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Graphical Abstract Angew. Chem. Int. Ed. 192005

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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:
R. Schiffmann, A. Heine, G. Klebe, C. D. P. Klein*
Metal Ions as Cofactors for Ligand Binding at Methionine
Aminopeptidase: A Critical View on the Relevance of In Vitro
Metalloenzyme Assays
R. Shintani, A. Tsurusaki, K. Okamoto, T. Hayashi*
Rhodium?Chiral Diene Catalyzed Highly Chemo- and
Enantioselective Arylative Cyclization of Alkyne-Tethered
Electron-Deficient Olefins
E. Ruiz,* G. Rajaraman, S. Alvarez, B. Gillon, J. Stride, R. Clrac,
J. Larionova, S. Decurtins
Symmetry and Topology Determine the MoV?CN?MnII Exchange
Interactions in High-Spin Molecules
A. Frstner,* L. Turet
Concise and Practical Synthesis of Latrunculin A by Ring-Closing
Enyne?Yne Metathesis
D. Wan, R. Tu, L. Zhang, H. Dai*
Deterministic One-to-One Synthesis of Germanium Nanowires
and Individual Gold Nanoseed Patterning for Aligned Nanowire
D. Cappel, S. Tllmann, A. Krapp, G. Frenking*
Direct Estimate of the Conjugative and Hyperconjugative
Stabilization in Diynes, Dienes, and Related Compounds
Meeting Reviews
Dendrimers: Platforms for Chemical Functionality
J.-F. Nierengarten
Chemogenomics in Drug Discovery
Hugo Kubinyi, Gerhard Mller
reviewed by U. Brjesson
Organic Electrochemistry
Hans J. Schfer
reviewed by R. Holze
V for victory? Theory has suggested that
V-shaped molecules may provide a route
to biaxial nematic liquid crystals (see
picture). The identification of a biaxial
nematic phase is, however, a challenging
task. Even if it is yet to be agreed that the
hunt is over, it appears that this path is
well worth pursuing.
Liquid Crystals
G. R. Luckhurst*
2834 ? 2836
V-Shaped Molecules: New Contenders for
the Biaxial Nematic Phase
A retrospective account of the discovery
through chemical synthesis of the secondgeneration epothilone drug candidates
the 9,10-dehydroepothilones
(e.g. fludelone (1)) is presented. The
importance of natural products as leads in
drug development is highlighted, as well
as the use of molecular editing through
chemical synthesis to fine-tune the biological and pharmacodynamic properties
of the natural product to develop a viable
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
Epothilone Derivatives
A. Rivkin, T.-C. Chou,
S. J. Danishefsky*
2838 ? 2850
On the Remarkable Antitumor Properties
of Fludelone: How We Got There
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Protein Recognition
L. J. Ball,* R. Khne,
J. Schneider-Mergener,
H. Oschkinat*
Solving the mystery of mutual attraction:
Proline-mediated protein?protein interactions are involved in the regulation of
numerous essential cellular processes.
Analysis of the structures of complexes
formed between proline-rich peptides and
2852 ? 2869
Recognition of Proline-Rich Motifs by
Protein?Protein-Interaction Domains
their respective binding domains (see
figure) reveals fundamental features of
this mechanism of recognition, which is
highly specific, yet only requires low
binding affinities.
Nanoparticle Synthesis
Accurate to size: Monodisperse magnetic
iron oxide nanoparticles with a continuous size spectrum of 6?13 nm have been
synthesized by a procedure similar to
seed-mediated growth and characterized
by transmission electron microscopy (see
picture) and magnetic measurements.
This method yields monodisperse nanoparticles directly without a size-selection
Three not of a kind: Two metal?organic
nets sustained by three different molecular building blocks, triangles, squares, and
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Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
J. Park, E. Lee, N.-M. Hwang, M. Kang,
S. C. Kim, Y. Hwang, J.-G. Park, H.-J. Noh,
J.-Y. Kim, J.-H. Park,
T. Hyeon*
2872 ? 2877
One-Nanometer-Scale Size-Controlled
Synthesis of Monodisperse Magnetic Iron
Oxide Nanoparticles
tetrahedra, are prepared and characterized. The shapes (see picture red triangles, green squares, yellow tetrahedra)
reveal how appropriate combinations of
vertex-linked polygons or polyhedra afford
novel topologies that could be prototypal
of an even wider range of organic and
metal?organic compounds.
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individuals who are personal members of a
Coordination Polymers
Z. Wang, V. Ch. Kravtsov,
M. J. Zaworotko*
2877 ? 2880
Ternary Nets formed by Self-Assembly of
Triangles, Squares, and Tetrahedra
national chemical society, or whose institution
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Postage and handling charges included. All
Wiley-VCH prices are exclusive VAT.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Microarray Immobilization
M.-r. Lee, I. Shin*
Fixed to the spot: A new, efficient, and
simple immobilization technique for the
construction of chemical microarrays has
been developed. This technique is applicable to the site-selective attachment of
diverse substances, including small
molecules, carbohydrates, and peptides,
to glass slides (see picture). The chemical
microarrays fabricated by using this
method were applied to screening peptide
and small-molecule binding to proteins.
2881 ? 2884
Fabrication of Chemical Microarrays by
Efficient Immobilization of HydrazideLinked Substances on Epoxide-Coated
Glass Surfaces
Anticancer Agents
Y. Najajreh, D. Prilutski, Y. Ardeli-Tzaraf,
J. M. Perez, E. Khazanov, Y. Barenholz,
J. Kasparkova, V. Brabec,
D. Gibson*
2885 ? 2887
Structure and Unique Interactions with
DNA of a Cationic Trans-Platinum
Complex with the Nonplanar Bicyclic
Piperidinopiperidine Ligand
Nanoporous Materials
Y. Wang, A. Yu, F. Caruso*
2888 ? 2892
Nanoporous Polyelectrolyte Spheres
Prepared by Sequentially Coating
Sacrificial Mesoporous Silica Spheres
Virus-Decorated Biocomposites
M. Fischlechner, O. Zschrnig,
J. Hofmann, E. Donath*
2892 ? 2895
Engineering Virus Functionalities on
Colloidal Polyelectrolyte Lipid Composites
Circumventing cisplatin resistance: The
trans-[PtCl2(NH3)(pip-pip)]+ ion (see
structure; red Pt, blue N, green Cl, gray C)
is a cytotoxic compound with a cationic
piperidinopiperidine ligand. The piperidine ring that is removed from the PtII
center is fluxional and acts as a hydrogenbond donor. The complex binds calf
thymus DNA directly and rapidly
(t1/2 = 11 min) without prior hydrolysis
and circumvents cisplatin resistance in
ovarian cancer cells.
A hole load of spheres: Nanoporous
polyelectrolyte (PE) spheres are prepared
through layer-by-layer deposition of
oppositely charged poly(acrylic acid) and
poly(allylamine hydrochloride) onto
mesoporous silica spheres (with crosslinking by heating in each step), and the
subsequent removal of the silica templates by hydrofluoric acid (HF; see
Engineered from the inside out: Polyelectrolyte-multilayered colloids were prepared employing the layer-by-layer technology. A lipid bilayer was then added, and
finally rubella-like particles were fused.
Immunofluorescence studies demonstrate that the colloidal biocomposites
have a virus-like surface. Indeed, they were
taken up into cells, while particles with an
outer lipid layer were rarely found inside
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
Asymmetric Synthesis
T. B. Poulsen, C. Alemparte, S. Saaby,
M. Bella, K. A. J鴕gensen*
2896 ? 2899
Metal-free catalysis: Highly functionalized
molecules with two contiguous stereocenters are easily accessed in high yield
with high enantio- and diastereoselectivity
by using a commercially available orga-
nocatalyst ((DHQD)2PYR, see scheme).
The easily removed Boc protecting group
in the product is an added value to this
method as an important tool in asymmetric synthesis.
Direct Organocatalytic and Highly
Enantio- and Diastereoselective
Mannich Reactions of a-Substituted
An effective macrocyclic ionophore for
F ions that contains an array of positively
charged imidazolium units has been prepared. The calix[4]imidazolium[2]pyridine
cation formed a complex with F ions in a
1:1 stoichiometry, as shown by binding
studies using 1H NMR spectroscopic
analysis, X-ray crystallographic determination (see structure), and density functional calculations.
Supramolecular Chemistry
Inhibitors of the interaction between protein VLA-4 and its natural ligand VCAM-1
have been designed, even though the
structure of the protein remains unresolved. The rational design relied on the
simulation of the steric and electronic
properties of the active loop of VCAM-1,
whose structure is known (see picture),
and the inhibitors were readily prepared
Synthetic Inhibitors
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
K. Chellappan, N. J. Singh, I.-C. Hwang,*
J. W. Lee, K. S. Kim*
2899 ? 2903
A Calix[4]imidazolium[2]pyridine as an
Anion Receptor
A. Zubia, L. Mendoza, S. Vivanco,
E. Aldaba, T. Carrascal, B. Lecea, A. Arrieta,
T. Zimmerman, F. Vidal-Vanaclocha,
F. P. Cosso*
2903 ? 2907
by stereoselective stepwise [3�
Application of Stereocontrolled Stepwise
[3� Cycloadditions to the Preparation of
Inhibitors of a4b1-Integrin-Mediated
Hepatic Melanoma Metastasis
Low-spin, high-valent iron centers: A highvalent iron?nitrido species containing a
FeV center is accessible by the photolysis
of [(cyclam-ac)FeIIIN3]+. The identity of the
resulting [(cyclam-ac)FeV(N)]+ species
was verified by spectroscopic methods,
magnetic susceptibility data, and DFT
calculations (see picture). Unexpectedly,
the analysis provides strong evidence for a
low-spin d3 (S = 1/2) ground-state electron configuration at the FeV center.
Bioinorganic Chemistry
N. Aliaga-Alcalde, S. DeBeer George,
B. Mienert, E. Bill, K. Wieghardt,*
F. Neese*
2908 ? 2912
The Geometric and Electronic Structure of
[(cyclam-acetato)Fe(N)]+: A Genuine
Iron(v) Species with a Ground-State Spin
S = 1/2
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
T. R. Tshikhudo, D. Demuru, Z. Wang,
M. Brust,* A. Secchi, A. Arduini,
A. Pochini*
2913 ? 2916
Molecular Recognition by Calix[4]areneModified Gold Nanoparticles in Aqueous
Extremely stable, water-soluble gold
nanoparticles 3 capable of specific molecular recognition of pyridinium ions in
aqueous systems are prepared. The particles are stabilized and solubilized by
thioalkylated oligoethylene glycol ligands
1. Specific recognition was achieved by
thiol-modified calixarene ligands 2. The
strongly colored gold particles also served
as readily detectable optical markers for
the specific binding events.
Boron gets cornered: On heating, the exoBH2 bridge on a {(Cp*Ru)2B9H14} framework (1; Cp* = C5Me5) inserts into the
cluster framework to form a 12-vertex
open-framework product
[(Cp*Ru)2B10H16] (2).
Functionalized mesoporous silica-based
solids can be functionalized with e.g.
guanidinium or polyol binding sites for
detection of citrate and borate, respectively, in water. The solids are loaded with
a dye (*; picture, left) that interacts with
its binding sites. The dye is displaced by
the target anions (*; right) and the
corresponding anion is then detected by
Fluorescent sensor for thiols: Deprotection of nonfluorescent 1 by thiols (R?SH)
proceeds rapidly and near-quantitatively
in aqueous solution (pH 7.4) to produce
highly fluorescent 2. Assays performed in
the presence of 1 provide a rapid and
simple method for the determination of
inhibitory constants for inhibitors such as
donepezil toward acetyl- and butyrylcholinesterases.
S. Ghosh, B. C. Noll,
T. P. Fehlner*
2916 ? 2918
Synthesis and Characterization of [exoBH2(Cp*M)2B9H14] (M = Ru, Re), and the
Conversion of the Ruthenaborane into
[(Cp*Ru)2B10H16] with an Open Cluster
Framework Based on a Capped Truncated
Anion Sensors
M. Comes, G. Rodrguez-Lpez,
M. D. Marcos, R. Martnez-Mez,*
F. Sancenn, J. Soto, L. A. Villaescusa,
P. Amors, D. Beltrn
2918 ? 2922
Host Solids Containing Nanoscale AnionBinding Pockets and Their Use in
Selective Sensing Displacement Assays
Fluorescent Probes
H. Maeda,* H. Matsuno, M. Ushida,
K. Katayama, K. Saeki,
N. Itoh
2922 ? 2925
2,4-Dinitrobenzenesulfonyl Fluoresceins
as Fluorescent Alternatives to Ellman?s
Reagent in Thiol-Quantification Enzyme
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
Several breakthroughs in nanowire synthesis are reported for germanium nanowires grown from gold nanoparticle seeds
by a low-temperature chemical vapor
deposition process. Conditions were
optimized to observe the formation of
nanowires in near-quantitative yields, and
post-growth flow-alignment was used to
obtain quasi-parallel nanowires that originate from well-controlled singleparticle
sites (see images).
The vibrational spectrum of [CH235ClI]+
(see formula) was recorded by massanalyzed threshold ionization (MATI)
Right angles: In solid-state magic-angle
spinning (MAS) NMR spectra, the line
widths of carbonyl carbon atoms in polycrystalline cholesteryl acetate are found to
be as narrow as 0.039 ppm if the magic
angle is adjusted very accurately, that is,
within 0.0048 (see picture). The line
broadening observed for slightly miss-set
angles is mostly due to residual chemical
shift anisotropy (CSA) interactions. Long
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
D. Wang, R. Tu, L. Zhang,
H. Dai*
2925 ? 2929
Deterministic One-to-One Synthesis of
Germanium Nanowires and Individual
Gold Nanoseed Patterning for Aligned
Nanowire Arrays
spectrometry. Spin?orbit effects were
used in density functional calculations to
determine the structure of the ground
state of the cation. The results suggest
that spin?orbit terms should be treated
the same as other relativistic effects in
some cases.
Dihalomethane Structures
Staircase-like structures in the hysteresis
loops at 0.04 K (see picture) are shown by
doped single crystals of
0:02Y0:98] (Pc = phthalocyaninato, TBA = tetrabutylammonium), the
first lanthanide single-molecule magnet.
They are assigned to resonant quantum
tunneling of magnetization between
entangled states of the electron and
nuclear spin systems. The Dy complex
was also studied.
Single-Molecule Magnets
M. Lee, H. Kim, Y. S. Lee,
M. S. Kim*
2929 ? 2931
A Dramatic Spin?Orbit Effect Observed in
the Vibrational Frequencies of the
Chloroiodomethane Cation
N. Ishikawa,* M. Sugita,
W. Wernsdorfer*
2931 ? 2935
Quantum Tunneling of Magnetization in
Lanthanide Single-Molecule Magnets:
Bis(phthalocyaninato)terbium and
Bis(phthalocyaninato)dysprosium Anions
NMR spectroscopy
S. Antonijevic,
G. Bodenhausen*
2935 ? 2938
High-Resolution NMR Spectroscopy in
Solids by Truly Magic-Angle Spinning
spin-echo life times up to T 02 = 3.6 s open
the way to sophisticated NMR methods.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Density Functional Calculations
Reactivity along two channels is shown by
the HOFeV=O species responsible for
Fe(tpa)-catalyzed olefin oxidation (tpa =
tris(2-pyridylmethyl)amine). Attack of the
oxo ligand on an olefinic carbon atom
yields epoxide and attack of the hydroxo
ligand affords cis-diol (see scheme).
Hybrid density functional theory now
demonstrates that the two processes have
comparable activation energies.
A. Bassan,* M. R. A. Blomberg,
P. E. M. Siegbahn,
L. Que, Jr.*
2939 ? 2941
Two Faces of a Biomimetic Non-Heme
HOFeV=O Oxidant: Olefin Epoxidation
versus cis-Dihydroxylation
Organometallic Chemistry
What are the limits for n in the case of
[M(EIR)n] (M = transition metal; E = Al,
Ga, In)? Is n = 5 possible, maybe n = 6, or
even more? A first insight is gained
through the reactions of Fe0 and Ru0
precursors with excess of AlCp*, leading
to CH activated isomers of [M(AlCp*)5]
(see picture for M = Fe, gray C, white H,
blue Al, red Fe, Cp* = C5Me5).
T. Steinke, M. Cokoja, C. Gemel,
A. Kempter, A. Krapp, G. Frenking,
U. Zenneck, R. A. Fischer* 2943 ? 2946
CH Activated Isomers of [M(AlCp*)5]
(M=Fe, Ru)
Cross-Coupling Reactions
T. J. Korn, P. Knochel*
2947 ? 2951
Cobalt(ii)-Catalyzed Cross-Coupling of
Polyfunctional Aryl Copper Reagents with
Aryl Bromides and Chlorides
Polyfunctionalized biphenyl and heteroaromatic compounds were formed in the
presence of [Co(acac)2], Bu4NI, and 4fluorostyrene (3) through a smooth crosscoupling reaction between organocopper
reagents 1, prepared by the transmetalation of functionalized aryl magnesium
halides with CuCN�LiCl, and aryl halides
2 that bear electron-withdrawing substituents. acac = acetylacetonate,
DME = 1,2-dimethoxyethane,
DMPU = 1,3-dimethyl-3,4,5,6-tetrahydro2(1H)-pyrimidinone.
A single precatalyst is used for the
sequential combination of the Ti-catalyzed hydroamination of alkynes with the
Ti-catalyzed hydrosilylation of imines. In
this way alkynes and primary amines are
converted efficiently into secondary
amines in a fully catalytic one-pot process
(see scheme).
Homogeneous Catalysis
A. Heutling, F. Pohlki, I. Bytschkov,
S. Doye*
2951 ? 2954
Sequence Catalyzed by Titanium
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
Reaction of a disilenide with SiCl4 produces a silicon cluster with p-bonding
topology reminiscent of a Mbius array, as
determined by structural data and DFT
calculations (see picture). Partially hydrogenated silicon clusters are important for
the optical properties of many silicon
materials. The availability of a derivative
that is stable in the absence of surrounding Si0 yields insight into the structure of
such compounds.
Cluster Compounds
It can come as a surprise to plant lovers to
find the fruit bodies of Leucocoprinus
birnbaumii (see picture) in their flower
pots. This fragile fungus, which is harmless to plants, owes its yellow color to the
unusual alkaloids birnbaumin A and B, in
which a 1-hydroxyindole-3-glyoxylic acid
amide is attached through a tetramethylene unit to N-hydroxyoxamidine. NHydroxyoxamidines have not been described previously.
Structure Elucidation
Mixed (pre)catalysts such as 1 arise when
[Rh(cod)2]BF4 is combined with a 1:1
mixture of a BINOL-derived monodentate
phosphonite or phosphite ligand and a
configurationally fluxional atropisomeric
phosphite with a biphenol backbone.
These systems provide excellent results
for the Rh-catalyzed asymmetric hydrogenation of b-acylamino acrylates.
BINOL = 2,2?-dihydroxy-1,1?-binaphthyl;
cod = cycloocta-1,5-diene.
Combinatorial Catalysis
D. Scheschkewitz*
2954 ? 2956
A Molecular Silicon Cluster with a
?Naked? Vertex Atom
A. Bartsch, M. Bross, P. Spiteller,
M. Spiteller, W. Steglich*
2957 ? 2959
Birnbaumin A and B: Two Unusual 1Hydroxyindole Pigments from the ?Flower
Pot Parasol? Leucocoprinus birnbaumii
M. T. Reetz,* X. Li
2959 ? 2962
Mixtures of Configurationally Stable and
Fluxional Atropisomeric Monodentate P
Ligands in Asymmetric Rh-Catalyzed
Olefin Hydrogenation
Combinatorial Catalysis
M. T. Reetz,* X. Li
6 2: The mixture of triphenylphosphine and phosphinine 1 with [Rh(acac)(CO)2] forms a hydroformylation
catalyst that effects the preferential formation of the branched product, even
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
though each ligand alone mediates the
opposite regioselectivity. Similar effects
were observed for a series of other ligand
2962 ? 2964
The Influence of Mixtures of Monodentate
Achiral Ligands on the Regioselectivity of
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Cluster Compounds
S. Tschirschwitz, P. Lnnecke, J. Reinhold,
E. Hey-Hawkins*
2965 ? 2969
From Racemic Primary
Complexes to a Lithium?Phosphorus closo
Li12P6 : The first two primary aminoalkyl(phosphanyl)ferrocene complexes 2(N,N-Dimethylaminomethyl)phosphanylferrocene (1) and N,N-dimethyl-1-(2phosphanylferrocenyl)ethylamine (2) are
prepared. Compound 1 readily undergoes
twofold deprotonation with nBuLi to form
the first lithium?phosphorus cluster (see
picture) which has the structure and
electronic properties of a closo cluster
according to Wade?s rules.
Cage Compounds
I. M. Mller,* D. Mller
According to plan: C2- and C3-symmetric
ligands are essential to the rational design
of a low-symmetry coordination cage with
the outer shape of a trigonal bipyramid
(view along the C3 axis shown; green: Pd,
red: ligand, blue: 5,5-diethylbarbiturate).
The characterization of an intermediate
gives insight to the mechanism of formation.
2969 ? 2973
Rational Design of a Coordination Cage
with a Trigonal-Bipyramidal Shape
Constructed from 33 Building Units
Cluster Compounds
T. Duan, G. St遝r,
H. Schnckel*
2973 ? 2975
Ga10Br10(4-tert-Butylpyridine)10 : A MixedValent Gallium(i) Subhalide as an
Intermediate during the Formation of
Elemental Gallium?
Fullerene-Based Micelles
S. Burghardt, A. Hirsch,* B. Schade,
K. Ludwig, C. Bttcher*
2976 ? 2979
Switchable Supramolecular Organization
of Structurally Defined Micelles Based on
an Amphiphilic Fullerene
Primary steps on the way towards Ga
metal: The second structurally characterized gallium(i) subhalide Ga10Br10(4-tertbutylpyridine)10 (see picture, blue Ga, yellow N, green Br) allows an insight into the
intra- and intermolecular redox process
during the formation of a-gallium by the
disproportionation reaction of a metastable GaBr solution. During this process,
metalloid clusters with an increasing
number of ?naked? Ga0 atoms in the core
and GaX2 entities in the periphery grow.
Exactly eight amphiphilic fullerene dendrimer molecules form a globular micelle
spontaneously in aqueous solution. This
supramolecular organization can be
turned on and off by an external stimulus
(pH). Owing to the remarkable structure
persistence of the micelles, their threedimensional structure could be determined from cryogenic transmission electron micrographic images and the molecular architecture was subsequently
modeled (see picture).
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
Angew. Chem. Int. Ed. 2005, 44, 2819 ? 2829
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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