarsson, O. K. Andersen,
M. Jansen*
4322 ? 4325
Ag13OsO6 : A Silver Oxide with Interconnected Icosahedral Ag134+ Clusters
and Dispersed [OsO6]4 Octahedra
delivery); for individuals who are personal
members of a national chemical society, or
whose institution already subscribes, or who
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Europe E 248.00/Outside Europe US$ 348.00.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4273
Contents
Asymmetric Heterogeneous Catalysis
M. D. Jones, R. Raja,* J. M. Thomas,*
B. F. G. Johnson,* D. W. Lewis, J. Rouzaud,
K. D. M. Harris
4326 ? 4331
Enhancing the Enantioselectivity of Novel
Homogeneous Organometallic
Hydrogenation Catalysts
By designing well-defined, single-site
asymmetric organometallic complexes
anchored to a concave siliceous support
(see picture) high ee values may be
obtained in heterogeneous catalytic
hydrogenations. O red, Si orange, Rh
yellow, C grey, N blue, F green, B pink,
H white.
CO2 Inclusion in Crystals
S. Takamizawa,* E.-i. Nakata,
H. Yokoyama, K. Mochizuki,
W. Mori
4331 ? 4334
Carbon Dioxide Inclusion Phases of a
Transformable 1D Coordination Polymer
Host [Rh2(O2CPh)4(pyz)]n
Spin?Spin Coupling Pathways
O. L. Malkina,*
V. G. Malkin*
4335 ? 4338
Visualization of Nuclear Spin?Spin
Coupling Pathways by Real-Space
Functions
CO2 is included: The one-dimensional
coordination polymer host
[Rh2(O2CPh)4(pyz)]n (pyz = pyrazine; see
picture, left) undergoes a reversible phase
transition under cooling that is induced by
CO2 adsorption to give an inclusion
complex, in which up to three CO2
molecules per polymer unit reside within
channels (right).
Spin, a yarn: A new approach for the
visualization of indirect nuclear spin?spin
coupling is presented, which allows for a
clear judgement on the importance of the
different possible coupling pathways that
exist. For example, it is possible to
examine coupling through space or
through hydrogen-bond interactions (the
picture describes the 3JP,P coupling energy
density in the C2H2(PH2)2 molecule).
Dendrimer Shape Control
V. Percec,* M. Glodde, G. Johansson,
V. S. K. Balagurusamy,
P. A. Heiney
4338 ? 4342
Transformation of a Spherical Supramolecular Dendrimer into a Pyramidal
Columnar Supramolecular Dendrimer
Mediated by the Fluorophobic Effect
4274
Shape control: Fluorination of the ndodecan-1-yloxy groups of the amphiphilic
(3,4,5)2G2-CO2Me monodendron changes
the shape of the monodendron from an
all-trans-conical to an all-gauche-crown or
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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all-trans-tapered conformation as well as
the mode of self-assembly from a spherical to a pyramidal columnar supramolecular dendrimer (see schematic
representation).
Angew. Chem. Int. Ed. 2003, 42, 4272 ? 4278
Angewandte
Chemie
Changing the dimensions of the mesh. A
robust sequence-dependent DNA device
termed a nanoactuator was incorporated
into a 2D parallelogram DNA lattice.
Conversion of the DNA nanoactuator
between two well-defined states (S1 and
S2, see picture) results in controlled
motion of the lattice.
Nanomechanical Device
1,2-Dehydro-o-carborane, a three-dimensional relative of benzyne, has been
successfully prepared and structurally
characterized for the first time in the form
of a zirconocene complex (see picture).
This carborane molecule exhibits unique
h3-bonding characteristics, with an
unprecedented Zr-H-B agostic interaction, as well as two Zr C bonds, which
serve to stabilize the cage.
Zirconocene?Carborane Complex
A Two-State DNA Lattice Switched by
DNA Nanoactuator
H. Wang, H.-W. Li, X. Huang, Z. Lin,*
Z. Xie*
4347 ? 4349
Synthesis, Structure, and Bonding of a
Zirconocene?1,2-Dehydro-o-carborane
Complex
Winding up helices: The title compounds
are prepared by a living polymerization of
optically active ferrocenyl isocyanides
initiated with a dinuclear Pt?Pd complex.
Electrolytic CD and UV spectra suggest
that the polymers exhibit reversible conformational change in response to oxidation and reduction of the ferrocenyl
pendants (see scheme).
Electroresponsive Polymers
Carbon nanocoils with nanometer-thick
graphitic fibers (see picture) were synthesized by the simple heat treatment of
nanocomposites of a carbon precursor,
silica, and a transition-metal salt. The
carbon nanocoils exhibited a high surface
area and a highly graphitized structure.
The nanocoils were then successfully
applied as catalyst supports for direct
methanol fuel cell electrodes.
Carbon Nanocoils
N. Hida, F. Takei, K. Onitsuka, K. Shiga,
S. Asaoka, T. Iyoda,
S. Takahashi*
4349 ? 4352
Helical, Chiral Polyisocyanides Bearing
Ferrocenyl Groups as Pendants:
Synthesis and Properties
T. Hyeon,* S. Han, Y.-E. Sung, K.-W. Park,
Y.-W. Kim
4352 ? 4356
High-Performance Direct Methanol Fuel
Cell Electrodes using Solid-PhaseSynthesized Carbon Nanocoils
Iron-Mediated Aminations
An iron(iii) anilide complex can be formed
through the reaction of phenyl-N-tosylimidoiodinane with the non-heme iron
complex [(6-PhTPA)FeII(NCCH3)2](ClO4)2
(TPA = tris(2-pyridylmethyl)amine), in
which an efficient transfer of the nitrene
moiety to the ortho position of the aphenyl substituent is achieved (a hypothetical structure of the complex is illustrated, in which the tolyl ring, except for
the ipso carbon atom, is excluded for
clarity; Fe pink, S yellow, O red, N blue).
Angew. Chem. Int. Ed. 2003, 42, 4272 ? 4278
L. Feng, S. H. Park, J. H. Reif,
H. Yan*
4342 ? 4346
M. P. Jensen, M. P. Mehn,
L. Que, Jr.*
4357 ? 4360
Intramolecular Aromatic Amination
through Iron-Mediated Nitrene Transfer
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4275
Contents
Chiral Resolution
M. Sakamoto,* N. Utsumi, M. Ando,
M. Saeki, T. Mino, T. Fujita, A. Katoh,
T. Nishio, C. Kashima
4360 ? 4363
Breaking the Symmetry of Axially Chiral
N-Aryl-2(1H)-pyrimidinones by
Spontaneous Crystallization
Structure of Ionic Liquids
A. Mele,* C. D. Tran,
S. H. De Paoli Lacerda
4364 ? 4366
The Structure of a Room-Temperature
Ionic Liquid with and without Trace
Amounts of Water: The Role of C HиииO
and C HиииF Interactions in 1-n-Butyl-3Methylimidazolium Tetrafluoroborate
Rings Cages and Polymers
V. Martinez, J.-C. Blais,
D. Astruc*
4366 ? 4369
A Fast Organometallic Route from
p-Xylene, Mesitylene, and p-Diisopropylbenzene to Organoiron and Polycyclic
Aromatic Cyclophanes, Capsules and
Polymers
Pyridinol-Based Antioxidants
M. Wijtmans, D. A. Pratt,* L. Valgimigli,*
G. A. DiLabio, G. F. Pedulli,*
N. A. Porter*
4370 ? 4373
6-Amino-3-Pyridinols: Towards DiffusionControlled Chain-Breaking Antioxidants
No outside source of chirality was needed
to resolve the racemate of an axially chiral
pyrimidinone (see scheme). Crystallization at high temperatures gave optically
active material in up to 73 % ee. The
resolved product could be reduced with
NaBH4 with high enantioselectivity.
Solvated solvents: Water molecules interact with the imidazolium cation and [BF4]
ion (see picture) of the molten ionic-liquid
salt 1-n-butyl-3-methylimidazolium tetrafluoroborate. Evidence for short C HиииO
and C HиииF interactions is provided by
1
H{1H} and 1H{19F} NMR spectroscopy
nuclear Overhauser enhancements.
New organic and organoiron polycyclic
paracyclophane cages (see picture) and
polymers are rapidly formed using two
different, extremely efficient C C bond
coupling reactions from p-xylene, mesitylene and p-diisopropylbenzene: the h5C5H5-Fe+-induced perallylation- or peralkenylation reaction followed by Rucatalyzed ring-closing and cross-coupling
metathesis by using the commercially
available Grubbs catalysts.
The incorporation of nitrogen in the
phenolic ring leads to compounds with
very low phenolic O H bond dissociation
enthalpies, and thus high reactivities
towards peroxyl radicals, but which are
reasonably stable to direct reactions with
air. The 3-pyridinols 1 and 2 are extremely
effective peroxyl-radical-trapping chainbreaking antioxidants.
Intramolecular Staudinger Ligation
O. David, W. J. N. Meester, H. BierPugel,
H. E. Schoemaker, H. Hiemstra,
J. H. van Maarseveen*
4373 ? 4375
Intramolecular Staudinger Ligation: A
Powerful Ring-Closure Method To Form
Medium-Sized Lactams
4276
Efficient access to medium-sized lactams
from w-amino acids that are resistant to
ring-closure by traditional strategies is
enabled by an intramolecular Staudinger
ligation approach. An undesired prema-
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
ture Staudinger reaction is avoided by
protecting the phosphane-containing
auxiliary as a borane complex (see
scheme; dabco = 1,4-diazabicyclo[2.2.2]octane).
Angew. Chem. Int. Ed. 2003, 42, 4272 ? 4278
Angewandte
Chemie
Carbonization of aromatic sources in an
aluminosilicate mesoporous template
yields mesoporous carbon materials with
highly graphitic framework structures and
excellent mechanical strength and thermal stability (see picture). TEM analysis
shows discoid graphitic layers that are
packed so that the most preferred orientation of the c axes is along the direction
of the template channels.
Mesoporous Carbon Materials
T.-W. Kim, I.-S. Park,
R. Ryoo*
4375 ? 4379
A Synthetic Route to Ordered Mesoporous Carbon Materials with Graphitic
Pore Walls
Synthesis of Carbon Nanotubes
Free-standing films of multiwalled carbon
nanotubes (see scanning electron micrograph) encapsulating crystalline metal
particles are obtained by the solid-state
thermolytic conversion of commercial
homogeneous organometallic systems
with a defined metal-to-carbon ratio.
V. S. Iyer, K. P. C. Vollhardt,*
R. Wilhelm
4379 ? 4383
Near-Quantitative Solid-State Synthesis of
Carbon Nanotubes from Homogeneous
Diphenylethynecobalt and -Nickel
Complexes
Contact Ion Pairs and Triples
Ioning in distortions: Severe ionic distortions of phenyl-substituted hydrocarbon
anions are observed on coordination to
Na+ or K+ ions. Alkali-metal salts of 1,2diphenylbenzene (see picture: Na green,
O red) and 1,2,3-triphenylbenzene dianions are prepared by reduction, structurally characterized, and analyzed by
density functional and natural bond order
calculations. The reduction and subsequent cation coordination of the phenylbenzene ions dramatically distorts the
structures of the hydrocarbon skeletons.
H. Bock,* Z. Havlas,*
K. Gharagozloo-Hubmann, S. Holl,
M. Sievert
4385 ? 4389
1,2-Diphenylbenzene Dianion: AlkaliMetal Salts with Drastically Spread
C6 Rings
Mixed In/Ge Oxide
D. Pitzschke, W. Bensch*
4389 ? 4391
In2Ge6O15(en)2 : A In?Ge Compound
Composed of Germanate Layers Linked by
Pillars of In2O6N4 Double Octahedra
Two metals in one net: GeO4 tetrahedra
and InO6N2 octahedra are primary building units in a new indium germanate. The
germanium layers (yellow) are linked by
the InO6N2 units (red) to form a 3D
Angew. Chem. Int. Ed. 2003, 42, 4272 ? 4278
network. The compound is prepared by a
hydrothermal synthesis using GeO2 and
In(OH)3 in an aqueous solution of ethylenediamine.
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4277
Contents
Coordination of Noble-Gas Atoms
I.-C. Hwang, S. Seidel,
K. Seppelt*
Noble-gas ligands: For the first time it has
been possible to prepare a gold(i) xenon
complex ([(F3As)AuXe]+, see picture) and
a mercury(ii) xenon complex. The syntheses of these compounds start from
precursors with weakly coordinated metal
ions and take place in a superacid
medium.
4392 ? 4395
Gold(i) and Mercury(ii) Xenon
Complexes
Organization of Peptide Helices
A. M. Brckner, P. Chakraborty,
S. H. Gellman,*
U. Diederichsen*
4395 ? 4399
Molecular Architecture with
Functionalized b-Peptide Helices
Specific recognition of b-peptide helices
can be achieved by the incorporation of
nucleo-b-amino acids in every third position of b-peptide oligomers. Pairing complexes (see picture) are formed with
extraordinary high stabilities in aqueous
buffer. A major contribution comes from
the high preorganization of the nucleobases by the 14-helix backbone.
Cycloadditions and Domino Reactions
G. Dyker,* D. Hildebrandt, J. Liu,
K. Merz
4399 ? 4402
Gold(iii) Chloride Catalyzed Domino
Processes with Isobenzopyrylium Cation
Intermediates
A potpourri of remarkable reactions is
initiated by the AuCl3-catalyzed cyclization
of an ortho-alkynyl benzaldehyde. In the
presence of an olefin or an electron-rich
heteroarene as a dienophile or nucleophile, this cyclization provides selective
access to a broad variety of polycyclic
structures (see scheme).
Communications labeled with this symbol have been judged by two referees as being ?very important papers?.
The publication of Communications labeled with this symbol has been accelerated because of their topical or highly competitive
nature.
Service
Keywords
4404
Authors
4405
Angewandte?s
Sister Journals
Preview
4278
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
4406 ? 4407
4409
Angew. Chem. Int. Ed. 2003, 42, 4272 ? 4278
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