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Graphical Abstract Angew. Chem. Int. Ed. 322005

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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:
A. C. Filippou,* G. Schnakenburg, A. I. Philippopoulos,
N. Weidemann
Bonding Analysis of the MGeGeM Chain in the Germylidyne
Complexes trans,trans-[Cl(depe)2MGeGeM(depe)2Cl]
M. Veith*
Cubane-Type Li4H4 and Li3H3Li(OH): Stabilized in Molecular
Adducts with Alane
S. Protti, M. Fagnoni,* A. Albini*
Photochemical Cross-Coupling Reactions of Electron-Rich Aryl
Chlorides and Aryl Esters with Alkynes: A Metal-Free Alkynylation
V. Lavallo, Y. Canac, C. Pr'sang, B. Donnadieu, G. Bertrand*
Stable Cyclic (Alkyl)(amino)carbenes as Rigid or Flexible, Bulky,
Electron-Rich Ligands for Transition-Metal Catalysts
H. Braunschweig,* K. Radacki, D. Rais, D. Scheschkewitz
A T-Shaped Platinum(II) Boryl Complex as the Precursor to a
Base-Stabilized Borylene of Platinum
S. Aime,* D. D. Castelli, E. Terreno
Highly Sensitive MRI-CEST Agents using Liposomes (LIPOCEST)
News
F. D. Toste Receives Pfizer Award
5004
A. Zumbusch Receives Sommerfeld Prize
and Goes to London
5004
Several Awards for A. M ller
5004
Modern Cyclophane Chemistry
Rolf Gleiter, Henning Hopf
reviewed by U. H. Bunz
5005
Strategic Applications of Named
Reactions in Organic Synthesis
Laszlo K rti, Barbara Czako
reviewed by S. R. Waldvogel
5005
Books
Highlights
Drug Research
T. Berg*
5008 – 5011
Cellular Profiling of Small-Molecule
Bioactivities: an Alternative Tool for
Chemical Biology
Ammonia Activation
T. Braun*
5012 – 5014
Oxidative Addition of NH3 to a TransitionMetal Complex: A Key Step for the MetalMediated Derivatization of Ammonia?
4992
Are they a good match? Target identification is critical to the success of chemical
genetics projects that start with phenotypic screens. The method highlighted
herein is a novel way to decrease the
number of potential biological targets of
compounds identified in phenotypic
screens by comparison of their cellular
activity profiles with those obtained with
reference compounds. Activity profiles for
hypothetical compounds A and B are
shown.
Bond cleavage with model character? The
oxidative addition of ammonia to a transition-metal complex to yield a terminal
amido complex was achieved for the first
time recently (see scheme). This model
reaction might provide new pathways to
use ammonia as a feedstock in catalytic
reactions.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
Angewandte
Chemie
Reviews
Any old ion? The title boron cations (see
scheme) are elusive and have largely been
regarded as chemical curiosities. How-
ever, as potent electrophiles the enormous potential of these species is beginning to be recognized. Advances in mass
spectrometry have made a systematic
investigation of the gas-phase chemistry
of these ions possible and have facilitated predictions of practical relevance
to their reactivity in the condensed phase.
Cationic Boron Compounds
W. E. Piers,* S. C. Bourke,
K. D. Conroy
5016 – 5036
Borinium, Borenium, and Boronium Ions:
Synthesis, Reactivity, and Applications
Communications
Nanodevices
Stand and deliver! The release of poreencapsulated fluorescein molecules from
a core/shell mesoporous silica nanorod/
superparamagnetic iron oxide nanoparticle carrier in the presence of an external
magnetic field and only in response to
cell-produced antioxidants indicates promise for such systems in controlledrelease drug delivery.
In a spin: The mixed-valent {MnIII20xMMnIIx} cage complexes (x = 2–6) have
structures corresponding to a fragment of
a cubic close-packed lattice (see picture,
Mn large sphere, O small sphere). Magnetic studies show for the cage with x = 2
that the ground state has a spin (S) of
19 1 in low field, which increases to
about S = 30 at higher fields. The cage is a
S. Giri, B. G. Trewyn, M. P. Stellmaker,
V. S.-Y. Lin*
5038 – 5044
Stimuli-Responsive Controlled-Release
Delivery System Based on Mesoporous
Silica Nanorods Capped with Magnetic
Nanoparticles
Molecular Magnets
S. Maheswaran, G. Chastanet, S. J. Teat,
T. Mallah, R. Sessoli,* W. Wernsdorfer,
R. E. P. Winpenny*
5044 – 5048
“single molecule magnet” with a high
energy barrier (43 K) to reorientation of
the magnetization.
Photochemistry
Affairs of state: Investigation of the
photochromic properties of a combined
naphthopyran and diarylethene biphotochromic system (1) has revealed that four
different states with entirely different
absorption behaviors are formed. Opening of the naphthopyran ring leads to
conjugation and electronic connection of
both photochromes, while closure of the
open diarylethene system extends the pelectron system over the whole molecule.
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ANGEWANDTE CHEMIE International
Edition (ISSN 1433-7851) is published weekly
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USA by Publications Expediting Inc. 200
Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
Phosphonate Ligands Stabilize MixedValent {MnIII20xMnIIx} Clusters with Large
Spin and Coercivity
M. Frigoli, G. H. Mehl*
5048 – 5052
Multiple Addressing in a Hybrid
Biphotochromic System
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
NJ 07030. Annual subscription price for institutions: US$ 4948.00/4498.00 (valid for print
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individuals who are personal members of a
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Wiley-VCH prices are exclusive VAT.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
4993
Angewandte
Chemie
Bioorganic Chemistry
A wide variety of well-defined multivalent
peptides and proteins can be made by
conjugating synthetic peptides and
recombinantly expressed proteins to
cysteine-functionalized dendrimers using
native chemical ligation (see picture).
This modular approach provides access to
dendrimers that are attractive both for
understanding fundamental issues of
multivalency in biological interactions as
well as for biomedical applications.
I. van Baal, H. Malda, S. A. Synowsky,
J. L. J. van Dongen, T. M. Hackeng,
M. Merkx,* E. W. Meijer*
5052 – 5057
Multivalent Peptide and Protein
Dendrimers Using Native Chemical
Ligation
Guanine Oxidation
C. Crean, N. E. Geacintov,
V. Shafirovich*
Under oxidative stress: The oxidation of
guanine and 8-oxo-7,8-dihydroguanine has
been monitored by 18O-labeling methods.
The combination of nucleobase radicals 1
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
with the carbonate radical anion 2 results
in the net transfer of O from CO3C to the
end products (see scheme).
5057 – 5060
Oxidation of Guanine and 8-oxo-7,8Dihydroguanine by Carbonate Radical
Anions: Insight from Oxygen-18 Labeling
Experiments
Placing fluorine atoms at selected positions allows enantiopure hexacoordinate
phosphate anions to behave as effective
chiral solvating and resolving agents for
RuII complexes (the structure of one of the
anions is shown: F: yellow; O: red; Cl:
green; P: purple). The structural features
of the asymmetric ion pairing can be
determined by NMR spectroscopy owing
to the presence of the fluorine atoms.
Chiral Resolution
Biological templates: Diatom cell walls
were coated with metallic films and then
subsequently dissolved to yield nanostructured metallic microshells that exhibit the structural characteristics of the
diatom templates. The unique nanostructural details of the microshells (see
image) make them useful as substrates
for surface-enhanced Raman scattering.
Nanostructure Synthesis
R. Frantz, A. Pinto, S. Constant,
G. Bernardinelli, J. Lacour* 5060 – 5064
Fluorinated TRISPHAT Anions:
Spectroscopic Probes for Detailed
Asymmetric Ion Pairing Studies
E. K. Payne, N. L. Rosi, C. Xue,
C. A. Mirkin*
5064 – 5067
Sacrificial Biological Templates for the
Formation of Nanostructured Metallic
Microshells
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
4995
Contents
Fluorescent Probes
Ion probes: A potassium-sensing oligonucleotide with terminal pyrene moieties
can be used as a fluorescent probe for the
real-time monitoring of the extracellular
concentration of K+ ions under physiological conditions. The excimer emission
intensity (b) of the chair-type quadruplex
structure formed depends on the K+ ion
concentration (0–200 mm), and differs
significantly from that in the absence of
potassium (a).
S. Nagatoishi, T. Nojima, B. Juskowiak,
S. Takenaka*
5067 – 5070
A Pyrene-Labeled G-Quadruplex
Oligonucleotide as a Fluorescent Probe
for Potassium Ion Detection in Biological
Applications
An inversion of the exciton chirality and
structural changes upon transformation
from kinetic to thermodynamic assembly
are features of helical bis(merocyanine)
dye nanorods (see picture), as elucidated
by time-dependent circular dichroism
(CD) spectroscopy and atomic force
microscopy.
Self-Assembled Nanostructures
A. Lohr, M. Lysetska,
F. W rthner*
5071 – 5074
Supramolecular Stereomutation in Kinetic
and Thermodynamic Self-Assembly of
Helical Merocyanine Dye Nanorods
Macrocycles
S. Odermatt, J. L. Alonso-GPmez, P. Seiler,
M. M. Cid,* F. Diederich*
5074 – 5078
Shape-Persistent Chiral Alleno-Acetylenic
Macrocycles and Cyclophanes by
Acetylenic Scaffolding with 1,3Diethynylallenes
Rings on her fingers: The chiral allenoacetylenic macrocycle 1 and the related
cyclophane 2 with intriguing threedimensional shapes were prepared and
isolated in diastereoisomerically pure
form. The symmetries and structures of
these novel unsaturated hydrocarbons
were elucidated by 1H NMR spectroscopy
and X-ray crystallography. The isolated
stereoisomeric cyclophanes undergo
photoisomerization; presumably the anthracene moieties serve as intramolecular
sensitizers.
Pseudopolymorphism
D. Lentz,* M. Szwak
5079 – 5082
Synthesis and Structure Determination of
Tellurium Tetracyanide Solvates:
Pseudopolymorphism of Te(CN)4 and
TeF4
4996
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
The pseudopolymorphic solvates
[{Te(CN)4(CH3CN)2}n] and [{Te(CN)4(thf)3}n] form coordination polymers in
the solid state in which Te(CN)3 units are
connected by CN groups in cis position to
form infinite chains. The picture shows a
section of [{Te(CN)4(thf)3}n]. In contrast,
the tellurium tetrafluoride solvate [TeF4(thf)2] contains monomeric y-trigonalbipyramidal TeF4 units.
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
Angewandte
Chemie
Keeping drugs under control: Hydrothermally stable, hollow mesoporous silica
spheres have a high drug storage capacity,
and polyelectrolyte multilayers coated on
the spheres act as a switch for drug
release which is controlled by the pH or
ionic strength of the release medium. The
picture shows the release of ibuprofen
(IBU) from spheres with and without
coatings of sodium polystyrene sulfonate
(PSS) and poly(allylamine hydrochloride)
(PAH).
Drug Delivery
Y. Zhu, J. Shi,* W. Shen, X. Dong, J. Feng,
M. Ruan, Y. Li
5083 – 5087
Stimuli-Responsive Controlled Drug
Release from a Hollow Mesoporous Silica
Sphere/Polyelectrolyte Multilayer Core–
Shell Structure
Radical reform: Cleavage of the enantiotopic C2C3 or C2C3’ bonds in bicyclic
1-hydroxy-1,4-biradicals (see structure)
leads to enantiomeric products. Absolute
configuration correlations demonstrate
that, in the crystalline state, cleavage
occurs mainly in one direction and is
controlled by the orientation of the
cleaving bonds with respect to the
p orbital at the C1 position.
Biradicals
Not all down-to-Earth: A stable aluminacyclopropene LAl(h2-C2H2) 1 was isolated
from the reaction of LAl with C2H2. Further
reaction of 1 with C2H2 results in terminal
CCH and CH=CH2 groups at the
Al center. The end-on insertion of an azide
into one AlC bond in 1 leads to the first
aluminaazacyclobutene 2. These reactions can be considered prebiotic, as AlI
species and acetylene are found in outer
space.
Metallacycles
C. Yang, W. Xia, J. R. Scheffer,*
M. Botoshansky, M. Kaftory 5087 – 5089
Orbital-Overlap Control of the Reactivity
of a Bicyclic 1-Hydroxy-1,4-Biradical
H. Zhu, J. Chai, H. Fan, H. W. Roesky,*
C. He, V. Jancik, H.-G. Schmidt,
M. Noltemeyer, W. A. Merrill,
P. P. Power
5090 – 5093
A Stable Aluminacyclopropene
LAl(h2-C2H2) and Its End-On Azide
Insertion to an Aluminaazacyclobutene
Synthetic Methods
M. Miyashita,* T. Mizutani, G. Tadano,
Y. Iwata, M. Miyazawa,
K. Tanino
5094 – 5097
Acyclic, cyclic, and optically active unsaturated g,d-epoxy esters are employed in a
highly stereoselective synthesis of functionalized amino alcohols, amino acids,
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
and a,a-disubstituted amino acids. The
key step of the reaction sequence is a
double inversion of configuration (see
scheme).
Pd-Catalyzed Stereospecific Azide
Substitution of a,b-Unsaturated g,dEpoxy Esters with Double Inversion of
Configuration
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
4997
Contents
Host–Guest Chemistry
K. Yoshizawa, S. Toyota, F. Toda,*
S. Chatziefthimiou, P. Giastas,
I. M. Mavridis, M. Kato
5097 – 5100
Control of Differential Inclusion
Complexation in the Solid State by Seed
Crystals
Sowing the seeds: Complexation of rac-1
in the solid state with a guest such as Et2O
in the gas phase proceeds in the presence
of a seed crystal of the inclusion complex
Nanobiotechnology
Nanogold may not glitter, but its presence
significantly improves the specificity and
yield of PCR reactions owing to the greater
affinity of gold nanoparticles to singlestranded DNA than to double-stranded
DNA which helps to reduce mispairing.
Indeed, gel electrophoresis shows a single
predominant band for the target DNA
obtained by this method, in contrast to
streaking bands for products obtained by
conventional PCR (lanes 1 and 2; see
image).
H. Li, J. Huang, J. Lv, H. An, X. Zhang,
Z. Zhang,* C. Fan,* J. Hu*
5100 – 5103
Nanoparticle PCR: Nanogold-Assisted
PCR with Enhanced Specificity
(see scheme). For example, passing Et2O
over a mixture of 1 and a seed of 1·(Et2O)3
gives rise to exclusive formation of the 1:3
complex.
Synthetic Methods
H. Ohno,* M. Yamamoto, M. Iuchi,
T. Tanaka*
5103 – 5106
Palladium-Catalyzed Tandem Cyclization
of Bromoenynes through Aromatic CH
Bond Functionalization
Fluorescence Imaging
H. Gai, Q. Wang, Y. Ma,*
B. Lin*
5107 – 5110
Correlations between Molecular Numbers
and Molecular Masses in an Evanescent
Field and Their Applications in Probing
Molecular Interactions
4998
www.angewandte.org
The direct approach: Tandem cyclization
of 1-aryl-4-aza-2-bromo-1-alken-6-ynes
with catalytic Pd(OAc)2 and cesium carbonate in EtOH led to direct construction
of tri- or tetracyclic heterocycles, through
intramolecular carbopalladation and aro-
matic CH bond functionalization (see
scheme). This route in which two CC
bonds are formed enables the construction of complex heterocyclic skeletons
directly from readily prepared enynes.
Complex numbers: The number of molecules detected in the evanescent field
during single-molecule fluorescence imaging decreases with increasing molecular
weight in free solution (see graphic;
FITC = fluorescein isothiocyanate). This
technique could be useful for screening
undefined molecular interactions at
extremely low concentrations without
separation.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
Angewandte
Chemie
Lectin Inhibitors
Inhibitors of galectin-3, which has been
implicated in cancer- and immunity-related processes, can be synthesized from
thiodigalactoside derivatives with aromatic amide substituents at both C3
positions (see structure). Dissociation
constant (Kd) values as low as 33 nm have
been obtained. Computer modeling
suggests that such high affinity stems
from double arginine–arene stacking
interactions.
I. Cumpstey, A. Sundin, H. Leffler,
U. J. Nilsson*
5110 – 5112
C2-Symmetrical Thiodigalactoside BisBenzamido Derivatives as High-Affinity
Inhibitors of Galectin-3: Efficient Lectin
Inhibition through Double Arginine–
Arene Interactions
Synthetic Methods
Squaring the circle: A route to bicyclo[4.2.0]octane derivatives has been developed by the [2þ2] cycloaddition of allenenes or allenynes. The thermal intramolecular [2þ2] cycloaddition of simple
allenes 1 with an additional multiple bond
leads to direct and regioselective formation of the distal adducts 2 in good to
excellent yields.
H. Ohno,* T. Mizutani, Y. Kadoh,
K. Miyamura, T. Tanaka*
5113 – 5115
Thermal Intramolecular [2þ2]
Cycloaddition of Allenenes and Allenynes:
Diastereoselective Access to Bicyclic
Nitrogen Heterocycles
Materials Science
X. Feng, J. Zhai, L. Jiang*
Wet and dry: Titanium dioxide nanorod
films with micro- and nanoscale hierarchical surface structures have been successfully prepared (left). The nanorod
films, which show superhydrophobicity
(middle), reversibly become superhydro-
philic (right) when exposed to UV light.
The mechanism involves the cooperation
of the special surface structures, the
orientation of crystal planes, and the
surface photosensitivity.
5115 – 5118
The Fabrication and Switchable
Superhydrophobicity of TiO2 Nanorod
Films
Computer Chemistry
M. Olivucci, A. Lami,
F. Santoro*
Excitement over something small: The
protonated Schiff base of retinal photoisomerizes on an excited-state hypersurface (S1) that connects the Franck–
Condon (FC) point via a flat valley centered on a planar structure (SP) to a
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
conical intersection (CI; see picture).
Wave-packet (gray hat) quantum dynamics shows that the depletion of the S1
population switches from mono- to biexponential when a small ridge (dotted line)
between SP and CI is present.
5118 – 5121
A Tiny Excited-State Barrier Can Induce a
Multiexponential Decay of the Retinal
Chromophore: A Quantum Dynamics
Investigation
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
4999
Contents
Surface Electrochemistry
T. J. Davies, M. E. Hyde,
R. G. Compton*
Watch your step! Decoupling the individual contributions of edge-plane steps (A)
and basal-plane terraces (B) to the voltammetry of graphite electrodes can provide information of fundamental importance. This was done by selectively blocking the basal-plane terraces with insulating material to form nanotrench arrays of
edge-plane graphite.
5121 – 5126
Nanotrench Arrays Reveal Insight into
Graphite Electrochemistry
Low-cost isotope dilution made easy: An
alternate reaction of an analyte in a matrix
and in a standard solution with isotopelabeled or unlabeled derivatizing reagents
allows quantification of zearalenone in
maize flour without the need for a calibration curve. This is possible by direct
calculation of the relative response factor
for the analyte/internal standard ratio of
the sample (see picture).
Food Chemistry
S. Sforza,* C. Dall’Asta, A. Moseriti,
G. Galaverna, A. Dossena,
R. Marchelli
5126 – 5130
Alternate Isotope-Coded Derivatization
Assay: An Isotope Dilution Method
Applied to the Quantification of
Zearalenone in Maize Flour
Cycloaddition
S. Carret, A. Blanc, Y. Coquerel,
M. Berthod, A. E. Greene,
J.-P. DeprUs*
5130 – 5133
Approach to the Blues: A Highly Flexible
Route to the Azulenes
A palette of blues: Chlorobicyclo[5.3.0]decatrienones are readily prepared
from cycloheptatrienes by cycloaddition of
dichloroketene, ring expansion with a
diazoalkane, and dehydrochlorination in
dimethylformamide. These compounds
are used as intermediates in the regiocontrolled synthesis of a wide variety of
natural and nonnatural azulenes (see
scheme).
Pi and doughnuts: Highly effective
through-space conjugation among cofacial (aromatic) redox centers is established in stable hexaanilinylbenzene radical cations (1C+; p conjugation shown by
toroid). The radical cations show unusual
intervalence absorption bands and are
quantitatively analyzed by Mulliken–Hush
formulation.
Conjugation
D. Sun, S. V. Rosokha,
J. K. Kochi*
5133 – 5136
Through-Space (Cofacial) pDelocalization among Multiple Aromatic
Centers: Toroidal Conjugation in
Hexaphenylbenzene-like Radical Cations
Catalytic Epoxidation
Y. Nakagawa, K. Kamata, M. Kotani,
K. Yamaguchi, N. Mizuno* 5136 – 5141
Polyoxovanadometalate-Catalyzed
Selective Epoxidation of Alkenes with
Hydrogen Peroxide
5000
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The bis(m-hydroxo)-bridged dioxovanadium site in [g-1,2-H2SiV2W10O40]4 catalyzes the epoxidation of alkenes in the
presence of only one equivalent of H2O2
with a high yield of epoxide, high efficiency
of H2O2 utilization, unusual regioselectivity, and unprecedented diastereoselectivity (see picture).
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
Angewandte
Chemie
Making contact: A protein–protein interface (see structure) can be identified
unambiguously from the dependence of
amide-proton relaxation on proton density, as demonstrated by the identification
of subunit contacts in hemoglobin. The
information on upper limits for effective
distances thus obtained allows the protein
complex structure to be modeled more
accurately with docking techniques.
Protein–Protein Interactions
X. G. Sui, Y. Q. Xu, J. L. Giovannelli,
N. T. Ho, C. Ho,
D. W. Yang*
5141 – 5144
Mapping Protein–Protein Interfaces on
the Basis of Proton Density Difference
Service
Keywords
5146
Authors
5147
Vacancies
Preview
Angew. Chem. Int. Ed. 2005, 44, 4992 – 5001
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
A45
5149
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5001
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