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Graphical Abstract Angew. Chem. Int. Ed. 102006

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The following Communications have been judged by at least two referees to be “very
important papers” and will be published online at soon:
D. P. Curran,* G. Moura-Letts, M. Pohlman
Solution-Phase Mixture Synthesis with Fluorous Tagging En
Route: Total Synthesis of an Eight-Member Stereoisomer Library
of Passifloricins
H. Zhang, H. Xia,* G. He, T. B. Wen, L. Gong, G. Jia*
Synthesis and Characterization of Stable Ruthenabenzenes
X. Mo, Y. An, C.-S. Yun, S. M. Yu*
Nanoparticle-Assisted Visualization of Binding Interactions
between Collagen Mimetic Peptide and Collagen Fibers
M. B. Harney, Y. Zhang, L. R. Sita*
Discrete, Multiblock Isotactic–Atactic Stereoblock Polypropene
Microstructures of Differing Block Architectures by
Programmable Stereomodulated Living Ziegler–Natta
Y. Weizmann, Z. Cheglakov, V. Pavlov, I. Willner*
Autonomous Fueled Mechanical Replication of Nucleic Acid
Templates for the Amplified Optical Detection of DNA
B. Botta, F. Caporuscio, D. Subissati, A. Tafi,* M. Botta, A. Filippi,
M. Speranza*
Flattened-Cone 2,8,14,20-Tetrakis(l-valinamido)[4]resorcinarene:
Enantioselective Allosteric Receptors in the Gas Phase
Arthur Schweiger (1946–2006)
G. Jeschke, S. Stoll
Soft Materials
John R. Dutcher, Alejandro G. Marangoni
reviewed by P. Baglioni
Inorganic and Organometallic Polymers
Vadapalli Chandrasekhar
reviewed by I. Manners
Bioorganometallic Chemistry
U. Schatzschneider,*
N. Metzler-Nolte*
Hard-core drugs: Recent structural and
spectroscopic studies demonstrate the
versatility of organometallic drug candidates, for example, as novel protein kinase
inhibitors and hormone-independent
breast cancer prodrugs. The presence of a
transition-metal center in such systems
allows both the organization of ligands in
3D space (see picture) and the control of
redox-activation processes in biological
1504 – 1507
New Principles in Medicinal
Organometallic Chemistry
Chemical Concepts
W. H. E. Schwarz*
1508 – 1517
Measuring Orbitals: Provocation or
Can complex orbitals really be measured?
Orbital functions can indeed be reconstructed from measured data by various
approaches. Now even femtosecond
measurements can be used, though the
results are still less accurate than those
achieved with purely theoretical methods.
The HOMO of the N2 molecule (see
picture) has been reconstructed directly
from experimental laser-spectroscopic
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
interference intensity measurements by
means of computer algorithms.
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
Reaction Mechanisms
Copied from Nature: A dominant
mechanism used by enzymes, substrate
activation by general acid catalysis, is
emerging as a powerful and versatile
strategy for enantioselective synthesis
with small-molecule catalysts (see
scheme). The mechanistic links between
natural and synthetic hydrogen-bonddonor catalysts are explored, and the
remarkable recent progress in asymmetric
catalysis is reviewed.
M. S. Taylor,
E. N. Jacobsen*
1520 – 1543
Asymmetric Catalysis by Chiral HydrogenBond Donors
Solids go with the flow: A monodisperse
flow in a microreactor provides an efficient method for keeping solid products
away from channel walls. The use of a
carrier phase, such as mineral oil, hexane,
or toluene, enables solids to be synthesized without clogging of the reactor
channels. Further injection points can be
added to the microreactor to perform
multistep syntheses (see picture).
S. L. Poe, M. A. Cummings, M. P. Haaf,
D. T. McQuade*
1544 – 1548
Solving the Clogging Problem:
Precipitate-Forming Reactions in Flow
Supramolecular Chemistry
Y. Kubo, Y. Kitada, R. Wakabayashi,
T. Kishida, M. Ayabe, K. Kaneko,
M. Takeuchi,* S. Shinkai*
1548 – 1553
All line up together! A new concept for the
alignment and assembly of conjugated
polymers through the action of supramolecular bundling (“aligner”) molecules
is inspired by actin-filament bundling
proteins. The approach provides a general
means of preparing complex, ordered
assemblies of conjugated polymers.
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Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
A Supramolecular Bundling Approach
toward the Alignment of Conjugated
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sales tax.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthetic Methods
C.-M. Yu,* J. Youn, J. Jung
More adventures of tin–tin: The stereospecific synthesis of 2-stannylvinyl-1,3diols was achieved through a one-pot
allylic transfer/distannation/allylic trans-
fer reaction sequence (see scheme). The
method was applied to the concise
asymmetric syntheses of ()-avenaciolide
and ()-isoavenaciolide.
Thermally robust porous metal–organic
frameworks (MOFs) with zeolitic topologies were constructed by means of a
ligand-directed strategy involving molecular tailoring of simple bridging imidazolates with coordinatively unimportant
substituents. This led to the isolation of
three new MOFs having unusually high
symmetries, intriguing topologies such as
the supercage shown in the picture, and
high thermal stability.
1553 – 1556
Asymmetric Sequential Allylic Transfer
Reaction for the Synthesis of
2-(1-Stannylvinyl)-1,3-diols: Concise
Synthesis of ()-Avenaciolide and
Metal–Organic Frameworks
X.-C. Huang, Y.-Y. Lin, J.-P. Zhang,
X.-M. Chen*
1557 – 1559
Ligand-Directed Strategy for Zeolite-Type
Metal–Organic Frameworks: Zinc(ii)
Imidazolates with Unusual Zeolitic
B. Wang, Q. Zhao, F. Wang,
C. Gao*
1560 – 1563
Biologically Driven Assembly of
Polyelectrolyte Microcapsule Patterns To
Fabricate Microreactor Arrays
Spaced capsules: Polyelectrolyte hollow
microcapsules are individually and covalently patterned on a flexible polymer film
through specific biotin–avidin recognition. ZnS quantum dots (QDs) and other
Finding flavins: A new class of DNAduplex aptamers that bind to riboflavin by
utilizing an abasic (AP) site has been
developed (see model). An optimized
duplex shows high selectivity for riboflavin
over flavin mononucleotide and flavin
adenine dinucleotide. Such riboflavin–
duplex interactions are discussed as a
basis for the further development of APsite-based DNA aptamers.
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
nanoparticles can be spatially synthesized
in situ by using the aligned capsules as
microreactors (see picture). Release of the
QDs can be tuned by additional layers on
the capsule walls.
N. B. Sankaran, S. Nishizawa, T. Seino,
K. Yoshimoto, N. Teramae* 1563 – 1568
Oligodeoxynucleotides as Aptamers for
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Transport of Nonviral Vectors
R. Bausinger, K. von Gersdorff,
K. Braeckmans, M. Ogris, E. Wagner,
C. BrNuchle,*
A. Zumbusch*
1568 – 1572
The Transport of Nanosized Gene Carriers
Unraveled by Live-Cell Imaging
Tracking transport: Cationic polyethylenimine nanoparticles serve as nonviral
vectors and deliver DNA to the nucleus of
cells. Fluorescence live-cell imaging highlights the interactions between these
polyplexes and the cytoskeleton during
the subsequent stages of transfection (see
picture). The analysis of the underlying
transport processes gives new impulse to
further chemical-synthesis approaches.
Enzyme Systems
Physio-logical: A system of four enzymes,
horseradish peroxidase, glucose dehydrogenase, glucose oxidase, and catalase,
operate in parallel in the presence of
NADH and NAD+ to yield AND and XOR
gates (see picture). Glucose and H2O2 act
as the inputs, and the absorbance that
follows the production of gluconic acid or
NADH provide the outputs of the AND
and XOR gates, respectively.
R. Baron, O. Lioubashevski, E. Katz,
T. Niazov, I. Willner*
1572 – 1576
Elementary Arithmetic Operations by
Enzymes: A Model for Metabolic Pathway
Based Computing
Protein Detection
H. Zhang, Z. Wang, X.-F. Li,
X. C. Le*
1576 – 1580
Ultrasensitive Detection of Proteins by
Amplification of Affinity Aptamers
Superdetective: The detection of
180 molecules of a protein was achieved
by amplification of DNA aptamers that
bind to the target protein. The protein–
aptamer complex is separated from the
unbound aptamer by capillary electro-
Bioinorganic Chemistry
J. O. Debreczeni, A. N. Bullock, G. E. Atilla,
D. S. Williams, H. Bregman, S. Knapp,*
E. Meggers*
1580 – 1585
Ruthenium Half-Sandwich Complexes
Bound to Protein Kinase Pim-1
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
phoresis (CE). The complex fraction is
collected and the aptamer amplified by
the polymerase chain reaction (PCR).
Such amplification dramatically improves
the sensitivity of the detection of proteins.
Keeping in shape with half a sandwich:
The structure of a picomolar organoruthenium inhibitor bound to the ATPbinding site of the protein kinase Pim-1
(see picture) demonstrates that the
ruthenium center has solely a structural
role in organizing the organic ligands in
the three-dimensional receptor space,
thus yielding a structure that is complementary in shape and functional group
presentation to the active site of Pim-1.
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
Currency exchange! Amphiphilic parahexanoylcalix[4]arenes can form hydrophobic van der Waals nanocapsules (see
picture) which are flexible enough to allow
efficient guest exchange without destroying the crystal lattice. Purple: C (dibenzylketone), green: Cl(CHCl3), red: O,
white: H.
Performance-enhancing ligands: Two new
bridged bicyclic phosphines 1 a,b based
on the “phoban” skeleton (see structures
of their naphth-2-ylmethyl bromide salts;
P yellow, Br brown, C white) are central to
a practical catalytic method for the direct
arylation of a variety of nitrogen heterocycles using aryl bromides. Broad functional-group tolerance was observed, and
the use of microwave radiation allowed for
short reaction times.
CH Activation
G. S. Ananchenko,* K. A. Udachin,
A. Dubes, J. A. Ripmeester, T. Perrier,
A. W. Coleman
1585 – 1588
Guest Exchange in Single Crystals of
van der Waals Nanocapsules
J. C. Lewis, J. Y. Wu, R. G. Bergman,*
J. A. Ellman*
1589 – 1591
Microwave-Promoted Rhodium-Catalyzed
Arylation of Heterocycles through CH
Bond Activation
P. Mukhopadhyay, Y. Iwashita,
M. Shirakawa, S.-i. Kawano, N. Fujita,
S. Shinkai*
1592 – 1595
Like a color palette: A naphthalenediimide-based organogel colorimetric
sensor allows recognition of the positional isomers of dihydroxynaphthalene in
the gel phase with the naked eye. Intercalation of the dihydroxynaphthalene into
the gel matrix produces a donor–acceptor
interaction, which gives the gel a distinct
color that depends on the strength of
noncovalent (H-bonding, p-stacking, van
der Waals) interactions.
Spontaneous Colorimetric Sensing of the
Positional Isomers of
Dihydroxynaphthalene in a 1D Organogel
A. G. Cheetham, M. G. Hutchings,
T. D. W. Claridge,
H. L. Anderson*
1596 – 1599
Selective digestion: a-Chymotrypsin was
used to synthesize a cyclodextrin azo dye
rotaxane and to digest it back to its
components. E!Z photoisomerization of
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
the rotaxane completely changes its affinity for the enzyme. The presence of the
cyclodextrin accelerates digestion of the E
isomer and prevents that of the Z isomer.
Enzymatic Synthesis and Photoswitchable
Enzymatic Cleavage of a Peptide-Linked
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Homogeneous Catalysis
F. Chevallier, B. Breit*
In pairs: Bidentate ligands are generated
by the self-assembly of monodentate
ligands through complementary hydrogen
bonding. A ruthenium complex bearing
such self-assembled heterodimeric
ligands is used as the catalyst in the
regioselective hydration of terminal
alkynes. FG = functional group, Piv =
1599 – 1602
Self-Assembled Bidentate Ligands for RuCatalyzed anti-Markovnikov Hydration of
Terminal Alkynes
Non-heme Iron Complex
A. Nielsen, F. B. Larsen, A. D. Bond,
C. J. McKenzie*
1602 – 1606
Regiospecific Ligand Oxygenation in Iron
Complexes of a Carboxylate-Containing
Ligand Mediated by a Proposed FeV–Oxo
Mimicked: Through biomimetic iron activation of peroxides (H2O2 or tBuOOH),
the shown N4O ligands in their iron(iii)
complexes can be oxygenated selectively
at either an aromatic carbon atom or an
aliphatic nitrogen atom.
The first FeII and NiII complexes with
bidentate pyrazolate ligands have been
prepared (see scheme; M = FeII, NiII ;
R = tBu, Me; Ar = 2,6-iPr2C6H3 ; X = Cl,
(m-Cl)2Li(thf)2). The coordination mode of
the pyrazolate ligand h2 or m-(h1:h1) and
the geometry of the resulting complex
depends on the steric bulk of the diketiminate ligand, the d-electron configuration of the metal center, the solvent, and
the relative stabilities of the s- and p-type
frontier orbitals.
Coordination Modes
J. Vela, S. Vaddadi, S. Kingsley,
C. J. Flaschenriem, R. J. Lachicotte,
T. R. Cundari,*
P. L. Holland*
1607 – 1611
Bidentate Coordination of Pyrazolate in
Low-Coordinate Iron(ii) and Nickel(ii)
Ambiphilic Ligands
S. Bontemps, H. Gornitzka, G. Bouhadir,
K. Miqueu, D. Bourissou*
1611 – 1614
Rhodium(i) Complexes of a PBP
Ambiphilic Ligand: Evidence for a
Metal!Borane Interaction
To and fro: Diphosphanylborane derivative 1 behaves as a tridentate, ambiphilic
ligand towards rhodium(i) fragments (see
picture). The presence of metal!borane
interactions in the resulting square-pyramidal complexes is highlighted by structural analyses and DFT calculations.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
Amino Acid Synthesis
H. Kiyohara, Y. Nakamura, R. Matsubara,
S. Kobayashi*
1615 – 1617
a-Amino acid derivatives are obtained in
high yields through the catalytic enantioselective allylation of iminoesters using
environmentally benign allylsilanes as
nucleophiles in the presence of a copper
complex prepared from Cu(OTf)2 and a
chiral diamine (see scheme; Tf = trifluoromethanesulfonyl, Nap = naphthyl). The
reaction is also extended to iminophosphonates.
Enantiomerically Enriched Allylglycine
Derivatives through the Catalytic
Asymmetric Allylation of Iminoesters and
Iminophosphonates with Allylsilanes
Heterogeneous Catalysis
P. Cheung, A. Bhan, G. J. Sunley,
E. Iglesia*
1617 – 1620
A simpler way: Acidic zeolites catalyze
dimethyl ether carbonylation to methyl
acetate at low temperatures with high
selectivity and catalyst stability. This
approach provides a halide-free heterogeneous catalytic route to acetic acid and
methyl acetate.
Cluster Compounds
Worth its weight in gold: A homoleptic
gold(i) glycosylated thiolate precursor for
the antiarthritic drug auranofin has been
structurally characterized. The undecagold(i) cluster forms an unusual chiral
[2]catenane (see picture; Au violet, S yellow) and displays interesting photophysical behavior in the solid state and in
S. S.-Y. Chui, R. Chen,
C.-M. Che*
1621 – 1624
A Chiral [2]Catenane Precursor of the
Antiarthritic Gold(i) Drug Auranofin
Photoswitching of the dielectric constant
has been observed for the first time in the
spin-crossover complex [Fe(L)(CN)2]·H2O
(L = 2,13-dimethyl-6,9-dioxa-3,12,18triazabicyclo[12.3.1]octadeca-1(18),2,12,
14,16-pentaene, see picture). The electrical detection of a photoinduced change in
spin state could allow the use of such
complexes in optical information-storage
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
Selective Carbonylation of Dimethyl Ether
to Methyl Acetate Catalyzed by Acidic
Spin-Crossover Complexes
S. Bonhommeau, T. Guillon,
L. M. Lawson Daku, P. Demont,
J. Sanchez Costa, J.-F. LRtard, G. MolnSr,
A. Bousseksou*
1625 – 1629
Photoswitching of the Dielectric Constant
of the Spin-Crossover Complex
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DNA Structures
in the guanine-rich strand of telomeric
DNA at a K+-ion concentration that is
unable to induce G-quadruplex formation
alone. The picture shows the folding and
unfolding of the telomeric DNA, revealed
by fluorescence resonance energy transfer
(FRET), the efficiency of which is inversely
dependent on the distance between the
donor (D) and acceptor (A).
Z.-y. Kan, Y. Yao, P. Wang, X.-h. Li,
Y.-h. Hao, Z. Tan*
1629 – 1632
Molecular Crowding Induces Telomere
G-Quadruplex Formation under SaltDeficient Conditions and Enhances its
Competition with Duplex Formation
Impact of crowding: Molecular crowding
with poly(ethylene glycol) (PEG) induces
the formation of a G-quadruplex structure
A break and a flip: Quantum mechanical/
molecular mechanical calculations are
used to investigate the structures of the
active sites in silicalite doped with
heteroatoms from Groups 4 and 14.
These calculations reveal that tripodal
(see picture; Si yellow, O red, H white,
heteroatom blue) or bipodal sites, formed
through hydrolysis and inversion, are
J. To,* A. A. Sokol, S. A. French,
C. R. A. Catlow, P. Sherwood,
H. J. J. van Dam
1633 – 1638
Formation of Heteroatom Active Sites in
Zeolites by Hydrolysis and Inversion
Tellurium Ligands
A. J. Gaunt, B. L. Scott,
M. P. Neu*
Are the actinides going soft? The first
molecular complexes containing an actinide–tellurium bond, [U{N(TePiPr2)2}3]
(see picture) and the isostructural complex [La{N(TePiPr2)2}3] have been crystallographically characterized. The UIIITe
bond is shorter than the LaIIITe bond by
0.06 X, which suggests a greater degree of
covalency in the bonding of actinides with
soft donors.
1638 – 1641
A Molecular Actinide–Tellurium Bond and
Comparison of Bonding in
[MIII{N(TePiPr2)2}3] (M = U, La)
Low-Valent Silicon Compounds
K. Abersfelder, D. GWclW,
D. Scheschkewitz*
1643 – 1645
An Unsaturated a,w-Dianionic
A trisilenediide: The reduction of dichlorotrisilene 1 with active magnesium leads
to a,w-dianionic trisilene 2, which is
characterized by NMR spectroscopy and
X-ray diffraction. The potential of 2 as a
precursor in the synthesis of heterocycles
incorporating a Si=Si double bond is
demonstrated by the formation of
stannatrisilacyclobutene 3.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
Phasing in: Miniemulsions are homogenous mixtures in which the organic phase
is dispersed in the form of nanometerscale droplets, which can act as efficient
“nanoreactors” for enantioselective
enzymatic transformations. Very high
substrate concentrations are possible,
and both a- and b-amino acids were
prepared with high conversions and up to
> 99 % ee.
It takes two to template: A cyclic hexaurea
with four xanthene and two diphenyl ether
units is predominantly formed by reaction
of two diisocyanate molecules with two
diamine molecules in the presence of
chloride (see picture; green Cl, blue N, red
O). The formation of a 1:2 complex with
chloride was confirmed by X-ray analysis,
solution NMR spectroscopy, and ESI-MS.
The complexation constants were determined by microcalorimetry and UV spectrometry.
Host–Guest Systems
H. GrYger,* O. May, H. HWsken,
S. Georgeon, K. Drauz,
K. Landfester*
1645 – 1648
Enantioselective Enzymatic Reactions in
Miniemulsions as Efficient
D. Meshcheryakov, V. BYhmer,*
M. Bolte, V. Hubscher-Bruder,
F. Arnaud-Neu, H. Herschbach,
A. Van Dorsselaer, I. Thondorf,
W. MYgelin
1648 – 1652
Two Chloride Ions as a Template in the
Formation of a Cyclic Hexaurea
Sister Journals
1656 – 1657
For more information on
ChemMedChem see
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Construction of Quaternary Stereocenters
by Efficient and Practical Conjugate
Additions to a,b-Unsaturated Ketones
with a Chiral Organic Catalyst
F. Wu, H. Li, R. Hong, L. Deng*
Footnotes [e] and [g] for Table 3 should read as follows:
[e] The reaction was performed by treatment of 2 B (0.3 mmol) with 5 a (0.75 mmol,
2.5 equiv) and QD-1 b in CH2Cl2 (0.6 mL).
[g] The reaction was performed by treatment of 2 B (0.3 mmol) with 5 b (0.75 mmol,
2.5 equiv) and QD-1 b in CH2Cl2 (0.6 mL).
Angew. Chem. Int. Ed. 2006, 45
DOI 10.1002/anie.200502658
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1488 – 1498
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