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Graphical Abstract Angew. Chem. Int. Ed. 402005

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The following Communications have been judged by at least two referees to be “very
important papers” and will be published online at soon:
S. Klaus, H. Neumann, A. Zapf, D. Strbing, S. Hbner, J. Almena,*
T. Riermeier, P. Groß, M. Sarich, W.-R. Krahnert, K. Rossen,
M. Beller*
A General and Efficient Method for the Formylation of Aryl and
Heteroaryl Bromides
N. Mart-n,* .. Mart-n-Domenech, S. Filippone, M. Altable,
L. Echegoyen,* C. M. Cardona
Retro-Cycloaddition Reactions of Pyrrolidinofullerenes
C. H2bartner, S. K. Silverman*
Modulation of RNA Tertiary Folding by Incorporation of Caged
M. Nakamura,* A. Hajra, K. Endo, E. Nakamura*
Synthesis of Chiral a-Fluoroketones through Catalytic
Enantioselective Decarboxylation
J. M. Macak, H. Tsuchiya, L. Taveira, S. Aldabergerova, P. Schmuki*
Smooth Anodic TiO2 Nanotubes
Y. Yamaguchi,* S. Kobayashi, T. Wakamiya, Y. Matsubara,
Zen-ichi Yoshida*
Banana-Shaped Oligo(aryleneethynylenes): Synthesis and
Light-Emitting Characteristics
Meeting Reviews
A Feast of Supramolecular Chemistry
D.-P. Funeriu*
Evaluation of Enzyme Inhibitors in Drug
Robert A. Copeland
reviewed by R. Breinbauer
Essential NMR
Bernhard Bl"mich
reviewed by A. Ltzen
Not only aesthetically appealing: The
motif of the double-stranded helix (see
picture) is found in DNA, which is able to
store and process “information”. It
inspires scientists to search for ways to
mimic not only its fascinating structure
but also to develop helical systems with
different functionalities and properties,
with which one day, likewise, information
storage and processing could be
Helical Structures
M. Albrecht*
6448 – 6451
Artificial Molecular Double-Stranded
Electron Transfer
R. J. Crutchley*
6452 – 6454
Charge-Transfer Isomers and MixedValence Properties
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
The unusual suspects: By using a series of
ruthenium clusters of the type [{Ru3O(mCH3COO)6(CO)L’}(m-l){Ru3O(mCH3COO)6(CO)L’’}] (see picture) it has
been possible to identify the existence of
charge-transfer isomers and establish
them as identifiable chemical entities that
exist in dynamic equilibrium.
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
Heterogeneous Catalysts
Living in isolation: Single-site heterogeneous catalysts offer a widely applicable
strategic principle for the design of new
mono- and bifunctional catalysts. They
combine the merits of homogeneous and
heterogeneous processes and permit the
preparation of high activity regio-, shape-,
and enantioselective solid catalysts. The
picture shows a spatially constrained
organometallic, RhI-based enantioselective catalyst.
J. M. Thomas,* R. Raja,
D. W. Lewis
6456 – 6482
Single-Site Heterogeneous Catalysts
Spinning out: A cyanide-bridged molecular square (see picture) has been isolated
and found to undergo thermally induced,
two-step spin crossover. Molecules with
more than one spin-crossover site are
suitable building blocks for multistepped
molecular switches.
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
M. Nihei, M. Ui, M. Yokota, L. Han,
A. Maeda, H. Kishida, H. Okamoto,
H. Oshio*
6484 – 6487
Two-Step Spin Conversion in a CyanideBridged Ferrous Square
Supramolecular Chemistry
Unusual octahedral hexamers built up
from triangular, corner-linked cobalt
trimers (see figure), form the basis of a
novel three-dimensional cobalt isophthalate obtained by a solvothermal
route. This structure provides a new
example of the concept of scale chemistry,
in which an {Na6Co6O26} “super octahedron” is connected in a classical ReO3
For the USA and Canada:
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Molecular Switches
C. Livage,* N. Guillou, J. Chaigneau,
P. Rabu, M. Drillon,
G. FBrey
6488 – 6491
A Three-Dimensional Metal–Organic
Framework with an Unprecedented
Octahedral Building Unit
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
M. E. Hyde, T. J. Davies,
R. G. Compton*
The unique structure of a highly ordered
pyrolytic-graphite (HOPG) surface is
employed as a template to fabricate large
random arrays of metal-nanoband electrodes. This process is achieved through
selective blocking of the basal-plane
HOPG (A) with a polymer film (B),
followed by metal coating (C) and
cleavage of the metal layer from the
HOPG substrate (D; see picture).
M. Affronte,* I. Casson, M. Evangelisti,
A. Candini, S. Carretta, C. A. Muryn,
S. J. Teat, G. A. Timco,* W. Wernsdorfer,
R. E. P. Winpenny*
6496 – 6500
Linking Rings through Diamines and
Clusters: Exploring Synthetic Methods for
Making Magnetic Quantum Gates
Polymer clay for chemists: High strengths
and high fracture energies of polymeric
hydrogels have been demonstrated by
incorporating a substantial amount of
nanodispersed inorganic clay during the
in situ free-radical polymerization of Nisopropylacrylamide. By varying the
amount of clay used, mechanical properties as well as the swelling and transparency of the nanocomposite (NC) could be
controlled (see picture; NC20 contains
more clay than NC5).
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
Fabrication of Random Assemblies of
Metal Nanobands: A General Method
Cage Compounds
Gates leading from cages: Linked paramagnetic cage complexes could potentially be used as quantum gates for
quantum information processing. Experiments demonstrate that it is possible to
link octanuclear {Cr7Ni} rings through
both organic and metal–organic fragments into supramolecular dimers (see
structure; Cr green, Ni light green, Cu
orange, F yellow, O red, N blue, C black).
Acid test: Macrocyclic compounds that
comprise a 9,10-anthracene subunit
linked by a C2-symmetric peptidomimetic
6491 – 6496
chain (see formula) are useful as fluorescent probes in a pH range of biomedical
interest. Changes in the size of the
macrocycle (n = 3,4,6,8) produce a shift in
the pKa values. Experiments with live
mouse macrophage cells show the selective localization of the probe in the acidic
organelles (see differential interference
contrast image).
K. Haraguchi,* H.-J. Li
6500 – 6504
Control of the Coil-to-Globule Transition
and Ultrahigh Mechanical Properties of
PNIPA in Nanocomposite Hydrogels
Fluorescent Probes
F. Galindo,* M. I. Burguete, L. Vigara,
S. V. Luis,* N. Kabir, J. Gavrilovic,
D. A. Russell*
6504 – 6508
Synthetic Macrocyclic Peptidomimetics as
Tunable pH Probes for the Fluorescence
Imaging of Acidic Organelles in Live Cells
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Host–Guest Systems
H.-B. Cui, K. Takahashi, Y. Okano,
H. Kobayashi,* Z. Wang,
A. Kobayashi
6508 – 6512
Dielectric Properties of Porous Molecular
Crystals That Contain Polar Molecules
Simply lowering the temperature changes
a polarizable molecular system, which
consists of H2O and CH3OH inserted into
the porous crystal [Mn3(HCOO)6] (see
structure; Mn pink, C gray, O red), into a
nonpolarizable one. Although a large drop
in the dielectric constant was observed
around 120 K, reminiscent of a
liquid$solid phase transition of the guest
molecules, the anisotropy cannot be
explained by a simple liquid model of the
guest molecules.
The problem of miniaturizing the mixing
process is a barrier to the advance of
microfluidic technology. Fluorescence
lifetime imaging is a powerful technique
for the quantitative mapping of mixing in
microfluidic systems, providing information essential to the design and evaluation
of next-generation devices. With the use of
a pulsed laser (B), mixing in a microfluidic
cell (A) can be measured with fluorescence (C); a sample image is shown
S. W. Magennis, E. M. Graham,
6512 – 6516
A. C. Jones*
Quantitative Spatial Mapping of Mixing in
Microfluidic Systems
Supramolecular Chemistry
V. Percec,* A. E. Dulcey, M. Peterca,
M. Ilies, J. Ladislaw, B. M. Rosen,
U. Edlund, P. A. Heiney
6516 – 6521
The Internal Structure of Helical Pores
Self-Assembled from Dendritic
Dipeptides is Stereochemically
Programmed and Allosterically Regulated
Keeping nature under control: The internal structure of helical porous protein
mimics self-assembled from hybrid dendritic dipeptides is programmed by the
stereochemistry of the dipeptide and
regulated allosterically. This is the first
example of a synthetic helical porous
supramolecular structure that is stable
both in solution and in the solid state, and
that is created by a sequence of events
related to those encountered in nature.
Synthetic Methods
O. JimBnez, G. de la Rosa,
R. Lavilla*
6521 – 6525
Straightforward Access to a Structurally
Diverse Set of Oxacyclic Scaffolds through
a Four-Component Reaction
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Just add CH3CN and stir! Four building
blocks taken in a multicomponent reaction (MCR, see picture; Tf = trifluoromethanesulfonyl) afford a b-aminoacetal
adduct, which can be further diversified by
post-condensation reactions. The modular character of this approach, the simplicity of the building blocks used, and the
structural diversity attained render this
process attractive for combinatorial as
well as target- and diversity-oriented
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
Helical Structures
Artificial a helices prepared by the replacement of a hydrogen bond between
residues i and i + 4 with a carbon–carbon
bond can stabilize biologically relevant
peptides in helical conformations (1,
internal constraint shaded in gray). a Helices based on hydrogen-bond surrogates
that mimic Bak BH3 (2, yellow) can bind
their expected protein receptor, Bcl-xL
(2, green), with high affinity and resist
proteolytic degradation.
D. Wang, W. Liao,
P. S. Arora*
Enhanced Metabolic Stability and ProteinBinding Properties of Artificial a Helices
Derived from a Hydrogen-Bond
Surrogate: Application to Bcl-xL
Au natural: A new class of synthesized
biomaterials (saccharide–peptide hybrid
copolymers shown) are biodegradable,
nontoxic, and nonimmunogenic. The cationic saccharide–peptide hybrid copolymers were also shown to be effective in
compacting and transferring plasmid
DNA into cells.
An efficient and highly diastereoselective
intramolecular Diels–Alder reaction is the
basis of a concise asymmetric synthesis of
the potent antibacterial natural product
abyssomicin C (see formula). The complexity of the target structure was reduced
to three fragments and required two
carbonyl addition reactions to achieve key
bond formations.
M. Metzke, N. O’Connor, S. Maiti,
E. Nelson, Z. Guan*
6529 – 6533
Saccharide–Peptide Hybrid Copolymers
as Biomaterials
Natural Product Synthesis
C. W. Zapf, B. A. Harrison, C. Drahl,
E. J. Sorensen*
6533 – 6537
A Diels–Alder Macrocyclization Enables
an Efficient Asymmetric Synthesis of the
Antibacterial Natural Product
Abyssomicin C
Illuminating quadruple bonds: The polymeric materials [M2(O2CC6H2-2,4,6Me3)2(O2C-(Thp)n-CO2)]n (M = Mo or W
(green); Thp = thiophene (S atoms
yellow); DMSO molecules also shown)
incorporate metal–metal quadruple
bonds and form thin films from THF
solutions. These films show electroluminescence when deposited on an indium–
tin oxide glass-coated plate followed by
vapor deposition of aluminum or calcium.
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
6525 – 6529
Metal–Metal Bonds
M. H. Chisholm,* A. J. Epstein,*
J. C. Gallucci, F. Feil,
W. Pirkle
6537 – 6540
Oligothiophenes Incorporating Metal–
Metal Quadruple Bonds
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Magnetic Clusters
R. T. W. Scott, S. Parsons, M. Murugesu,
W. Wernsdorfer, G. Christou,
E. K. Brechin*
6540 – 6543
Linking Centered Manganese Triangles
into Larger Clusters: A {Mn32} Truncated
Cutting Corners: Elaborate triangular
arrays of Mn ions are stabilized by the
tripodal ligand 1,1,1-tris(hydroxymethyl)ethane. The self-assembled {Mn32} truncated cube (see picture) is further stabilized by end-on-bridging azide ligands and
acetate groups. Such stabilization could
prove to be useful in the preparation of
single-molecule magnets.
Asymmetric Synthesis
X.-X. Yan, C.-G. Liang, Y. Zhang, W. Hong,
B.-X. Cao, L.-X. Dai,
X.-L. Hou*
6544 – 6546
Highly Enantioselective Pd-Catalyzed
Allylic Alkylations of Acyclic Ketones
Pocket the difference: Highly enantioselective allylic alkylation of simple acyclic
ketones is carried out by using a Pd
catalyst with a “chiral pocket” ligand 1
(see scheme). The addition of a Lewis acid
such as AgBr and the selection of one
enolate form over another dramatically
affect the enantioselectivity of the
Surprising rearrangements in a rigid
system: A cyclopropyl ring is formed
unexpectedly when a trienone substrate is
subjected to the Nazarov cyclization (see
scheme). The participation of the unconjugated alkene unit present in the sub-
strate might be a consequence of the
complete torquoselectivity of the initial
electrocyclic closure. A subsequent rearrangement by a homo-1,5-hydrogen shift
occurs cleanly to give the final product.
Domino Pericyclic Processes
S. Giese, R. D. Mazzola, Jr., C. M. Amann,
A. M. Arif, F. G. West*
6546 – 6549
Unexpected Participation of an
Unconjugated Olefin during Nazarov
Cyclization of Bridged Bicyclic Dienones
Electrode Materials
F. Jiao, K. M. Shaju,
P. G. Bruce*
6550 – 6553
Synthesis of Nanowire and Mesoporous
Low-Temperature LiCoO2 by a PostTemplating Reaction
Giving in to templation: Lithium-containing nanostructured transition metal
oxides have been prepared by a templating route with preservation of the nanostructure. Both one-dimensional nanowire
and three-dimensional mesoporous samples of low-temperature (LT)-LiCoO2 with
highly crystalline structures (see image)
have been obtained, and these perform
better than “normal” LT-LiCoO2 as intercalation electrodes in lithium batteries.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
Delocalization in heterocycles: Reaction
of hexaphenylstannole with excess lithium
gives the dilithium stannole as deep-red
crystals. The aromaticity of the dianion
was examined by NMR spectroscopy, Xray analysis (see picture), and calculations. The dianion has considerable aromatic character and is reported to be the
first tin-containing carbocyclic aromatic
Thrifty catalysis: Tungsten carbide microspheres with high surface area and CO
chemisorption capacity were prepared by
heating mixtures of a resorcinol–formaldehyde polymer and ammonium metatungstate. Platinum supported on these
microspheres (see electron micrograph)
shows higher activity than the commercial
catalyst with 20 % Pt–Ru (1:1) on C for the
electrooxidation of methanol.
Take the rough with the smooth: Conducting silica microspheres with different
morphologies—rough, dotted, and
smooth (see picture)—have been rapidly
synthesized in an ionic liquid under
various experimental conditions. The
conducting property of the silica particles
is attributed to the presence of entrapped
molecules of ionic liquid and water.
M. Saito,* R. Haga, M. Yoshioka,
K. Ishimura, S. Nagase
6553 – 6556
The Aromaticity of the Stannole Dianion
Heterogeneous Catalysis
R. Ganesan, J. S. Lee*
6557 – 6560
Tungsten Carbide Microspheres as a
Noble-Metal-Economic Electrocatalyst for
Methanol Oxidation
Conducting Materials
D. S. Jacob, A. Joseph, S. P. Mallenahalli,
S. Shanmugam, S. Makhluf,
J. Calderon-Moreno, Y. Koltypin,
A. Gedanken*
6560 – 6563
Rapid Synthesis in Ionic Liquids of RoomTemperature-Conducting Solid Microsilica
T. Kubo,* A. Shimizu, M. Sakamoto,
M. Uruichi, K. Yakushi, M. Nakano,
D. Shiomi, K. Sato, T. Takui, Y. Morita,
K. Nakasuji*
6564 – 6568
A phenalenyl-based Kekul> hydrocarbon
with singlet biradical character has been
isolated and characterized. Strong intraand intermolecular interactions between
the unpaired electrons lead to short p–
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
p contacts and formation of one-dimensional chains (see picture). Thus, wide
valence and conduction bands are established, and the compound shows semiconductive behavior.
Synthesis, Intermolecular Interaction, and
Semiconductive Behavior of a Delocalized
Singlet Biradical Hydrocarbon
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. Ghosh,* B. C. Noll,
T. P. Fehlner*
6568 – 6571
Borane Mimics of Classic Organometallic
Compounds: [(Cp*Ru)B8H14(RuCp*)]0,+,
Isoelectronic Analogues of Dinuclear
Pentalene Complexes
Body doubles: An isolectronic borane
analogue of a dinuclear ruthenium–pentalene (C8H6) p complex (see picture) has
been prepared and isolated. It is found to
Bioinorganic Chemistry
Y. Oaki, H. Imai*
be an intermediate in the growth of the
borane fragment of a diruthenaborane
Mother-of-pearl has a three-level nanoscopic-to-macroscopic hierarchical architecture, which provides storage for
organic molecules at the nanoscale. A
material that mimics the hierarchical
architecture and nanostorage properties
of nacre emerges from the simple crystallization of potassium sulfate and
poly(acrylic acid) (see picture).
6571 – 6575
The Hierarchical Architecture of Nacre
and Its Mimetic Material
Asymmetric Synthesis
R. P. Herrera, V. Sgarzani, L. Bernardi,
A. Ricci*
6576 – 6579
Catalytic Enantioselective Friedel–Crafts
Alkylation of Indoles with Nitroalkenes by
Using a Simple Thiourea Organocatalyst
A facile access to optically active 2-indolyl1-nitro derivatives, which can be easily
transformed into highly valuable compounds such as tryptamines and 1,2,3,4tetrahydro-b-carbolines, is provided by the
J. C. Slootweg, S. Krill, F. J. J. de Kanter,
M. Schakel, A. W. Ehlers, M. Lutz,
A. L. Spek,
K. Lammertsma*
6579 – 6582
Valence Isomerization of 2Phosphabicyclo[1.1.0]butanes
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
first catalytic enantioselective Friedel–
Crafts alkylation of indoles with nitroalkenes (see scheme; e.g. R1 = R2 = H,
R3 = Ph).
Remarkably stable 2-phosphabicyclo[1.1.0]butanes (see picture; O red, P violet,
W turquoise) were synthesized from the
complexed phosphinidene PhP=W(CO)5
and cyclopropenes. These compounds
undergo valence isomerization to form 3phosphacyclobutenes via 1-phosphabutadienes at elevated temperatures.
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
Conjugate Additions
J. Barluenga,* A. de Prado, J. SantamarUa,
M. TomVs
6583 – 6585
A simple start: A tungsten carbene 3, 2trimethylsilyloxyfuran (4), and an enantiopure aldehyde 5 provide easy access to
enantiopure butenolides 2. The metal
carbene increases the accepting character
of the C=C bond and allows further
transformations into butenolide structures such as 1.
Uncatalyzed Mukaiyama–Michael
Reaction: Rapid Access to Simple and
Complex Enantiopure g-Butenolides
Computational Chemistry
M. Harańczyk,
M. Gutowski*
Enamine–imine transformations of
guanine lead to tautomers that support
valence anionic states which are adiabatically bound by as much as 8 kcal mol1
(see scheme). The valence anions might
be formed by dissociative electron
attachment followed by attachment of a
hydrogen atom to a carbon atom. Such
tautomers might affect the structure and
properties of DNA and RNA exposed to
low-energy electrons.
6585 – 6588
Finding Adiabatically Bound Anions of
Guanine through a Combinatorial
Computational Approach
DNA Replication
P. Hagenbuch, E. Kervio, A. Hochgesand,
U. Plutowski, C. Richert*
6588 – 6592
Chemical Primer Extension: Efficiently
Determining Single Nucleotides in DNA
Rapid replication: Non-enzymatic primer
extension has previously been studied in
the context of prebiotic chemistry, but not
for practical applications. Reactions with
primers featuring a 3’-amino-2’,3’-dideoxynucleotide can be rapid and selective for
all four templating nucleobases (see
scheme). On a chip with immobilized
capture strands, 500 fmol of template
suffice for single-nucleotide determinations within 2.7 h.
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ADHOC 2005 in Cologne: The Latest in
Dioxygen Activation and Homogeneous
Catalytic Oxidation
C. Limberg*
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200502936
Some sentences in the meeting review of ADHOC 2005 in Cologne were incorrect at the
time of press.
Page 6102, column 1, line 11 should read: To gain better insights, model systems with
well-defined active sites are being developed; on the other hand problems are
approached with the aid of kinetic measurements, sophisticated isotope-labeling
experiments, molecular probes, and especially computational chemistry which allows
the discussion of structure–activity relationships and can either support or reject
proposed mechanisms.
Page 6102, column 3, line 6 should read: On the other hand, A. Griesbeck (University of
Cologne, Germany) described how 1O2 with the aid of tetraarylporphyrin-loaded
polystyrene can be used for ene reactions and [4þ2] cycloadditions, and how it can even
be “made chiral” through organocatalysts.
Page 6103, column 2, line 7 should read: these effect the oxidation of bromide to
bromonium ions, which in turn can be reacted under nonacidic conditions with olefins
and aromatic compounds.
Page 6103, column 3, line 5 should read: The latter, however, are apparently stabilized by
POM ligands; their use recently afforded the synthesis of a Pt=O complex as described by
C. L. Hill (Emory University, Atlanta, USA), and now he reported the isolation and
characterization of the first Pd=O complex, K9Na4[(O=PdIV-OH)WO(OH2)L2]
(L = [PW9O34]9).
Page 6103, column 3, line 21 should read: Altogether, there is still great interest in the
oxidation of methane, the simplest yet most resistant C1 hydrocarbon source.
Page 6104, column 1, line 27 should read: … R. Hage (Unilever, The Netherlands)…
Page 6104, column 1, line 29 should read: The lecture given by G. Reinhardt (Clariant,
Germany) made it clear that there is not, and yet cannot be, a panacea for the bleaching
Page 6104, column 3, line 22 should read: The mechanistic understanding was
broadened, refined, and even renewed, and many novel systems have been developed.
Page 6104, column 3, last sentence: The pronounced relation to application was
underscored by the fact that this year’s meeting was, for the first time, organized jointly
by both the industrial and academic spheres as well as through the strong participation
and generous support of industry (especially BASF).
The Editorial Office apologizes for the oversight.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6430 – 6440
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