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Graphical Abstract Angew. Chem. Int. Ed. 262005

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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:
F. Studt, F. Tuczek*
Energetics and Mechanism of a Room Temperature Catalytic
Synthesis of Ammonia (Schrock Cycle): Comparison with
Biological Nitrogen Fixation
C. Schaefer, G. C. Fu*
Catalytic Asymmetric Couplings of Ketenes with Aldehydes to
Generate Enol Esters
M. Capdevila,* J. Domnech, A. Pagani, L. To, L. Villarreal,
S. Atrian
Zn and Cd Metallothionein Recombinant Species from the Most
Diverse Phyla May Contain Sulfide (S2 ) Ligands
H. Zhu, J. Chai, H. Fan, H. W. Roesky,* C. He, V. Jancik,
H.-G. Schmidt, M. Noltemeyer, W. A. Merrill, P. P. Power
A Stable Aluminacyclopropene LAl(h2-C2H2) and Its End-On
Azide Insertion to an Aluminaazacyclobutene
D. Loffreda,* F. Delbecq, F. Vign, P. Sautet
Catalytic Hydrogenation of Unsaturated Aldehydes on Pt (111):
Understanding the Selectivity from First-Principles Calculations
R. Shintani, W.-L. Duan, T. Nagano, A. Okada, T. Hayashi*
Chiral Phosphine–Olefin Bidentate Ligands in Asymmetric
Catalysis: Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl
Boronic Acids to Maleimides
News
K. Nakanishi Awarded Gold Nagoya
Medal 2005
3956
M. Suginome Receives Silver Nagoya
Medal 2005
3956
M. Shibasaki Receives Japan Academy
Prize
3956
Dietrich Stoltzenberg
reviewed by B. Friedrich
Revamped for the 21st century: The
original Stille protocols for crosscouplings are difficult to recognize in the
newer nickel-catalyzed reactions of
monoorganotin compounds with secondary alkyl halides (see scheme). This new
coupling scheme avoids the formation of
toxic byproducts.
Cationic polycyclization cascades: The
stereoselective transformations of linear
polyolefins to give cyclic triterpenes (see
scheme) have fueled half a century of
intense research. Structures of triterpene
cyclases complexed with the substrate
analogue 2-azasqualene and the reaction
product lanosterol provide new insights
into the elegant mechanisms of these
enyzmes.
Books
Fritz Haber: Chemist, Nobel Laureate,
German, Jew
3957
Highlights
Cross-Coupling Reactions
A. M. Echavarren*
3962 – 3965
Couplings with Monoorganotin
Compounds: A “Radical” Twist from the
Original Stille Reaction
Cyclizations
K. U. Wendt*
3966 – 3971
Enzyme Mechanisms for Triterpene
Cyclization: New Pieces of the Puzzle
3946
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
Angewandte
Chemie
Reviews
Among the numerous synthetic methods
for the preparation of chiral products with
high enantiomeric excess, kinetic resolution is the oldest. It is unique, as it has
been applied to practically every type of
chiral substrate, and can be combined
with any method of enantioselective
synthesis. The scheme shows an example
of dynamic kinetic resolution through the
enantioselective catalytic hydration of an
equilibrated racemic b-ketoester.
Chiral Resolution
E. Vedejs,* M. Jure*
3974 – 4001
Efficiency in Nonenzymatic Kinetic
Resolution
Communications
A network of platinum nanotubes with
diameters of about 15 nm and walls 1 nm
thick that interconnect to form an open,
doubly bicontinuous structure (see highresolution electron micrograph) is formed
by coating platinum on a nanoporous
gold template then dissolving away the
mold. The structure is stable at 125 8C for
at least 24 hours, but starts to deform at
150 8C and eventually forms nanoparticles.
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
Y. Ding, A. Mathur, M. Chen,
J. Erlebacher*
4002 – 4006
Epitaxial Casting of Nanotubular
Mesoporous Platinum
Chiroptical Probes
Z for zinc and Z-DNA: As a result of
different binding modes, a cationic zinc
porphyrin discriminates between B and
Z conformations of DNA and holds promise as a probe for Z-DNA. A very intense
induced circular dichroism (ICD) effect
with a bisignate spectrum is observed
upon interaction of the porphyrin with
Z-DNA (see graphic; porphyrin red,
Z-DNA green), whereas only a weak ICD
spectrum results upon its interaction with
B-DNA.
For the USA and Canada:
ANGEWANDTE CHEMIE International
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USA by Publications Expediting Inc. 200
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Materials Science
M. Balaz, M. De Napoli, A. E. Holmes,
A. Mammana, K. Nakanishi, N. Berova,*
R. Purrello*
4006 – 4009
A Cationic Zinc Porphyrin as a Chiroptical
Probe for Z-DNA
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3947
Angewandte
Chemie
Nanotechnology
R. Baron, C.-H. Huang, D. M. Bassani,*
A. Onopriyenko, M. Zayats,
I. Willner*
4010 – 4015
Trapping the light fantastic-ally! Enhanced
photocurrents are observed for hydrogenbonded gold nanoparticle/CdS nanoparticle arrays associated with a gold elec-
A one-component acceptor-donor-acceptor compound based on a rigid TCNQ-sTTF-s-TCNQ system (see picture) exhibits
trode surface (see scheme) as a result of
charge separation and controlled electron
transfer at the electrode interface.
a unique case of both intramolecular
charge and electron transfer through
space that is strongly dependent on the
polarity of the medium. The strong
dependence of the ground-state electronic
structure on the solvent polarity provides
an unprecedented case of solvatochromism.
Donor–Acceptor Systems
E. Tsiperman, J. Y. Becker,*
V. Khodorkovsky,* A. Shames,
L. Shapiro
4015 – 4018
A Rigid Neutral Molecule Involving TTF
and TCNQ Moieties with Intrinsic Chargeand Electron-Transfer Properties that
Depend on the Polarity of the Solvent
Phase Transitions
No added salt: Transmission electron
microscopy and small-angle X-ray scattering studies have shown that uni- and
multilamellar vesicles with radii of 25.5
and 366 nm (see schematic diagram; the
hydrophilic cation/anion groups are
shown as green spheres and the hydrocarbon chains in blue), respectively, are
formed from trimethyltetradecylammonium hydroxide and oleic acid in water.
The multilamellar phase consists of seven
bilayers.
A. Song, S. Dong, X. Jia, J. Hao,*
W. Liu,* T. Liu
4018 – 4021
An Onion Phase in Salt-Free Zero-Charged
Catanionic Surfactant Solutions
Carefully selected combinations of directional forces can be used to rationally
engineer crystals with particular anisotropic features. This approach has led to the
generation of cleavable molecular crystals
with parallel 15- channels by dipoledirected stacking of hydrogen-bonded
sheets (see crystal structure). The network
remains undeformed when guests included in the channels are exchanged.
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
Hydrogen-Bonded CdS Nanoparticle
Assemblies on Electrodes for
Photoelectrochemical Applications
www.angewandte.org
Dipoles in Crystal Engineering
N. Malek, T. Maris, M.-ð. Perron,
4021 – 4025
J. D. Wuest*
Molecular Tectonics: Porous Cleavable
Networks Constructed by Dipole-Directed
Stacking of Hydrogen-Bonded Sheets
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3949
Contents
Zintl Anions
J. M. Goicoechea,
S. C. Sevov*
Under wraps: A linear nickel filament is
“wrapped” inside an eighteen-atom germanium enclosure made of two nineatom deltahedral clusters (see structure;
green Ge, yellow Ni).
4026 – 4028
[(Ni-Ni-Ni)@(Ge9)2]4 : A Linear Triatomic
Nickel Filament Enclosed in a Dimer of
Nine-Atom Germanium Clusters
A NADH turnover rate of 741 min 1 in the
oxidition of ethane to ethanol is observed
with an engineered form of the heme
monooxygenase cytochrome P450cam—
the first example of such activity for a
P450 enzyme (GC analysis shown).
Ethanol is formed at 78 min 1 (10.5 %
coupling). The mutant is 45 % highspin in the absence of substrate, making it
a useful platform for P450 structure–
function studies.
Enzyme Engineering
F. Xu, S. G. Bell, J. Lednik, A. Insley,
Z. Rao,* L.-L. Wong*
4029 – 4032
The Heme Monooxygenase
Cytochrome P450cam Can Be Engineered
to Oxidize Ethane to Ethanol
Organocatalysis
Y. Hoashi, T. Okino,
Y. Takemoto*
4032 – 4035
Enantioselective Michael Addition to
a,b-Unsaturated Imides Catalyzed by a
Bifunctional Organocatalyst
High enantioselectivities (up to 94 % ee)
were attained in the Michael addition of a
variety of a,b-unsaturated imides 1 and
malononitrile (2) catalyzed by bifunctional
thiourea 4. The pyrrolidinone moiety of 1
Natural Product Synthesis
D. Muri, N. Lohse-Fraefel,
E. M. Carreira*
A cycloaddition comes of age: The focal
points of a stereoselective total synthesis
of erythronolide A (see structure) are two
MgII-mediated cycloadditions of nitrile
oxides. Of broader significance, the strategy not only facilitates the synthesis of
specific polyketide targets (i.e. natural
products) but also opens up new possibilities for the preparation of non-natural
analogues.
4036 – 4038
Total Synthesis of Erythronolide A by MgIIMediated Cycloadditions of Nitrile Oxides
3950
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
plays a key role in the reaction. The
reaction provides access to a variety of
Michael adducts 3 (see scheme; R = aryl
and alkyl groups).
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
Angewandte
Chemie
A cyclophane with allene and acetylene
bridges has been prepared as a single
enantiomer. This acetylenic allenophane
(see structure) was synthesized by a
series of palladium- and copper-mediated
coupling reactions. The allene bridge was
derived from the ring opening of a chiral
epoxy alkyne, which was prepared by a
Sharpless asymmetric epoxidation of an
allylic alcohol.
Asymmetric Synthesis
The base-free anti-Markovnikov addition
of secondary amides, anilides, lactams,
ureas, bislactams, and carbamates to
terminal alkynes is accomplished, for the
first time, by a ruthenium-catalyzed reaction. Two complementary protocols provide stereoselective synthetic entries to
either the E or the Z isomers (see scheme;
cod = cycloocta-1,5-diene; DMAP = 4(N,N-dimethylamino)pyridine).
Homogeneous Catalysis
M. D. Clay, A. G. Fallis*
4039 – 4042
Acetylenic Allenophanes: An Asymmetric
Synthesis of a Bis(alleno)-bis(butadiynyl)meta-cyclophane
L. J. Gooßen,* J. E. Rauhaus,
G. Deng
4042 – 4045
Ru-Catalyzed Anti-Markovnikov Addition
of Amides to Alkynes: A Regio- and
Stereoselective Synthesis of Enamides
C H Activation
O. Daugulis,* V. G. Zaitsev
A thousand turnovers in bi- and triaryl
formation: Substituted anilides have been
ortho-arylated by aryl iodides under palladium catalysis (see scheme). This method
is highly tolerant of the presence of
additional functional groups (FGs). Even
an iodo functionality on the anilide moiety
and a bromo functionality on the aryl
iodide are compatible with this methodology.
Protein binders: Three representative
polyoxometalate (POM) compounds, for
example 1, which is of the Wells–Dawson
class, were found to interact with the basic
fibroblast growth factor (bFGF, right). The
binding induces dramatic conformational
changes in the growth factor. POMs are
promising leads for compounds that may
represent a new avenue for the development of therapeutic agents against bFGFinduced angiogenesis.
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
www.angewandte.org
4046 – 4048
Anilide ortho-Arylation by Using C H
Activation Methodology
Polyoxometalates
Q. Wu, J. Wang, L. Zhang, A. Hong,
J. Ren*
4048 – 4052
Molecular Recognition of Basic Fibroblast
Growth Factor by Polyoxometalates
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3951
Contents
Sapphyrins
P. K. Panda, Y.-J. Kang,
C.-H. Lee*
Within the framework: The fused benzodipyrrole unit within the sapphyrin 1 has a
significant influence on its structure as
compared to those of usual sapphyrins.
The fused benzene ring partly inhibits
distortion of the macrocycle about the
dipyrrole unit (see structure of
1·2 H+ 2 (p-CH3C6H4SO3 ); C gray, N blue,
O red, S yellow) and contributes to the
significant red-shift of Q-bands.
4053 – 4055
A Benzodipyrrole-Derived Sapphyrin
Heterocyclic Chemistry
M. Kuratsu, M. Kozaki,
K. Okada*
4056 – 4058
2,2’:6’,2’’:6’’,6-Trioxytriphenylamine:
Synthesis and Properties of the Radical
Cation and Neutral Species
A flat radical: Oxygen-bridged triphenylamine 1 and its radical cation 2 were
prepared. The neutral compound has a
shallow bowl structure, whereas the radical cation is planar. The properties of the
highly stable radical cation were clarified;
such compounds have potential applicability in electronic and magnetic materials.
Tumor Imaging Agents
Specific targeting of tumors with radioactive isotopes is the key for high-sensitivity scintigraphy detection. A labeled
neutral endopeptidase (NEP) inhibitor is
described that accumulates in vivo in
tumor cells expressing this enzyme, which
makes it a potential tool for noninvasive
evaluation of NEP expression. Its structure (black with the label depicted in red,
DTPA = diethylenetriaminepentaacetic
acid) is shown in a model of the NEP
active site (blue).
O. Raguin, M.-C. Fourni-Zaluski,
A. Romieu, A. Plegrin, F. Chatelet,
D. Plaprat, J. Barbet, B. P. Roques,*
A. Gruaz-Guyon*
4058 – 4061
A Labeled Neutral Endopeptidase
Inhibitor as a Potential Tool for Tumor
Diagnosis and Prognosis
Drug Design
Designer drug: A polymer therapeutic was
designed for a combination therapy of
breast cancer. N-(2-Hydroxypropyl)methacrylamide was used as the model
polymer platform to prepare a unimolecular polymer conjugate (see picture,
radius of gyration: 12.8 nm) that combines an endocrine (the aromatase inhibitor aminoglutethimide, blue) and a
chemotherapeutic agent (the anthraxcycline antibiotic doxorubicin, red).
M. J. Vicent,* F. Greco, R. I. Nicholson,
A. Paul, P. C. Griffiths,
R. Duncan*
4061 – 4066
Polymer Therapeutics Designed for a
Combination Therapy of HormoneDependent Cancer
3952
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
Angewandte
Chemie
Supported Catalysts
A. Abad, P. Concepcin, A. Corma,*
H. Garca
4066 – 4069
A Collaborative Effect between Gold and a
Support Induces the Selective Oxidation
of Alcohols
Ceria nanoparticles as a support stabilize
positive gold species and provide oxygen
vacancies. The resulting solid exhibits an
exceedingly high efficiency for the sol-
ventless aerobic oxidation of primary and
secondary alcohols to carbonyl compounds (see picture).
Spin Crossover
In the loop: A reversible spin transition
was observed by Raman spectroscopy on
application of a single laser pulse (8 ns) in
the hysteresis loop of the spin-crossover
complex [Fe(pyrazine){Pt(CN)4}]. This bidirectional, photoinduced spin switching
occurs at room temperature over a wide
region of bistability and involves magnetization as well as color changes (see
picture).
S. Bonhommeau, G. Molnr, A. Galet,
A. Zwick, J.-A. Real, J. J. McGarvey,
A. Bousseksou*
4069 – 4073
One Shot Laser Pulse Induced Reversible
Spin Transition in the Spin-Crossover
Complex [Fe(C4H4N2){Pt(CN)4}] at
Room Temperature
Hopping holes: Oligopeptides with a
photosensitive charge-injection system
were synthesized and irradiated by a
nanosecond laser. A multistep electrontransport process occurred which uses
aromatic side chains as hole carriers (see
scheme). The rates of this process indicate through-space electron transfer (a
hopping mechanism).
Electron Transfer in Peptides
The C3 equivalent dihydroxyacetone was
used in its protected form in prolinecatalyzed Mannich reactions (see
scheme). As little as 5 mol % catalyst is
required when using 2,2,2-trifluoroethanol
as solvent. The reaction is improved
further (reaction time 10 min) under
microwave conditions. PMP = p-methoxyphenyl.
Organocatalysis
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
B. Giese,* M. Napp, O. Jacques,
H. Boudebous, A. M. Taylor,
J. Wirz
4073 – 4075
Multistep Electron Transfer in
Oligopeptides: Direct Observation of
Radical Cation Intermediates
B. Westermann,*
C. Neuhaus
4077 – 4079
Dihydroxyacetone in Amino Acid
Catalyzed Mannich-Type Reactions
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3953
Contents
Amino Sugars
D. Enders,* C. Grondal, M. Vrettou,
G. Raabe
4079 – 4083
Asymmetric Synthesis of Selectively
Protected Amino Sugars and Derivatives
by a Direct Organocatalytic Mannich
Reaction
Short and sweet: Starting from the commercially available precursors 1–3, selectively protected amino sugars and derivatives are obtained in one step and with
high diastereo- and enantiomeric purity by
means of a proline-catalyzed three-com-
ponent Mannich reaction (see scheme,
PMP = para-methoxyphenyl). This efficient organocatalytic procedure can be
carried out smoothly on a multigram
scale.
Sequential Enzymatic Oxidation of
Aminoarenes to Nitroarenes via
Hydroxylamines
The at-line detection of an amino group
oxidation catalyzed by the N-oxygenase
AurF provides the first direct evidence for
a stepwise enzymatic oxidation of
aromatic amines to nitro groups via a
hydroxylamine intermediate (see
scheme). The sequential nature of this
reaction is further supported by biotransformation of the intermediate and the
identification of a p-aminobenzoatederived azoxy side product.
Crystal Engineering
Precipitation of charged amino acids in
the presence of oppositely charged polyelectrolytes leads to liquid droplets of the
corresponding polymer/amino acid complexes in water. The resulting emulsions
are stable against crystallization and
Ostwald ripening for several months but
can also be used as a starting situation for
crystallization of spherical, porous crystal
superstructures (see SEM image of
l-lysine).
Enzyme Catalysis
R. Winkler, C. Hertweck*
S. Wohlrab, H. Clfen,*
M. Antonietti
4083 – 4087
4087 – 4092
Crystalline, Porous Microspheres Made
from Amino Acids by Using PolymerInduced Liquid Precursor Phases
Enantiomer Separation
G. Sicoli, Z. Jiang, L. Jicsinsky,
V. Schurig*
4092 – 4095
Modified Linear Dextrins
(“Acyclodextrins”) as New Chiral
Selectors for the Gas-Chromatographic
Separation of Enantiomers
3954
Cyclic or acyclic: Not only modified
cyclodextrins but also modified linear
dextrins like the silylated (R)and acetylated (R1) maltoheptaose derivatives 1 are
suitable selectors for separating racemic
N-trifluoroacetyl-O-alkyl esters of a-amino
acids by gas chromatography. In the
example shown, racemic N-trifluoroacetylserine O-ethyl ester is resolved.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
Angewandte
Chemie
Catalyst Recycling
L. V. Dinh, J. A. Gladysz*
4095 – 4097
“Catalyst-on-a-Tape”—Teflon: A New
Delivery and Recovery Method for
Homogeneous Fluorous Catalysts
Nothing sticks to Teflon? Going one
better than “soap on a rope”, a recyclable
fluorous rhodium hydrosilylation catalyst
is described that is released from Teflon
tape into dibutyl ether upon warming, and
readsorbed upon cooling (see scheme).
Service
Keywords
4098
Authors
4099
Preview
4101
Corrigendum
*
The compounds in Equation (1) of this Communication were renumbered before
printing, yet the requisite change to the text was not made. The sentence that begins on
the last line preceding Equation (1) should therefore read: “Compound 1 exhibits
strong fluorescence not only in concentrated solution but also in the solid state.”
A Novel Fluorescent Dye with Strong,
Anisotropic Solid-State Fluorescence,
Small Stokes Shift, and High
Photostability
H. Langhals,* O. Krotz, K. Polborn,
P. Mayer
2427–2428
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200461610
Angew. Chem. Int. Ed. 2005, 44, 3946 – 3955
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3955
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