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Graphical Abstract Angew. Chem. Int. Ed. 332006

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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:
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
M. B. Harney, Y. Zhang, L. R. Sita*
Bimolecular Control over Polypropene Stereochemical
Microstructure in a Well-Defined Two-State System and a New
Fundamental Form: Stereogradient Polypropene
J. G. Cordaro, D. Stein, H. R'egger, H. Gr'tzmacher*
Making the True "CP" Ligand
H. Niu, M. Gao*
Synthesis of Diameter-Tunable CdTe Nanotubes Templated by
One-Dimensional Nanowires of Cadmium Thiolate Polymer
N. Shimokhina, A. Bronowska, S. Homans*
Contribution of Ligand Desolvation to Binding Thermodynamics
in a Ligand–Protein Interaction
Y. Li, B. S. Lokitz, C. L. McCormick*
Thermally Responsive Vesicles and Their Structural "Locking"
through Polyelectrolyte Complex Formation
B. Gutte
Robert Bruce Merrifield (1921–2006)
5412 – 5413
Voltage-Gated Ion Channels as Drug
David J. Triggle, Murali Gopalakrishnan,
David Rampe, Wei Zheng
reviewed by P. Reiß, U. Koert
Molecular Modeling Techniques in
Material Sciences
J.rg-R/diger Hill, Lalitha Subramanian,
Amitesh Maiti
reviewed by R. Q. Snurr
Molecular Devices
Y. Yu,* T. Ikeda*
5416 – 5418
Soft Actuators Based on Liquid-Crystalline
Molecules that twitch: Liquid-crystalline
elastomers (LCEs) show promise in applications as soft actuators, with advantages such as large deformations and
high-speed, two- (contraction) or threedimensional (bending) actions. Earlier
systems were macroscopic (mm/cm) in
size; however, a soft lithography technique called replica molding was recently
used to create LCE pillars on the micrometer scale.
Microscopic Machines
W. F. Paxton, S. Sundararajan,
T. E. Mallouk, A. Sen*
5420 – 5429
Chemical Locomotion
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Doing the locomotion! As an alternative
to using localized physical interactions
and chemical reactions to propel small
objects, catalysis can be used to translate
the free chemical energy of the surroundings into asymmetric gradients, which
result in directed mechanical motion.
These approaches and some aspects of
converting chemical energy into mechanical energy on the micrometer scale are
discussed in the Minireview.
Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
Organofluorine Compounds
Doesn’t grow on trees: Trifluoromethylsubstituted substances are “unnatural”
without exception. To prepare them, one
has to choose among principal synthetic
strategies: to replace other heteroatoms
by fluorine, to transfer the CF3 entity as a
whole from a small precursor to a preconstructed skeleton, or to start with a
CF3-bearing core compound and to add
the missing structural parts, in particular
functionality (see scheme).
5432 – 5446
M. Schlosser*
CF3-Bearing Aromatic and Heterocyclic
Building Blocks
Aggregation in coordinating solvents:
A giant oxido cluster [Bi38O45(hfac)24]
(hfac = hexafluoroacetylacetonate),
formed in solutions of bismuth oxido
diketonate [Bi9O7(hfac)13], has been
isolated and fully characterized. The
[Bi38O45]24+ core (see picture: orange Bi,
red O; central Bi6O9 unit is highlighted) is
capped by 24 hfac ligands, has a size
larger than 2 nm, and may serve as a
model for investigating the chemistry of
bismuth oxide nanoparticles.
Cluster Compounds
Going for gold: AuI-catalyzed cyclizations
of functionalized enynes lead to the ready
assembly of tricyclic carbon skeletons that
are present in a number of naturally
occurring compounds. An alkenyl gold
intermediate is formed in the cyclization
of the enynes and can be trapped in 5-exodig or 6-endo-dig Prins reactions to form
an additional CC bond. Z = C(CO2Me)2,
NTs; R = H, Me, iPr.
For the USA and Canada:
Edition (ISSN 1433-7851) is published weekly
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Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
E. V. Dikarev,* H. Zhang,
B. Li
5448 – 5451
From a Bismuth Oxido Diketonate to a
Giant Bismuth Oxido Cluster
E. JimBnez-NfflEez, C. K. Claverie,
C. Nieto-Oberhuber,
A. M. Echavarren*
5452 – 5455
Prins Cyclizations in Au-Catalyzed
Reactions of Enynes
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sales tax.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
In close contact: The first gold(I) complexes of simple arenes show a separation
between the Au center and the mean
aromatic plane of 2.20–2.24 U, which is
much shorter than the related silver(I)–
arene bonds.
Arene Complexes
E. Herrero-GQmez, C. Nieto-Oberhuber,
S. LQpez, J. Benet-Buchholz,
A. M. Echavarren*
5455 – 5459
Cationic h1/h2-Gold(I) Complexes of
Simple Arenes
An [FeII3O]4+ core in a candy wrapper:
3,5-Bis(pyridin-2-yl)pyrazolate (L) and
iron(II) ions undergo homochiral selfassembly into a bis(triple-helical) cluster
(see picture), in which a triangular
[FeII3O]4+ core (Fe orange and yellow,
O red) is surrounded by two [FeIIL3] units
(Fe purple, L gray).
Cluster Compounds
K. Yoneda, K. Adachi, K. Nishio,
M. Yamasaki, A. Fuyuhiro, M. Katada,
S. Kaizaki,* S. Kawata*
5459 – 5461
An [FeII3O]4+ Core Wrapped by Two
[FeIIL3] Units
Host–Guest Systems
M. Kondo, M. Murata, H. Nishihara,*
E. Nishibori, S. Aoyagi, M. Yoshida,
Y. Kinoshita, M. Sakata
5461 – 5464
Both porous and nonporous structures
are formed by crystals of donor–acceptor
(D–A) compound 1,4-bis(ferrocenylethynyl)anthraquinone. The guest-incorporating porous and guest-free nonporous
structures can interchange instantly and
The ins and outs of binding: Supramolecular control of carbohydrate–protein interactions has been achieved
through the design of b-cyclodextrin
(bCD) based conjugates whose conformation is dependent on a reversible selfinclusion process. The accessibility of
glycoligands to the lectin binding site is
then regulated by allosteric inclusion of
effector/antagonist-like molecules in the
bCD cavity (see scheme).
Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
reversibly by desorption and adsorption of
guest molecules, which cause alternation
of D–A and D–A–A arrangements in the
one-dimensional columnar structure (see
Guest-Induced Instant and Reversible
Crystal-to-Crystal Transformation of
Noncovalent Interactions
N. Smiljanic, V. Moreau, D. Yockot,
J. M. Benito, J. M. GarcRa FernSndez,*
F. DjedaTni-Pilard*
5465 – 5468
Supramolecular Control of
Oligosaccharide–Protein Interactions:
Switchable and Tunable Ligands for
Concanavalin A Based on b-Cyclodextrin
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Attaching Cells
C. Zhao, I. Witte,
G. Wittstock*
5469 – 5471
Switching On Cell Adhesion with
Stick it! A microelectrochemical method
was developed for in situ manipulation of
the cell-adhesive property of an oligo-
(ethylene glycol)-terminated self-assembled monolayer substrate (OEG SAM)
and subsequent cell adhesion and growth.
Sensing within the cell: Microspheres
(2 mm) covalently loaded with calcium
sensors can be delivered efficiently into
living cells to analyze the intracellular
changes in the concentration of Ca2+ ions
in real time. The figure shows the realtime ratiometric fluorescent analysis
(400/475 nm ratio) of the release of Ca2+
ions in cells loaded with the microspheres.
R. M. SSnchez-MartRn, M. Cuttle,
S. Mittoo, M. Bradley*
5472 – 5474
Microsphere-Based Real-Time Calcium
A real turn-on: Two nonplanar threecoordinate boron compounds were synthesized as fluorescent sensors for fluoride that utilize charge-transfer emission.
The fluorescence of one of the sensors
turns on (see picture) and the other turns
off in the presence of fluoride.
X. Y. Liu, D. R. Bai, S. Wang* 5475 – 5478
Charge-Transfer Emission in Nonplanar
Three-Coordinate Organoboron
Compounds for Fluorescent Sensing of
G. Gopalakrishnan, C. Danelon,
P. Izewska, M. Prummer, P.-Y. Bolinger,
I. Geissb/hler, D. Demurtas, J. Dubochet,
H. Vogel*
5478 – 5483
Multifunctional Lipid/Quantum Dot
Hybrid Nanocontainers for Controlled
Targeting of Live Cells
Hydrophobic quantum dots can be incorporated into the bilayer membrane of lipid
vesicles for selective delivery into either
plasma membranes or the cytoplasm of
living cells (see picture). The cell and lipid
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
membranes can integrate any kind of
hydrophobic nanoparticle whose size
matches the membrane thickness, thus
opening possibilities for their manipulation in nanobiotechnology applications.
Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
Hairy molecules! The numerous benzyloxy side chains sticking out of a helically
folded pyridine carboxamide oligomer
bring about considerable stabilization to
its double-helical conformation. The
structure of the duplex was studied both
in solution and in the solid state.
Helical Structures
D. Haldar, H. Jiang, J.-M. LBger,
I. Huc*
5483 – 5486
Interstrand Interactions between Side
Chains in a Double-Helical Foldamer
An attractive target: Multiple porphyrin
systems (see picture for example) are at
the center of many synthetic efforts, and
efficient strategies for preparing valuable
building blocks for these polycycles are
much sought after. Herein such a strategy
for the synthesis of [1,2,3]triazolo[4,5-b]porphyrin building blocks is presented.
P. S. S. Lacerda, A. M. G. Silva, A. C. TomB,
M. G. P. M. S. Neves, A. M. S. Silva,
J. A. S. Cavaleiro,*
A. L. Llamas-Saiz
5487 – 5491
[1,2,3]Triazolo[4,5-b]porphyrins: New
Building Blocks for Porphyrinic Materials
Ion balls: The composition of nano- and
microparticles made from infinite coordination polymers can be chemically transformed through ion-exchange reactions
without substantially changing the particle size and morphology. This approach is
a straightforward and useful way of creating one precursor set of particles whose
composition can be controllably transformed into that of a new set of compounds with different properties.
Nano- and Microstructures
M. Oh, C. A. Mirkin*
5492 – 5494
Ion Exchange as a Way of Controlling the
Chemical Compositions of Nano- and
Microparticles Made from Infinite
Coordination Polymers
M. Takeuchi,* C. Fujikoshi, Y. Kubo,
K. Kaneko, S. Shinkai*
5494 – 5499
Straight curls: Conjugated polymers are
aligned through the use of twining porphyrin oligomers (twimers), which act as
helical “hosts” that twine around and are
included within a single conjugated poly-
Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
mer. The resulting composites aggregate
into relatively large 2D structures in the
solid state and exhibit well-oriented periodic striping.
Conjugated Polymers Complexed with
Helical Porphyrin Oligomers Create
Micron-Sized Ordered Structures
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DNA Conductance
H. van Zalinge, D. J. Schiffrin, A. D. Bates,
E. B. Starikov, W. Wenzel,
R. J. Nichols*
5499 – 5502
Variable-Temperature Measurements of
the Single-Molecule Conductance of
Double-Stranded DNA
Computational Models
J. C. Ianni, V. Annamalai, P.-W. Phuan,
M. Panda, M. C. Kozlowski* 5502 – 5505
A Priori Theoretical Prediction of
Selectivity in Asymmetric Catalysis:
Design of Chiral Catalysts by Using
Quantum Molecular Interaction Fields
A sound result: Calculations have
demonstrated a strong influence of
acoustic modes on the conductance of
double-stranded DNA (transmission
spectrum of a duplex in its ideal B-DNA
conformation is shown in red, that with
deformations along DNA acoustic modes
in green). The observed temperature
independence of the conductivity at and
above room temperature arises from a
high overall population of such modes
above the Debye temperature.
Excellent forecast: The selectivities for a
set of chiral catalysts were predicted by
methods derived from quantum mechanical molecular interaction fields that were
applied to ground-state structures rather
than transition-state structures. The predictions for the asymmetric addition of
Et2Zn to PhCHO are in remarkable
agreement with the experimental results
(r 2pred: = 0.87).
Natural Products (1)
A. F/rstner,* M. D. B. Fenster, B. Fasching,
C. Godbout, K. Radkowski
5506 – 5510
Toward the Total Synthesis of
Spirastrellolide A. Part 1: Strategic
Considerations and Preparation of the
Southern Domain
Natural Products (2)
A. F/rstner,* M. D. B. Fenster, B. Fasching,
C. Godbout, K. Radkowski
5510 – 5515
Toward the Total Synthesis of
Spirastrellolide A. Part 2: Conquest of the
Northern Hemisphere
North and South: The unique biological
activity of the natural product spirastrellolide A renders it an attractive lead for
anticancer agents. The southern hemisphere (C1–C25) and the northern hemisphere (including the chlorinated [5,6,6]bis-spiroacetal entity and the lateral C42–
C47 chain) are prepared by concise and
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
efficient routes. Consequently, the entire
carbon framework of this potent phosphatase inhibitor, which contains 21 chiral
centers, is prepared in an optically active
form, and an important step toward
structure determination by total synthesis
is achieved.
Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
Asymmetric Catalysis
New couple: A novel combination of
phosphine and phosphoramidite groups
is applied to the preparation of pseudo-C2symmetric triphosphorous bidentate
phosphine–phosphoramidite ligands 1.
Unprecedented enantioselectivities
toward ortho-substituted aryl enamides
and a 1-naphthylenamide in Rh-catalyzed
hydrogenation reactions are obtained.
W. Zhang, X. Zhang*
5515 – 5518
Synthesis of Triphosphorous Bidentate
Phosphine–Phosphoramidite Ligands:
Application in the Highly Enantioselective
Hydrogenation of ortho-Substituted Aryl
Fluorescent Probes
A xanthone-based chemosensor bears two
2,2’-dipicolylamine–zinc(II) sites and displays changes in the excitation spectrum
at three wavelengths upon binding phosphates (see picture). These changes in the
signals arise from the coordination rearrangement of the xanthone fluorophore
around the zinc centers, which modulates
the photophysical property of the chemosensor, thus enabling ratiometric fluorescent analysis.
A. Ojida, H. Nonaka, Y. Miyahara,
S.-i. Tamaru, K. Sada,
I. Hamachi*
5518 – 5521
Bis(Dpa-ZnII) Appended Xanthone:
Excitation Ratiometric Chemosensor for
Phosphate Anions
Free-Radical Chemistry
J. M. Cuerva,* A. G. CampaEa, J. Justicia,
A. Rosales, J. L. Oller-LQpez, R. Robles,
D. J. CSrdenas,* E. BuEuel,
J. E. Oltra*
5522 – 5526
Hydrogen-atom transfer from water to
free radicals can be mediated by aqua
complexes of titanium(III) (see scheme).
Asymmetric epoxidation in combination
with [Cp2TiCl]/H2O-mediated reductive
epoxide opening can be viewed as an
alternative with complementary stereoselectivity to the hydroboration–epoxidation
method for the enantioselective synthesis
of anti-Markovnikov alcohols from
Water: The Ideal Hydrogen-Atom Source
in Free-Radical Chemistry Mediated by TiIII
and Other Single-Electron-Transfer
Y. Hayashi,* S. Aratake, T. Okano,
J. Takahashi, T. Sumiya,
M. Shoji
5527 – 5529
Why not combine the two? The asymmetric direct aldol reaction of two different aldehydes was catalyzed by a combined proline–surfactant organic catalyst
in the presence of water. A stable emul-
Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
sion was formed in the reaction mixture,
and the aldols were obtained with excellent diastereo- and enantioselectivities
(see scheme).
Combined Proline–Surfactant
Organocatalyst for the Highly Diastereoand Enantioselective Aqueous Direct
Cross-Aldol Reaction of Aldehydes
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Proton Transfer
C.-W. Lee, P.-R. Lee,
H. Kang*
5529 – 5533
Protons at Ice Surfaces
Starry, starry ice: A study of proton
transfer and H/D exchange in ice films
shows that the proton mainly resides at
their surface. It can move a short distance
by a hopping relay mechanism (see
picture) even when molecular motion is
virtually frozen. This unique mobility and
surface affinity suggest the possibility for
proton-catalyzed reactions on cold ice
surfaces, such as on interstellar dust
Y. Sun, H.-S. Chan, H. Zhao, Z. Lin,*
Z. Xie*
5533 – 5536
Ruthenium-Mediated Coupling/
Cycloaddition of the Cyclopentadienyl
Ligand in [{h5 :s-Me2C(C5H4)(C2B10H10)}Ru(NCCH3)2] with Alkynes
Facile formation of tricycles: Rutheniummediated coupling/cycloaddition of a
cyclopentadienyl ligand with aromatic
alkynes offers a facile route to tricyclic
compounds (see scheme). The sterically
Supramolecular Chemistry
demanding carborane moiety plays a
crucial role in regioselective dimerization
of alkynes (to give head-to-tail coupling
products) and prevents alkyne trimerization.
Playing with blocks: Zinc phosphate
cubes with molecular structures that
resemble the double-four-ring (D4R)
secondary building unit of zeolites are
prepared. When the appropriate ligands
are chosen, the cubes assemble into 1D,
2D (see picture), or 3D supramolecular
networks through hydrogen bonds that
involve their surface functional groups.
R. Murugavel,* S. Kuppuswamy,
R. Boomishankar, A. Steiner 5536 – 5540
Hierarchical Structures Built from a
Molecular Zinc Phosphate Core
I. Braun, F. Rudroff, M. D. Mihovilovic,
T. Bach*
5541 – 5543
Synthesis of Enantiomerically Pure
Bicyclo[4.2.0]octanes by Cu-Catalyzed
[2þ2] Photocycloaddition and
Enantiotopos-Differentiating Ring
Fooling Mother Nature: When the
bicyclo[4.2.0]octanes A are bridged as in
precursors B (Z = CO), the otherwise
impossible [2þ2] photocycloaddition
reaction of 1,7-dienes is possible with
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
substrates such as C. A subsequent
Baeyer–Villiger oxidation serves to
desymmetrize substrates B and establishes a general approach to enantiomerically pure products A.
Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
Unknown terrain: Mg(GaH4)2·4 OEt2 (see
molecular structure; blue Ga, green Mg,
red O, gray C, white H) can be regarded as
a parent compound for the essentially
unexplored group of alkaline-earth tetrahydridogallates. Reaction of Mg(GaH4)2·4 OEt2 with tert-butyl alcohol
leads to {Mg(OtBu)[GaH2(OtBu)2]}2.
Metal Hydrides
M. Veith,* M. Burkhart,
V. Huch
5544 – 5546
Magnesium Bis(tetrahydridogallate(III)):
Structure and Reaction with tert-Butyl
New variants of the iridium-catalyzed
allylic substitution allow N-protected and
non-protected chiral allylamines to be
prepared with high enantio- and regioselectivity. The allylamines are used as
nucleophiles in highly diastereoselective,
catalyst-controlled allylic aminations. The
products are transformed into N-nonprotected 2,5-disubstituted 3,4-dehydropyrrolidines by ring-closing metathesis
(RCM; see scheme).
Allylic Amination
Maturation process: Micro RNAs represent a recently (re-)discovered group of
regulators of gene expression. Ligands of
the inactive precursor RNAs (premiRNAs) inhibit the formation of the
respective miRNAs. Such ligands could
potentially be used as tools in biomedicine. A doubly labeled RNA beacon allows
simple screening of potential pre-miRNA
Micro RNAs
R. Weihofen, O. Tverskoy,
G. Helmchen*
5546 – 5549
Salt-Free Iridium-Catalyzed Asymmetric
Allylic Aminations with N,N-Diacylamines
and ortho-Nosylamide as Ammonia
B. P. Davies, C. Arenz*
5550 – 5552
A Homogenous Assay for Micro RNA
Sister Journals
Angew. Chem. Int. Ed. 2006, 45, 5400 – 5409
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5556 – 5557
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