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Graphical Abstract Angew. Chem. Int. Ed. 232005

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Contents
The following Communications have been judged by at least two referees to be “very
important papers” and will be published online at www.angewandte.org soon:
C.-J. Wang, X. Sun, X. Zhang*
Enantioselective Hydrogenation of Allylphthalimides: An
Efficient Method For Synthesis of b-Methyl Chiral Amine
T. Matsuda, M. Makino, M. Murakami*
Synthesis of Seven-Membered-Ring Ketones by Arylative Ring
Expansion of Alkyne-Substituted Cyclobutanones
G. Gopalakrishnan, J.-M. Segura, D. Stamou, C. Gaillard, M. Gjoni,
R. Hovius, K. J. Schenk, P. A. Stadelmann, H. Vogel*
Synthesis of Nanoscopic Optical Fibers using Lipid Membranes
as Templates
K. Ohmori, M. Tamiya, M. Kitamura, H. Kato, M. Oorui, K. Suzuki*
Regio- and Stereocontrolled Total Synthesis of Benanomicin B
Y. Ding, A. Mathur, M. Chen, J. Erlebacher*
Epitaxial Casting of Nanotubular Mesoporous Platinum
N. Shibata,* J. Kohno, K. Takai, T. Ishimaru, S. Nakamura, T. Toru,*
S. Kanemasa
Highly Enantioselective Catalytic Fluorination and Chlorination
Reactions of Carbonyl Compounds Capable of Two-Point Binding
Meeting Reviews
Swiss Delight: Brgenstock 2005
M. Oestreich
3512
Books
The Nano-Micro Interface
Hans-Jrg Fecht, Matthias Werner
reviewed by G. Cao
3514
Chiral Photochemistry
Yoshihisa Inoue, Vaidhyanathan
Ramamurthy
reviewed by A. von Zelewsky
3515
CN bond formation by nitrene-induced
CH amination is an elegant class of
reaction (see scheme). The Highlight
describes how such intramolecular pro-
cesses are catalytic with transition metals
and display enantioselectivity to provide a
powerful synthetic tool ideally suited to
the synthesis of natural products.
Highlights
CH Aminations
H. M. L. Davies,*
M. S. Long
3518 – 3520
Recent Advances in Catalytic
Intramolecular CH Aminations
Lab on a Chip
D. Belder*
Chipping in for microlabs: A capillary with
segmented sample droplets was coupled
to a microfluidic chip for the highthroughput screening of samples on the
nanoliter scale. A three-phase system was
developed for the segmentation; the
sample droplets are surrounded by a
fluorinated carrier fluid and additionally
separated by gas bubbles. The ultimate
goal in this area of research is a pocketsized laboratory.
3521 – 3522
Microfluidics with Droplets
3500
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
Angewandte
Chemie
Reviews
Informative patterns: Cell membranes can
respond to chemical interactions with the
surface in ways not seen with inorganic
materials. One example is the formation
of a spatial pattern at membrane junctions during intercellular signaling. The
formation of such a pattern in immunological synapses (see picture; right: fluorescence image) is examined in this
Review through the use of model systems
and imaging technologies.
Membrane Junctions
J. T. Groves
3524 – 3538
Molecular Organization and Signal
Transduction at Intermembrane Junctions
Communications
Small but influential: Chirality transfer
from a small chiral organic unit (d- or ltartrate) to a very large metal–oxide
framework is demonstrated by the enantiomerically pure, nonracemizing polytungstates d- or l-1 (see picture, the
central part is shown in polyhedral form;
purple Zr, gray W, blue P, black C, red O).
The tartrate unit determines the absolute
configuration of the inorganic moiety,
offering a new method to control the
chirality of polyoxoanions.
Chirality Transfer
Split into seven sizes: Highly ordered
cleavage of supercoiled plasmid DNA by
S1 nuclease was accomplished through
DNA complexation with water-soluble
cationic block copolymers (see schematic
representation). The results provide
insights into the mechanisms of endogenous protein-induced modification of
DNA and into the design of artificial
restriction enzymes through the supramolecular assembly of synthetic macromolecules.
DNA Cleavage
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Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
X. Fang, T. M. Anderson,
C. L. Hill*
3540 – 3544
Enantiomerically Pure Polytungstates:
Chirality Transfer through Zirconium
Coordination Centers to Nanosized
Inorganic Clusters
K. Osada, Y. Yamasaki, S. Katayose,
K. Kataoka*
3544 – 3548
A Synthetic Block Copolymer Regulates
S1 Nuclease Fragmentation of
Supercoiled Plasmid DNA
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Postage and handling charges included. All
Wiley-VCH prices are exclusive VAT.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3501
Angewandte
Chemie
Reaction Dynamics
Deuterium labeling experiments on the
rearrangement of methylenebicycloalkene
1 to 3 show stereoselectivity despite the
intermediacy of a stabilized diradical
structure 2. A theoretical model built from
computational studies explains the
observed product ratios. Stereoselectivity
among [3,3] (minor) products implicates
an unusual bifurcation of reaction trajectories after the initial bond-breaking
transition state.
C. P. Suhrada, C. Seluki, M. Nendel,
C. Cannizzaro, K. N. Houk,* P.-J. Rissing,
D. Baumann,
D. Hasselmann*
3548 – 3552
Dynamic Effects on [3,3] and [1,3] Shifts of
6-Methylenebicyclo[3.2.0]hept-2-ene
Like zeolites, K6Sn[Zn4Sn4S17] (see structure) has remarkable ion-exchange properties and forms CsK5Sn[Zn4Sn4S17] and
RbK5Sn[Zn4Sn4S17] in the presence of the
Cs+ and Rb+ ions, respectively. These
compounds have an open framework
comprising [Zn4Sn4S17]10 clusters linked
by Sn4+ centers and are remarkably stable.
One-fifth of the K+ ions play an important
templating role in stabilizing the framework. Zn blue, Sn red, S yellow, K orange.
M. J. Manos, R. G. Iyer, E. Quarez,
J. H. Liao,
M. G. Kanatzidis*
3552 – 3555
{Sn[Zn4Sn4S17]}6 : A Robust Open
Framework Based on Metal-Linked PentaSupertetrahedral [Zn4Sn4S17]10 Clusters
with Ion-Exchange Properties
Nanostructures
Group 5 telluride nanostructures have
been grown through chemical vapor
transport from the elements. The novel
nanostructured chalcogenide Nb3Te4 (a
cluster of Nb3Te4 nanowires is pictured) is
the first example of this type of nanowire
grown with a pseudo-1D structural basis.
The wires are single crystalline with longitudinal axes aligned along the crystallographic c axis. The nanowires are
metallic but do not exhibit superconductivity above 1.8 K.
Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
Ion Exchange
H. K. Edwards, P. A. Salyer, M. J. Roe,
G. S. Walker, P. D. Brown,*
D. H. Gregory*
3555 – 3558
Metallic Nanowires of Nb3Te4 : A
Nanostructured Chalcogenide
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3503
Contents
Molecular Targeting
N. Kanoh, K. Honda, S. Simizu, M. Muroi,
H. Osada*
3559 – 3562
Photo-Cross-Linked Small-Molecule
Affinity Matrix for Facilitating Forward and
Reverse Chemical Genetics
A photoaffinity reaction has been used to
photo-cross-link small molecules on
agarose beads to identify and purify the
binding proteins (see picture; PMF: peptide mass fingerprinting). This technology
Nanostructure Synthesis
X. Wen, Y. Fang, S. Yang*
The key component in the synthesis of
zinc nanowires and nanotubes by vapor
transport is a molecular directing agent,
such as H2O or NH3. Ultrathin zinc
nanowires and nanotubes with diameters
of 3–8 nm have thus been prepared (see
images), and both materials display a
single-crystalline structure.
3562 – 3565
Synthesis of Ultrathin Zinc Nanowires and
Nanotubes by Vapor Transport
Photocatalysis
I. Tsuji, H. Kato, A. Kudo*
is considered potentially useful for the
confirmation of specificity between a
small molecule and a protein of interest in
the field of reverse chemical genetics.
On the sunny side: A new photocatalyst
effects hydrogen evolution from an aqueous solution containing S2 and SO32
ions. The photocatalyst is a Ru-loaded
solid solution of ZnS–CuInS2–AgInS2 and
works in visible light, e. g. under simulated
solar irradiation (l 420 nm; see picture:
CB conducting band, VB valence band).
3565 – 3568
Visible-Light-Induced H2 Evolution from
an Aqueous Solution Containing Sulfide
and Sulfite over a ZnS–CuInS2–AgInS2
Solid-Solution Photocatalyst
Self-Assembly
Q. Chu, D. C. Swenson,
L. R. MacGillivray*
3569 – 3572
A Single-Crystal-to-Single-Crystal
Transformation Mediated by Argentophilic
Forces Converts a Finite Metal Complex
into an Infinite Coordination Network
3504
Reactions in crystals: Interactions
between AgI ions are used to preorganize
olefins for a regiocontrolled single-crystalto-single-crystal (SCSC) [2þ2] photodi-
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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merization that results in a quantitative
conversion of a finite dinuclear complex
into a one-dimensional coordination network (see scheme).
Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
Angewandte
Chemie
Under pressure! The synthesis of crystalline silicon nanowires can be carried out
in organic solvents at reaction temperatures of up to 450–5008C under highpressure conditions. Gold particles are
used as seeds, and organosilanes are
employed as the silicon source. The
decomposition chemistry of the organosilanes determines the quality of the
Nanostructures
D. C. Lee, T. Hanrath,
B. A. Korgel*
3573 – 3577
The Role of Precursor-Decomposition
Kinetics in Silicon-Nanowire Synthesis in
Organic Solvents
nanowires formed (see picture of an
Si nanowire with an Si/Au tip).
Hydrogen-rich materials infused in
nanoscaffolds offer a promising approach
to on-board hydrogen storage. A mesoporous scaffold decreases the temperature for hydrogen release from ammonia
borane (AB), a conventional hydrogenstorage material, to below 80 8C and leads
to an increase in the purity of the hydrogen released. (See schematic representation of a hydrogen-bonded AB network in
the cross-section of a single pore.)
Hydrogen Storage
Strands of gold: Extended one-dimensional arrays of gold nanoparticles up to
4 mm long can be assembled by hybridization between thiolated DNA/nanoparticle 1:1 conjugates and long DNA templates, which were prepared by rollingcircle polymerization (see picture). The
linear self-assembled structures could link
the nanometric properties of materials
with the convenience of micrometric
manipulation.
Nanoparticle Arrays
A. Gutowska, L. Li, Y. Shin, C. M. Wang,
X. S. Li, J. C. Linehan, R. S. Smith,
B. D. Kay, B. Schmid, W. Shaw,
M. Gutowski, T. Autrey*
3578 – 3582
Nanoscaffold Mediates Hydrogen Release
and the Reactivity of Ammonia Borane
Z. Deng, Y. Tian, S.-H. Lee, A. E. Ribbe,
3582 – 3585
C. Mao*
DNA-Encoded Self-Assembly of Gold
Nanoparticles into One-Dimensional
Arrays
C–H Activation
C. Boldron, P. Gamez, D. M. Tooke,
A. L. Spek, J. Reedijk*
3585 – 3587
Copper-Mediated Selective Oxidation of a
CH Bond
An environmentally friendly procedure
has been developed for the oxidation of
2,4,6-trimethylphenol (TMP) at the para
Csp3–H bond. Upon reaction with H2O2 in
the presence of catalytic amounts of CuII
Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
and neocuproine in methanol at 65 8C, 4(methoxymethyl)-2,6-dimethylphenol
(MDP) or 4-hydroxy-3,5-dimethylbenzaldehyde (HDB) is formed (see reaction).
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3505
Contents
Selenenylation
K. Okamoto, Y. Nishibayashi,* S. Uemura,
A. Toshimitsu*
3588 – 3591
Asymmetric Carboselenenylation
Reaction of Alkenes with Aromatic
Compounds
Electron Transfer
K. Akiyama,* S. Hashimoto, S. Tojo,
T. Ikoma, S. Tero-Kubota,
T. Majima
3591 – 3594
Study of Anisotropic Interfacial Electron
Transfer Across a Semiconductor/
Solution Interface by Time-Resolved EPR
Spectroscopy
High diastereoselectivity is attained in the
carboselenenylation reaction of simple
alkenes with aromatic compounds by
using a C2-symmetric areneselenenyl
triflate (see scheme). This asymmetric
Friedel–Crafts-type reaction is a conveni-
Xanthene dyes absorbed onto colloidal
TiO2 exhibit spin-polarized EPR spectra
when excited with pulses of visible light at
low temperatures (see schematic representation). Analysis of the spectra enables
the range of distances between the electron and the dye radical cation as well as
their relative orientations to be determined. Furthermore, an orientational
selectivity in electron transfer across the
semiconductor nanoparticle is observed.
Molecular Dynamics
K. Ruud,* R. Zanasi
3594 – 3596
The Importance of Molecular Vibrations:
The Sign Change of the Optical Rotation
of Methyloxirane
Sign language: The experimentally
observed sign change of the optical rota-
Self-Assembled Monolayers
M. Geissler, J. M. McLellan, J. Chen,
Y. Xia*
3596 – 3600
Side-by-Side Patterning of Multiple
Alkanethiolate Monolayers on Gold by
Edge-Spreading Lithography
3506
ent procedure for the preparation of chiral
hydrocarbons bearing an aryl moiety at
the stereogenic carbon atom.
Tf = trifluoromethanesulfonyl;
M.S. = molecular sieves.
tion of (S)-methyloxirane when varying the
wavelength of incident light from 589 to
355 nm is a result of zero-point vibrational
corrections. Agreement between theory
and experiment is obtained when coupled-cluster (CC3) equilibrium optical
rotations are combined with the reported
zero-point vibrational (ZPV) contributions
(see picture).
Going round in circles: Multiple selfassembled monolayers of thiols on gold
are patterned as concentric rings with
sub-100-nm resolution by edge-spreading
lithography. A 2D array of silica beads on
gold is used as a guide for thiol molecules
delivered by successive printing with
planar elastomeric stamps. This process
can form chemically complex patterns
(see picture), as revealed by lateral force
microscopy.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
Angewandte
Chemie
Multicomponent Reactions
P. G. Cozzi,* E. Rivalta
3600 – 3603
Highly Enantioselective One-Pot, ThreeComponent Imino-Reformatsky Reaction
A key to molecular diversity is the preparation of new frameworks in multicomponent condensations of three or
more reactants. A new highly enantioselective one-pot, three-component, nickel-
catalyzed, imino-Reformatsky reaction
affords b-amino esters with 64–92 % ee
(see scheme). The simplicity and broad
scope of our method provide a practical
access to useful building blocks.
A masked variant of the first coordinatively unsaturated [Cp*Ru(k2-P,N)]+
cation (1) is reported, which has proven
capable of single intramolecular CH
activation. In contrast, the isostructural
zwitterionic complex 2 apparently rearranges to a hydridocarbene by way of a
remarkably facile, ligand-assisted double
CH bond activation process (see
scheme).
M. A. Rankin, R. McDonald,
M. J. Ferguson,
M. Stradiotto*
3603 – 3606
Coordinatively Unsaturated Cationic and
Zwitterionic [Cp*Ru(k2-P,N)] Complexes:
Ligand-Assisted Double-Geminal CH
Bond Activation and Reversible a-H
Elimination at Ruthenium
Sensors
Appropriate linking of Lewis acidic and
Lewis basic components—in this case
boronic acid and tertiary amine functionalities—allows the construction of a
robust organometallic receptor capable of
selectively binding hydrogen fluoride. This
system can differentiate between exposure to HF and to related acids, such as
HCl, by providing opposing electrochemical responses (see picture).
C. Bresner, S. Aldridge,* I. A. Fallis,*
C. Jones, L.-L. Ooi
3606 – 3609
Selective Electrochemical Detection of
Hydrogen Fluoride by Ambiphilic
Ferrocene Derivatives
The identification of enzyme pairs with
overlapping substrate specificity and
enantiocomplementary transformations
is a key challenge in biocatalysis. Enantioand regiodivergent Baeyer–Villiger oxidations were successfully carried out by
using a small library of recombinant
Escherichia coli strains expressing monooxygenases of various microbial origin
(see picture). The clustering of enzymes
based on stereopreference is in good
agreement with phylogenetic similarity.
Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
C–H Activation
www.angewandte.org
Biotransformations
M. D. Mihovilovic,* F. Rudroff, B. Grtzl,
P. Kapitan, R. Snajdrova, J. Rydz,
R. Mach
3609 – 3613
Family Clustering of Baeyer–Villiger
Monooxygenases Based on Protein
Sequence and Stereopreference
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3507
Contents
EPR Spectroscopy
Caught in the act: Until now, the spatial
property of the hyperfine interaction
between the S = 2 electronic spin and the
I = 5/2 nuclear spin in any chemically
relevant MnIII compound has escaped
observation. By taking multifrequency
electron paramagnetic resonance measurements (see graph) on the [Mn(OH2)6]3+ ion doped into Cs[Ga(OH2)6](SO4)·6 H2O, ground-state spin Hamiltonian parameters have been determined at
an unprecedented level of precision.
I. Krivokapic̃, C. Noble, S. Klitgaard,
P. Tregenna-Piggott,* H. Weihe,*
A.-L. Barra
3613 – 3616
Anisotropic Hyperfine Interaction in the
Manganese(iii) Hexaaqua Ion
Bonding Analysis
D. Cappel, S. Tllmann, A. Krapp,
G. Frenking*
3617 – 3620
Direct Estimate of the Conjugative and
Hyperconjugative Stabilization in Diynes,
Dienes, and Related Compounds
The intrinsic strength of the conjugation
and hyperconjugation in 1,3-butadiene,
1,3-butadiyne, and related compounds
was determined by energy decomposition
analysis. The calculations indicate that the
p conjugation in 1,3-butadiyne is roughly
Metalloenzyme Inhibitors
Thiabendazole is a potent inhibitor of
E. coli methionine aminopeptidase
(MetAP) in vitro. Crystallographic structures of MetAP complexed with this and
two other inhibitors show that binding is
mediated by an auxiliary metal ion (see
picture). This effect results from the high
concentration of metal ions under in vitro
conditions, and should be taken into
account in assays for inhibitors of metaldependent enzymes.
R. Schiffmann, A. Heine, G. Klebe,
C. D. P. Klein*
3620 – 3623
Metal Ions as Cofactors for the Binding of
Inhibitors to Methionine
Aminopeptidase: A Critical View of the
Relevance of In Vitro Metalloenzyme
Assays
Chiral Molecules
Electroweak quantum chemistry leads to
the prediction of a new isotope effect for
molecules that are chiral as a result of
isotopic substitution (see picture). The
electron–nucleon interaction mediated by
the Z-boson results in surprisingly large
parity-violating energy differences DpvE
between isotopic enantiomers. For isotopic substitution of heavier atoms such as
35
Cl/37Cl DpvE is almost as large as in
ordinary chiral molecules. This is important for spectroscopic experiments on
parity violation.
R. Berger, G. Laubender, M. Quack,*
A. Sieben, J. Stohner,
M. Willeke
3623 – 3626
Isotopic Chirality and Molecular Parity
Violation
3508
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
twice as strong as that in 1,3-butadiene,
and that the hyperconjugative interactions
of CH and CC bonds with CC multiple
bonds are about half as strong as the p
conjugation between multiple bonds.
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Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
Angewandte
Chemie
Service
Keywords
3628
Authors
3629
Angewandte’s
Sister Journals
Preview
3630 – 3631
3633
Corrigendum
*
Amino Acids—Valuable Organocatalysts
in Carbohydrate Synthesis
U. Kazmaier*
2186–2188
In this Highlight, the reaction scheme for a proline-catalyzed carbohydrate synthesis
was rendered incorrectly at the bottom of Scheme 4. The correct Scheme is shown, and
the sentence that begins at the bottom of the first column on page 2188 should read:
“For example, the 2-methyl-2-deoxymannose derivative 21 was obtained as a single
stereoisomer from a-benzyloxyacetaldehyde (20) and propionaldehyde (6).”
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200462873
Stretched Gelatin Gels as Chiral
Alignment Media for the Discrimination
of Enantiomers by NMR Spectroscopy
K. Kobzar, H. Kessler,
B. Luy*
In Figure 3 of this Communication, the label for f1 was positioned incorrectly. The
correct figure is shown here.
3145–3147
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200462736
Angew. Chem. Int. Ed. 2005, 44, 3500 – 3509
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3509
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