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Graphical Abstract Angew. Chem. Int. Ed. 282005

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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. Dom2nech, A. Pagani, L. T3o, 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
Carbohydrates: R. R. Schmidt
Awarded
Catalysis: H. Kagan Receives Prize
4284
4284
Organometallic Chemistry:
L. Oro Honored
4284
Books
Asymmetric Organocatalysis
Albrecht Berkessel, Harald Gr#ger
reviewed by M. J. Krische
4285
Analytical Chemistry
Robert Kellner, Jean-Michel Mermet,
Matthias Otto, Miguel Valc)rel,
H. Michael Widmer
reviewed by J. Bettmer
4286
The glycine-dependent riboswitch is a
high-precision molecular RNA switch to
control the use of glycine as a “fuel” (in
energy-yielding catabolism) or as a “chemical” (in anabolism and protein biosynthesis).
Highlights
Gene Regulation
B. Kr+utler*
4288 – 4290
A High-Precision Switch on an RNA
Message
Minireviews
Synthetic Methods
J. M. Janey*
Chiral Lewis acids and Lewis bases catalyze the a amination and the
a oxygenation of aldehydes, ketones, and
esters (see scheme). This is a powerful
way to directly introduce a heteroatom
adjacent to a carbonyl group, and this
reaction provides access to important
enantiomerically pure building blocks
such as a-amino acids.
4292 – 4300
Recent Advances in Catalytic,
Enantioselective a Aminations and
a Oxygenations of Carbonyl Compounds
4274
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 4274 – 4282
Angewandte
Chemie
Reviews
Reaction Kinetics
D. G. Blackmond*
4302 – 4320
Reaction Progress Kinetic Analysis: A
Powerful Methodology for Mechanistic
Studies of Complex Catalytic Reactions
Intuitive and precise: Kinetic measurements are often considered time-intensive
and routine studies required to determine
concentration dependences and help distinguish between different proposed
reaction mechanisms. This Review
describes step by step how this can be
achieved from a minimal number of
experiments with the help of intuitive
“graphical rate equations” (see picture)
without prior mechanistic knowledge of a
catalytic reaction cycle.
Communications
Chiral Polymerization
Contagious chirality: A chiral polymer (see
image) was obtained from the polycondensation of an achiral monomer by using
a chiral nematic liquid crystal (N*-LC) as
an inert reaction solvent. The chirality of
the polymer is thought to derive from the
asymmetry produced by the chiral
medium during polymerization.
H. Goto, K. Akagi*
4322 – 4328
Optically Active Conjugated Polymers
Prepared from Achiral Monomers by
Polycondensation in a Chiral Nematic
Solvent
Iron Oxide Nanotubes
C.-J. Jia, L.-D. Sun,* Z.-G. Yan, L.-P. You,
F. Luo, X.-D. Han, Y.-C. Pang, Z. Zhang,
C.-H. Yan*
4328 – 4333
Single-Crystalline Iron Oxide Nanotubes
Phosphate ions play a crucial role not only
for the formation of the spindlelike precursors of the single-crystalline hematite
nanotubes that were synthesized by a
facile hydrothermal method. They are also
important for the adsorption and coordination effects. The mechanism of tube
formation was deduced through EM
observations as a coordination-assisted
dissolution process (see picture).
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individuals who are personal members of a
Angew. Chem. Int. Ed. 2005, 44, 4274 – 4282
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national chemical society, or whose institution
already subscribes, or who are retired or selfemployed consultants, print only: US$ 394.00.
Postage and handling charges included. All
Wiley-VCH prices are exclusive VAT.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4275
Angewandte
Chemie
Protein Nanoarrays
Y. Liu, C. Lin, H. Li, H. Yan* 4333 – 4338
Aptamer-Directed Self-Assembly of
Protein Arrays on a DNA Nanostructure
Lined up nicely: The self-assembly of
proteins on rationally designed nanostructures into periodic linear arrays has
been demonstrated. Triple-crossover DNA
tiles 1 containing an aptamer sequence
(AS) to which thrombin specifically binds
can form linear arrays 2. These direct the
ultimate positioning of thrombin proteins
(green spheres) in 3. This system should
facilitate the construction of other such
programmable nanoscale protein arrays.
A windmill-like trititanium cluster with
side-on-bonded CO ligands (see picture),
which may have antiaromatic character,
was revealed by FTIR spectroscopy and
DFT calculations. It is generated, along
with other side-on-bonded mono- and
polycarbonyl di- and trititanium clusters,
in the reaction of laser-ablated Ti atoms
with CO in a solid argon matrix.
Reactor core: Hollow core–shell Au–TiO2
nanocomposites can be prepared by a wet
chemical method to form reactors that
contain a catalyst core with a shell that is
permeable to reactants. The core can be
enlarged, and modification of the synthesis produces flowerlike nanostructures
(see picture). Catalytic reactions in both
the gaseous and liquid phase can be
conducted in this type of photosensitized
metal–semiconductor nanoreactor.
Cluster Compounds
Q. Xu,* L. Jiang, N. Tsumori 4338 – 4342
cyclo-Ti3[h2(m2-C,O)]3 : A Side-on-Bonded
Polycarbonyl Titanium Cluster with
Potentially Antiaromatic Character
Nanoreactors
J. Li, H. C. Zeng*
4342 – 4345
Size Tuning, Functionalization, and
Reactivation of Au in TiO2 Nanoreactors
Alkane Activation
Rich activity from a few coppers: Di-, tri-,
tetra-, and polynuclear copper triethanolamine complexes are easily prepared and
are selective and efficient catalysts for
alkane peroxidative oxidation under mild
conditions (see picture).
A. M. Kirillov, M. N. Kopylovich,
M. V. Kirillova, M. Haukka,
M. F. C. G. da Silva,
A. J. L. Pombeiro*
4345 – 4349
Multinuclear Copper Triethanolamine
Complexes as Selective Catalysts for the
Peroxidative Oxidation of Alkanes under
Mild Conditions
Angew. Chem. Int. Ed. 2005, 44, 4274 – 4282
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4277
Contents
Copolymer Synthesis
A. Kros,* W. Jesse, G. A. Metselaar,
J. J. L. M. Cornelissen*
4349 – 4352
Synthesis and Self-Assembly of Rod–Rod
Hybrid Poly(g-benzyl l-glutamate)-blockPolyisocyanide Copolymers
Carbon Dioxide Fixation
L.-Y. Kong, Z.-H. Zhang, H.-F. Zhu,
H. Kawaguchi, T.-a. Okamura, M. Doi,
Q. Chu, W.-Y. Sun,*
N. Ueyama
4352 – 4355
Copper(ii) and Zinc(ii) Complexes Can
Fix Atmospheric Carbon Dioxide
Molecular Devices
Y. Tian, Y. He, Y. Chen, P. Yin,
C. Mao*
4355 – 4358
A DNAzyme That Walks Processively and
Autonomously along a One-Dimensional
Track
Connecting rods: Rigid rod–rod block
copolymers are synthesized from peptide
and polyisocyanide blocks (see picture:
blue = poly(g-benzyl l-glutamate); red =
poly(methylbenzyl isocyanide) or poly(l-isocyanoalanyl-l-alanine methyl ester).
The polyisocyanide helix has side arms
organized in a parallel b-sheet (light blue).
Some copolymers self-assemble into
ordered layers of hollow capsules.
Carbonato bridges from atmospheric
carbon dioxide: The copper(ii) and
zinc(ii) complexes of the novel imidazolecontaining polyamine ligand N1-(2-aminoethyl)-N1-(2-imidazolethyl)ethane-1,2diamine are found to fix carbon dioxide by
hydration to m3-carbonate ligands. This is
revealed by IR and solid-state 13C NMR
spectroscopic and X-ray crystallographic
studies of the two-dimensional complexes
(see picture).
Inching its way forward: A DNA nanodevice is presented which can autonomously
and processively move on a well-defined
track with a 7-nm step size. The moving
principle integrates DNAzyme activity and
a strand-displacement strategy, which
resembles the behavior of a caterpillar
eating its way through a row of plants (see
picture).
Molecular Devices
J. Bath,* S. J. Green,
A. J. Turberfield
4358 – 4361
A Free-Running DNA Motor Powered by a
Nicking Enzyme
4278
DNA burns its bridges: A unidirectional
molecular motor that moves an oligonucleotide cargo along a self-assembled
track is powered by restriction endonuclease hydrolysis of the phosphodiester
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
backbone (see scheme). Damage caused
to the track by the restriction enzyme
prevents the cargo from stepping backwards and therefore imposes directionality.
Angew. Chem. Int. Ed. 2005, 44, 4274 – 4282
Angewandte
Chemie
Coordination Modes
Newcomers in the family: Pd–Pt heterobimetallic and Cu–Cu homobimetallic
species (see picture) bearing bridging
phosphane ligands are reported. Their
structural arrangement reveals a continuum between semi-bridging and bridging coordination modes.
F. Leca, C. Lescop, E. Rodriguez-Sanz,
K. Costuas, J.-F. Halet,
R. RQau*
4362 – 4365
Bridging Phosphanes: Exotic or Versatile
Binucleating Ligands?
Asymmetric Mannich Reaction
S. Harada, S. Handa, S. Matsunaga,*
M. Shibasaki*
4365 – 4368
Stretching the limits of the Mannich
reaction: A new indium–binol catalyst was
used to generate the enolate of the esterequivalent donor in situ (see scheme).
The donor, an N-acylpyrrole, has many
similarities to an aromatic ketone, in
295 nm
67%
90%
615 nm
particular the enolates should have the
same coordination mode. Versatile
b-amino-a-hydroxy carboxylic acid derivatives were obtained in high yield and ee
values.
Direct Catalytic Asymmetric MannichType Reactions of N-(2-Hydroxyacetyl)pyrrole as an Ester-Equivalent Donor
A star in the making: Star-shaped block
copolymers have been synthesized by
reversible addition–fragmentation chaintransfer (RAFT) polymerization to obtain
light-harvesting systems with an energy
gradient from the periphery to the core.
Excitation-energy transfer in the block
copolymers occurs through an energy
cascade from the excited acenaphthenyl
units to the coumarin chromophores and
hence to the RuII complex core (red
sphere: see picture).
Light-Harvesting Polymers
M. Chen, K. P. Ghiggino,* S. H. Thang,
G. J. Wilson
4368 – 4372
Star-Shaped Light-Harvesting Polymers
Incorporating an Energy Cascade
Amino Sugar Synthesis
T. Nishiyama, M. Isobe,
Y. Ichikawa*
4372 – 4375
Total Synthesis of Glycocinnasperimicin D
A three-fragment coupling strategy afforded the antibiotic glycocinnasperimicin D
(1). The convergent total synthesis features a Heck reaction to form the cinnamoyl glycoside, the [3,3] sigmatropic
Angew. Chem. Int. Ed. 2005, 44, 4274 – 4282
rearrangement of an allyl cyanate for the
stereoselective synthesis of the allyl
amine, and the coupling of a glycosyl
isocyanate with an amino sugar for the
construction of the urea glycoside linkage.
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4279
Contents
Nanostructures
M. A. Correa-Duarte, J. PQrez-Juste,
A. S)nchez-Iglesias, M. Giersig,
L. M. Liz-Marz)n*
4375 – 4378
Aligning Au Nanorods by Using Carbon
Nanotubes as Templates
With strings attached: Gold nanorods
undergo uniform electrostatic assembly
on multiwall carbon nanotubes (MWNTs)
to form strings of rods with end-to-end
contacts (see picture, PSS = polystyrene
sulfonate, PDDA = poly(diallyldimethyl)ammonium chloride). This arrangement
results in uniaxial plasmon coupling, and
the polarization-dependent optical
response has been used to monitor the
degree of alignment of carbon nanotubes
within polymer films.
Prodrug Activation
R. J. Amir, M. Popkov, R. A. Lerner,
C. F. Barbas III, D. Shabat* 4378 – 4381
Prodrug Activation Gated by a Molecular
“OR” Logic Trigger
Molecules that define logic: A molecular
“OR” logic gate trigger has been demonstrated by masking a functional group in a
doxorubicin prodrug with a linker that
contains two cleavable substrates (input).
The prodrug molecule was activated by
two different enzymes to release the
parent drug (see scheme; input red;
output (drug) blue).
Gasoline from methane: Methane can be
activated nonoxidatively and converted
into higher hydrocarbons over bifunctional zeolite catalysts at low temperatures ( 600 8C; see scheme). The amount
of methane converted per mole of
methanol by this process can meet or
even exceed 1 mol. This approach could
potentially lead to an economically
feasible technology for the commercial
conversion of methane into liquid
hydrocarbons.
Hydrocarbon Chemistry
V. R. Choudhary,* K. C. Mondal,
S. A. R. Mulla
4381 – 4385
Simultaneous Conversion of Methane and
Methanol into Gasoline over Bifunctional
Ga-, Zn-, In-, and/or Mo-Modified ZSM-5
Zeolites
Homogeneous Catalysis
Contrary to earlier speculation, mononuclear rhodium species that contain
trans diphosphines, such as SPANphos,
are inactive towards the oxidative addition
of methyl iodide, whereas the corresponding dinuclear species are very reactive. Thus, the active species in methanol
carbonylation is most likely the dimeric
system (see scheme; P orange, O red,
Rh blue, Cl green).
Z. Freixa,* P. C. J. Kamer, M. Lutz,
A. L. Spek,
P. W. N. M. van Leeuwen
4385 – 4388
Activity of SPANphos Rhodium Dimers in
Methanol Carbonylation
4280
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 4274 – 4282
Angewandte
Chemie
Asymmetric Catalysis
Bishydroxamic acid derivatives are used
as ligands for a vanadium catalyst in the
preparation of epoxy alcohols (see
scheme). The methodology uses aqueous
tert-butyl hydroperoxide (TBHP) as an
achiral oxidant, low catalyst loading, low
reaction temperatures (0 8C to room
temperature), and simple workup procedures. The reaction is applied to the
kinetic resolution of a secondary allylic
alcohol and the preparation of small epoxy
alcohols. R1, R2, R3 : alkyl, aryl, H.
“Hedgehog” or “nest” microspheres of
V2O5 are formed when nanorods of V2O5
are synthesized in a mediated polyol
process. When the concentration of the
starting material is low, a nest shape is
preferred, whereas a high concentration of
[V(acac)3] affords hedgehog-shaped
microspheres (see picture). The V2O5
microspheres exhibit remarkable electrochemical properties when used as the
cathode material in a lithium-ion battery.
W. Zhang, A. Basak, Y. Kosugi, Y. Hoshino,
H. Yamamoto*
4389 – 4391
Enantioselective Epoxidation of Allylic
Alcohols by a Chiral Complex of
Vanadium: An Effective Controller System
and a Rational Mechanistic Model
Battery Materials
A.-M. Cao, J.-S. Hu, H.-P. Liang,
L.-J. Wan*
4391 – 4395
Self-Assembled Vanadium Pentoxide
(V2O5) Hollow Microspheres from
Nanorods and Their Application in
Lithium-Ion Batteries
Branching out: A previously unrecognized
ruthenium carbonate intermediate is
formed during the reaction of an allylic
tert-butoxycarbonate with the ruthenium
complex [Ru(Cp*)(CH3CN)3]PF6 (1; see
scheme). The isolatable carbonate–allyl
complex functions very effectively as an
allylic alkylation catalyst. These results
provide new insights into the mechanism
of this ruthenium-catalyzed reaction.
Homogeneous Catalysis
The aromatic box formed by the side
chains Phe 174, Tyr 99, and Trp 215 in the
S4-pocket of Factor Xa is a very effective
onium binding site (see picture; red O,
blue N, green Cligand, gray Cprotein). The free
enthalpy increment for cation–p interactions between quaternary ammonium
ions and aromatic groups in this box is
determined to be DDG = 2.8 kcal mol 1.
Database searches reveal that similar
cation binding sites are not uncommon in
biological systems.
Molecular Recognition
Angew. Chem. Int. Ed. 2005, 44, 4274 – 4282
R. Hermatschweiler, I. Fern)ndez,
F. Breher, P. S. Pregosin,* L. F. Veiros,
M. J. Calhorda
4397 – 4400
Ruthenium-Catalyzed Allylic Alkylation
Reactions: Carbonate-Based Catalysts and
Intermediates
K. Sch+rer, M. Morgenthaler, R. Paulini,
U. Obst-Sander, D. W. Banner,*
D. Schlatter, J. Benz, M. Stihle,
F. Diederich*
4400 – 4404
Quantification of Cation–p Interactions in
Protein–Ligand Complexes: CrystalStructure Analysis of Factor Xa Bound to a
Quaternary Ammonium Ion Ligand
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4281
Contents
Analytical Chemistry
J. V. Ros-Lis, M. D. Marcos,
R. M)rtinez-M)Sez,* K. Rurack,*
J. Soto
4405 – 4407
A Regenerative Chemodosimeter Based
on Metal-Induced Dye Formation for the
Highly Selective and Sensitive Optical
Determination of Hg2+ Ions
Into the blue: Hg2+ -ion-triggered formation of a brightly fluorescent squaraine dye
is used as a novel approach for the design
of highly selective and sensitive chromofluorogenic probes for the analysis of
Hg2+ ions down to concentrations below
2 ppb (see picture). Through the adsorption of the sensor on a solid support a
prototype reusable test strip is also generated.
Service
Keywords
4408
Authors
4409
Preview
4411
Corrigendum
*
Photo-Cross-Linked Small-Molecule
Affinity Matrix for Facilitating Forward and
Reverse Chemical Genetics
In this communication, the structure of activated CH agarose 4B beads (2), which were
purchased from Amersham Bioscience, and the following structures (3 and 4) in
Scheme 1 were rendered incorrectly; the correct structures are shown. The authors
apologize for this oversight.
N. Kanoh, K. Honda, S. Simizu, M. Muroi,
H. Osada*
3559–3562
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200462370
4282
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 4274 – 4282
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