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Graphical Abstract Angew. Chem. Int. Ed. 342006

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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:
Jean-P. Leclerc, K. Fagnou*
Palladium-Catalyzed Cross-Coupling Reactions of Diazine
N-Oxides with Aryl Chlorides, Bromides, and Iodides
J. W. Lee, Jun-S. Lee, Young-T. Chang*
Colorimetric Identification of Carbohydrates by a pH
Indicator/pH-Change-Inducer Ensemble
Zhi-M. Cui, Q. Liu, Wei-G. Song*, Li-J. Wan*
Insights into the Mechanism of Methanol-to-Olefin Conversion
from Zeolites with Systematically Selected Framework Structures
J. A. Porco, Jr.,* S. Su, X. Lei, S. Bardhan, S. D. Rychnovsky
Total Synthesis and Structure Assignment of (+)-Hexacyclinol
S. Hiraoka, K. Harano, M. Shiro, Y. Ozawa, N. Yasuda, K. Toriumi,
M. Shionoya*
Isostructural Coordination Capsules with a Series of 10 Different
d5–d10 Transition-Metal Ions
J. G. Cordaro, D. Stein, H. R3egger, H. Gr3tzmacher*
Making the True "CP" Ligand
News
Chemistry:
Whitesides honored
5576
Medicinal Chemistry:
Kubinyi recognized
5576
Electrochemistry:
Prize for Wang
5576
Books
Crystalline Molecular Complexes and
Compounds
Frank H. Herbstein
reviewed by A. Gavezzotti
5577
Value Creation
Florian Budde, Utz-Hellmuth Felcht,
Heiner Frankem&lle
reviewed by A. Kleemann
5577
Highlights
Nitrogen-Substituted Ketenes
T. T. Tidwell*
5580 – 5582
Blue, but Not a Mirage: Stable
Aminoketenes by Carbene Carbonylation
DNA Repair
H.-A. Wagenknecht*
5583 – 5585
The Search for Single DNA Damage
among Millions of Base Pairs: DNA
Glycosylases Trapped at Work
5564
A true oasis: The preparation of the first
isolable aminoketenes by carbon monoxide addition to nitrogen-substituted carbenes (see scheme; Ar = 2,6-iPr2C6H3) fills
a void in ketene chemistry in unexpected
ways, and further provides a visual
demonstration of ketene HOMO–LUMO
interactions.
Flipped out? The location of base lesions
by DNA glycosylases does not necessarily
need complete base-flipping into the
active site as recent structures of DNAprotein complexes show (see picture;
oG = 8-oxoguanine).
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
Angewandte
Chemie
Reviews
One hand washes the other: The methods
of inorganic chemistry have for many
years supported biology. It is now time to
show what new biological techniques can
do for inorganic chemistry.
Chemical Biology
5588 – 5601
Y. Lu*
Biosynthetic Inorganic Chemistry
Communications
The lone (ar)ranger: The structure of
Cu20Sb35O44Cl37 is divided up into two
parts: ionically bonded Cu+–Cl supertetrahedra (green) and covalently bonded
clusters that resemble zeolite b cages.
The Sb3+ ions (gray) lie at the vertices of
the cages, while their lone pairs of electrons form surfaces that separate the
covalent and ionic parts.
For the USA and Canada:
ANGEWANDTE CHEMIE International
Edition (ISSN 1433-7851) is published weekly
by Wiley-VCH PO Box 191161, D 69451 Weinheim, Germany. Air freight and mailing in the
USA by Publications Expediting Inc. 200
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
Inorganic Chemistry
Z. Mayerov=, M. Johnsson,*
S. Lidin
5602 – 5606
Lone-Pair Interfaces That Divide Inorganic
Materials into Ionic and Covalent Parts
Double or nothing: Large-scale density
functional calculations are used to study
the formation of a large polaron on three
proximal guanines (see picture). The formation was observed by step by step
following of a proton-coupled charge
transfer. The role played by the double
proton transfer and a new and unexpected
role for the tautomers of G and C were
found.
Charge Transfer
Down to the wire: PtII···PtII interactions
provide the cohesive driving force for the
construction of micro- and nanometerscale luminescent wires, such as nanowires of [Pt(CNtBu)2(CN)2] (see picture;
Pt pink, N blue, C gray), which is a
potential candidate for applications in
nano-optical, electronic, and sensory
devices.
Nanowires
Meacham Ave., Elmont, NY 11003. Periodicals
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$ 5685/5168 (valid for print and
F. L. Gervasio,* M. Boero,
M. Parrinello
5606 – 5609
Double Proton Coupled Charge Transfer in
DNA
Y. Sun, K. Ye, H. Zhang, J. Zhang, L. Zhao,
B. Li, G. Yang, B. Yang, Y. Wang,* S.-W. Lai,
C.-M. Che*
5610 – 5613
Luminescent One-Dimensional
Nanoscale Materials with PtII···PtII
Interactions
electronic / print or electronic delivery); for
individuals who are personal members of a
national chemical society prices are available
on request. Postage and handling charges
included. All prices are subject to local VAT/
sales tax.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5565
Angewandte
Chemie
A novel construction: The reaction of
[FeCl4] with (Me3Sn)3N leads to the
cluster [Fe14N8(NSnMe3)4Cl12]4 (see picture; Fe red, N blue, Sn yellow, Cl green;
Me groups omitted), which has a core
built from 16 Fe2N2 rhombs. M&ssbauer
spectroscopy indicates the presence of
12 FeIII and 2 FeII ions, and magnetic
measurements suggest an S = 2 ground
state for the cluster.
Iron Nitride Clusters
Reversal: Simple peptide-based nucleophilic catalysts can perturb the inherent
reactivity hierarchy of the polyol natural
product erythromycin A (see picture).
Such catalyst-dependent modifications
that reorganize natural product architecture may be of utility for generation of
natural product analogs.
Natural-Product Modification
5613 – 5616
Self-Assembly of a Tetradecanuclear Iron
Nitride Cluster
C. A. Lewis, S. J. Miller*
5616 – 5619
Site-Selective Derivatization and
Remodeling of Erythromycin A by Using
Simple Peptide-Based Chiral Catalysts
Structure Determination
Twists in a spin: RNA structural constraints have been obtained directly by
exploiting the dependence of inter- and
intranucleotide 1H–1H interactions on
RNA conformation through the use of 13C
MAS solid-state NMR spectroscopy. The
data provide evidence that (CUG)97 RNA
principally adopts an A-form helix conformation with a C3’-endo sugar pucker
and an anti glycosidic torsion angle c (see
model).
K. Riedel, C. Herbst, S. HMfner,
J. Leppert, O. OhlenschlMger,
M. S. Swanson, M. G&rlach,
R. Ramachandran*
5620 – 5623
Constraints on the Structure of (CUG)97
RNA from Magic-Angle-Spinning SolidState NMR Spectroscopy
A sticky end: Two DNA strands that
produce three contiguous mismatches
(5’-TGG-3’/5’-TGG-3’ sequence) do not
hybridize spontaneously, but are adhered
by the mismatch-binding ligand naphthyridine carbamate dimer (NC; see picture, red rectangles: naphthyridine rings).
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
M. V. Bennett, R. H. Holm*
DNA Hybridization
T. Peng, C. Dohno,
K. Nakatani*
5623 – 5626
Mismatch-Binding Ligands Function as a
Molecular Glue for DNA
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5567
Contents
Electron Transfer
M. P. Eng, B. Albinsson*
5626 – 5629
Non-Exponential Distance Dependence of
Bridge-Mediated Electronic Coupling
Donor chromophores attached to oligo(phenyleneethynylene) molecular bridges
of varying length have attenuation factors
for electron tunneling b that vary systematically with the donor–bridge (DB) energy
gap (see picture). Investigations show
that for bridges with ethynylene and
vinylene repeating subunits, the electronic
coupling increases with increasing donor–
acceptor (DA) distance. A simple model
accounts for this unexpected observation.
Molecular Recognition
T. Ito, T. Yamaguchi*
In full swing: Nonlinear oscillations by
molecular signals are one of the inherent
properties of life. An artificial ion-gating
membrane, which was synthesized from a
thermosensitive polymer and a crown
ether, generated a relaxation oscillation
similar to that of neurons in response to a
specific ion signal (see picture).
5630 – 5633
Nonlinear Self-Excited Oscillation of a
Synthetic Ion-Channel-Inspired
Membrane
Protein Engineering
D. Sharma, Y. Cao, H. Li*
The power of recombination: A DNAshuffling-based recombination technique
was used to recombine protein fragments
from two parent proteins to generate
hybrid proteins, which can fold into threedimensional structures similar to those of
the parent proteins. These designed
hybrid proteins are mechanically stable
and display novel mechanical properties.
5633 – 5638
Engineering Proteins with Novel
Mechanical Properties by Recombination
of Protein Fragments
Bismuth Clusters
P. C. Andrews,* G. B. Deacon,
C. M. Forsyth, P. C. Junk, I. Kumar,
M. Maguire
5638 – 5642
Towards a Structural Understanding of the
Anti-Ulcer and Anti-Gastritis Drug
Bismuth Subsalicylate
5568
www.angewandte.org
The action of Pepto-Bismol arising from
the structure and hydrolysis of bismuth
subsalicylate (BSS) is not yet understood.
Two bismuth oxosalicylate clusters,
[Bi38O44(HSal)26(Me2CO)16(H2O)2] (1) and
[Bi9O7(HSal)13(Me2CO)5] (2), have been
characterized which provide structural
insight into the nature of BSS. A Bi9O7
cluster forms the core of 2 and is found at
the heart of 1 (see picture; core Bi atoms:
green, core O atoms: red).
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
Angewandte
Chemie
Porphyrinoids
C. P. Gros, J.-M. Barbe,* E. Espinosa,
R. Guilard*
5642 – 5645
Room-Temperature Autoconversion of
Free-Base Corrole into Free-Base
Porphyrin
As easy as AB2C: Irradiation of a solution
of the free-base corrole 1 with a 400-W
lamp led to its conversion into the
corresponding trans-AB2C-porphyrin 2 and
an open-chain biliverdin-type by-product.
Bioorganometallic Chemistry
C. Streu, E. Meggers*
5645 – 5648
Ruthenium-Induced Allylcarbamate
Cleavage in Living Cells
Easy going: A ruthenium-catalyzed
release of amines from their respective
allylcarbamates is disclosed and is a step
towards the design of catalysts as tools for
cellular biology. The reaction tolerates the
combination of water, air, and thiols and
can be performed inside living mammalian cells. Cp* = pentamethylcyclopentadienyl, cod = 1,5-cyclooctadiene.
Problem child: The application of signaling DNA-aptamer technology to the
development and execution of a highthroughput screen for an otherwise problematic target, adenosine deaminase
(ADA), is reported. The approach
employed a signaling DNA aptamer that
reports on adenosine concentration (see
scheme). The assay was robust in a screen
of more than 44 000 molecules and
revealed a new competitive inhibitor of the
deaminase.
Screening
Superduper: A practical and cleaner synthetic protocol for various glycosides was
established by means of a recyclable solid
superacid promoter in supercritical
carbon dioxide (scCO2). Anomeric mixtures composed of a- and b-isomers were
successfully separated by employing
supercritical fluid chromatography (SFC)
with scCO2 and methanol. L = leaving
group, P = protecting group, ROH =
sphingosine, sugar, etc.
Glycosidation
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
N. H. Elowe, R. Nutiu, A. Allali-Hassani,
J. D. Cechetto, D. W. Hughes, Y. Li,*
E. D. Brown*
5648 – 5652
Small-Molecule Screening Made Simple
for a Difficult Target with a Signaling
Nucleic Acid Aptamer that Reports on
Deaminase Activity
X.-B. Li, M. Ogawa, T. Monden, T. Maeda,
E. Yamashita, M. Naka, M. Matsuda,
H. Hinou, S.-I. Nishimura* 5652 – 5655
Glycosidation Promoted by a Reusable
Solid Superacid in Supercritical Carbon
Dioxide
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5569
Contents
Thermoelectric Materials
A new strategy to grow thermoelectric
nanostructures on a wide variety of substrates is introduced. The synthesis
involves the reduction of a selenium
precursor to promote nucleation with
bismuth ions to produce Bi2Se3 nanostructured films (see picture, scale bar
10 mm) under thermodynamic control.
Thermoelectric transport measurements
of the nanostructured films were performed from 6 to 300 K.
X. Qiu, L. N. Austin, P. A. Muscarella,
J. S. Dyck,* C. Burda*
5656 – 5659
Nanostructured Bi2Se3 Films and Their
Thermoelectric Transport Properties
Labeled Amino Acids
P. K. Mikhailiuk, S. Afonin, A. N. Chernega,
E. B. Rusanov, M. O. Platonov,
G. G. Dubinina, M. Berditsch,
A. S. Ulrich,* I. V. Komarov* 5659 – 5661
Conformationally Rigid TrifluoromethylSubstituted a-Amino Acid Designed for
Peptide Structure Analysis by Solid-State
19
F NMR Spectroscopy
Superlattices
Y. Yang, S. Liu, K. Kimura*
5662 – 5665
Superlattice Formation from Polydisperse
Ag Nanoparticles by a Vapor-Diffusion
Method
Designing a sturdy label: The fluorinated
amino acid l-CF3-Bpg (see picture), which
was specifically designed as a 19F NMR
label for structure analysis of membranebound peptides, does not display the
A self-correction process that is time- and
pH-dependent results in growth of perfect
superlattices from a bulk solution of
hydrophilic Ag nanoparticles, despite their
polydispersity, by a vapor-diffusion technique. After 12 weeks, three-dimensional
rhombic superlattices are obtained (see
picture).
Heterocycles
M. Pittelkow, T. K. Reenberg, K. T. Nielsen,
M. J. Magnussen, T. I. Sølling, F. C. Krebs,
J. B. Christensen*
5666 – 5670
Synthesis, Structure, and Properties of
4,7-Dimethoxybenzo[c]tellurophene:
A Molecular Pyroelectric Material
5570
www.angewandte.org
drawbacks of previously used labels. The
amino acid can be readily incorporated
into peptides and is particularly suitable
as a substitute for Leu, Ile, and Met.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
More than just curiosities: The synthesis
and characterization of a stable benzo[c]tellurophene are presented. Te Te interactions are shown to be one of the main
driving forces for the crystal-packing
properties of this electron-rich benzo[c]tellurophene; furthermore, investigation
of its pyroelectric properties reveals a
secondary pyroelectric effect.
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
Angewandte
Chemie
Porphyrinoid Chemistry
The expanded phthalocyanine dicarbahemiporphyrazine forms complexes in
which the arene CH groups are in close
proximity to the metal center. In the case
of the copper adduct, one of the two C H
bonds is attacked by a solvent pyridine
molecule, thereby forming a C N bond
(see picture; C gray, N blue, H light
green). This reaction may proceed by
oxidative nucleophilic substitution of
hydrogen.
R. Wu, A. Çetin, W. S. Durfee,*
C. J. Ziegler*
5670 – 5673
Metal-Mediated C H Bond Activation in a
Carbon-Substituted Hemiporphyrazine
Asymmetric Catalysis
C. Walter, G. Auer,
M. Oestreich*
Missing linkage: A chiral cationic rhodium
complex catalyzes the enantioselective
conjugate addition of silyl anion equivalents to cyclic a,b-unsaturated ketones
(X = CH2) and esters (X = O; see
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
5675 – 5677
scheme). This unprecedented catalytic
process enables the asymmetric formation of a carbon–silicon bond, thus providing a facile access to a-chiral organosilicon compounds.
Rhodium-Catalyzed Enantioselective
Conjugate Silyl Transfer: 1,4-Addition of
Silyl Boronic Esters to Cyclic Enones and
Lactones
Productive cells: In a simple, highly
efficient process for the synthesis of
optically active alcohols, ketones are
reduced by “designer cells” at high substrate concentrations and without the
addition of an “external” cofactor in
aqueous reaction medium. A wide range
of R and S alcohols can be prepared with
conversions of > 90 % and enantioselectivities of > 99 % ee (scheme shows
results from the application on a 10-L
scale).
Enzyme Catalysis
A ferryl cation in water: Iron(II) coordinated by the pentadentate ligand L reacts
with H2O2 to form a low-spin FeIV=O
complex with S = 1 (2 in scheme) under
conditions similar to those of the classical
Fenton reaction. Complex 2 differs from a
recently obtained high-spin aquated
oxoiron(IV) species and demonstrates the
role of the supporting polydentate ligand
in controlling spin state and product
formation.
Coordination Chemistry
H. Gr&ger,* F. Chamouleau, N. Orologas,
C. Rollmann, K. Drauz, W. Hummel,
A. Weckbecker, O. May*
5677 – 5681
Enantioselective Reduction of Ketones
with “Designer Cells” at High Substrate
Concentrations: Highly Efficient Access to
Functionalized Optically Active Alcohols
J. Bautz, M. R. Bukowski, M. Kerscher,
A. Stubna, P. Comba,* A. Lienke,
E. MTnck,* L. Que, Jr.*
5681 – 5684
Formation of an Aqueous Oxoiron(IV)
Complex at pH 2–6 from a Nonheme
Iron(II) Complex and H2O2
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5571
Contents
Biosynthetic Pathways
M. S. Abdelfattah, J. Rohr*
5685 – 5689
Premithramycinone G, an Early Shunt
Product of the Mithramycin Biosynthetic
Pathway Accumulated upon Inactivation
of Oxygenase MtmOII
The unusual dodecaketide premithramycinone G (see formula), which possesses
a five-membered ring with two ketide
chains in its tetracyclic structure, was
accumulated upon inactivation of an early
acting oxygenase of the mithramycin
biosynthetic pathway. This unexpected
structure allows novel hypothetic conclusions to be drawn regarding the early
mithramycin pathway and suggestions for
the involvement of three previously unassigned oxygenases.
Coordination Polymers
A fragile coordination polymer: The pentaphosphaferrocene [Cp*Fe(h5-P5)] reacts
with the AgI salt of the weakly coordinating anion [Al{OC(CF3)3}4] to yield a
polymer comprising cyclo-P5 moieties in
an unprecedented 1,2,3-coordination
mode (see figure). Analytical data and
DFT calculations support the existence of
a monomer/dimer/oligomer equilibrium
in solution, which is entirely in favor of the
monomer at room temperature and shifts
to the dimer/oligomer at reduced temperatures.
M. Scheer,* L. J. Gregoriades,
A. V. Virovets, W. Kunz, R. Neueder,
I. Krossing
5689 – 5693
Reversible Formation of Polymeric Chains
by Coordination of Pentaphosphaferrocene with Silver(I) Cations
Asymmetric Rearrangement
M. E. Weiss, D. F. Fischer, Z.-q. Xin,
S. Jautze, W. B. Schweizer,
R. Peters*
5694 – 5698
Practical, Highly Active, and
Enantioselective Ferrocenyl–Imidazoline
Palladacycle Catalysts (FIPs) for the AzaClaisen Rearrangement of N-paraMethoxyphenyl Trifluoroacetimidates
Molecular Knots
M. Feigel,* R. Ladberg
S. Engels, R. Herbst-Irmer,*
R. Fr&hlich*
5698 – 5702
A Trefoil Knot Made of Amino Acids and
Steroids
5572
www.angewandte.org
Just a pinch of catalyst: Just 0.05 mol % of
a novel planar chiral ferrocenyl–imidazoline palladacycle catalyst (FIP) is sufficient
to catalyze a highly efficient aza-Claisen
rearrangement of N-para-methoxyphenyl
trifluoroacetimidates and thereby provide
access to chiral protected primary allylic
amines with unprecedentedly high enantioselectivities (see scheme).
Tying up the loose ends: Cyclization of a
linear hexapeptide made from alternating
valine and a-aminodeoxycholanic acid
units yielded two macrolactams: cyclo(valine-3-a-aminodeoxycholic acid
amide)3 and cyclo(valine-3-a-aminodeoxycholic acid amide)6, the product of a
cyclodimerization (see structure). X-Ray
diffraction studies confirmed that the
latter compound has the structure of a
trefoil knot.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
Angewandte
Chemie
Open sesame: The proteasome complex
is a nanodegradation machine that is
essential for cellular protein turnover. A
multivalent chelator head (MCH) was
exploited for the specific binding to histidine-tagged proteasomes, even in crude
cell lysates. Acting as synthetic gatekeepers, this MCH controls the access and
thus the proteolytic activity of the nanomachinery.
Abstract art: Bare [MgO]+ ions can activate methane in a thermal ion/molecule
reaction to afford [MgOH]+ + CH3C as
major products and Mg+ + CH3OH in a
side reaction. In conjunction with ab initio
calculations, the results strongly support
an hydrogen-atom abstraction mechanism which is assisted by a metal–carbon
interaction (see scheme). Hydrocarbons
(except methane) can also be activated by
the magnesium-oxide cluster [Mg2O2]+.
Nanobiotechnology
K. Schulze, A. Mulder, A. Tinazli,
R. TampX*
5702 – 5705
Controlling the Activity of the 20S
Proteasome Complex by Synthetic
Gatekeepers
Methane Activation
D. Schr&der,* J. Roithov=*
5705 – 5708
Low-Temperature Activation of Methane:
It also Works Without a Transition Metal
Service
Angewandte’s
Sister Journals
5710 – 5711
Keywords
5712
Authors
5713
Vacancies
Preview
A45
5715
For more information on
Chemistry—An Asian Journal see
www.chemasianj.org
Angew. Chem. Int. Ed. 2006, 45, 5564 – 5573
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5573
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