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Graphical Abstract Angew. Chem. Int. Ed. 412005

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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:
C. Drago, L. Caggiano, R. F. W. Jackson*
Vanadium-Catalyzed Sulfur Oxidation/Kinetic-Resolution
Process for the Synthesis of Enantiomerically Pure Alkyl Aryl
G. C. Lloyd-Jones,* R. G. Margue, J. G. de Vries
Rate Enhancement by Ethylene in the Ru-Catalyzed Ring-Closing
Metathesis of Enynes: Evidence for an “Ene-then-Yne” Pathway
that Diverts through a Second Catalytic Cycle
Q. Qing, F. Chen, P. Li, W. Tang, Z. Wu, Z. Liu*
Finely Tuning the Metallic Nanogap Size with Electrodeposition
Utilizing High-Frequency Impedance in Feedback
S. Klaus, H. Neumann, A. Zapf, D. Str3bing, S. H3bner, J. Almena,*
T. Riermeier, P. Groß, M. Sarich, W.-R. Krahnert, K. Rossen,
M. Beller*
A General and Efficient Method for the Formylation of Aryl and
Heteroaryl Bromides
X. Rocquefelte,* S. E. Boulfelfel, M. B. Yahia, J. Bauer, J.-Y. Saillard,*
and J.-F. Halet*
The Structural Preferences of Boron and Carbon within MB2C2
(M = Mg,Sc,Ca,Y,Ln) Phases: The “Coloring Problem” Revisited
by DFT Calculations
N. Mart6n,* 7. Mart6n-Domenech, S. Filippone, M. Altable,
L. Echegoyen,* C. M. Cardona
Retro-Cycloaddition Reactions of Pyrrolidinofullerenes
Organometallic Chemistry: P. Braunstein
Surface Chemistry: Science Academy
Membership for J.-M. Basset
Organic Chemistry: P. Metrangolo
Life Saving Drugs
John Mann
reviewed by O. Prien
Fundamentals of Molecular Symmetry
Philip R. Bunker, Per Jensen
reviewed by H. Bettermann
Metallomesogenic Polymers
L. Oriol, J. L. Serrano*
A challenging strategy for the design of
metal-containing polymeric systems with
a controlled nanostructure is the introduction of polymerizable groups that are
both compatible with the mesomorphic
order and reactive in the presence of
metals. 1,3-Diene groups have recently
been reported to offer such compatibility
and reactivity, leading to efficient polymerization (see picture).
6618 – 6621
Metal-Containing Nanostructured
Materials through In Situ Polymerization
of Reactive Metallomesogens
Asymmetric Catalysis
K. Mu-iz*
6622 – 6627
Bifunctional Metal–Ligand Catalysis:
Hydrogenations and New Reactions
within the Metal–(Di)amine Scaffold
No metal–substrate interactions: A transition-metal complex of a primary amine
can serve as an efficient bifunctional
metal–ligand catalyst that functions
without direct interaction of the metal and
the substrate. The example shows the
transition-state structure of the enantioselective reduction of acetophenone at the
molecular surface of a ruthenium hydride
complex bearing a diamine with one free
NH2 group (O red, Ru green, N blue).
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
Ruthenium Catalysis
B. M. Trost,* M. U. Frederiksen,
M. T. Rudd
6630 – 6666
Ru complexes emerged from obscurity to
become accepted as ideal catalysts for
diverse CC bond-forming reactions
beyond the more-well-known redox and
metathesis processes. These reactions are
highly selective and atom-economic pro-
cesses for the synthesis of complex
molecules (see scheme). Mechanistic
principles provide the basis for the semirational design of new reactions, notably
for CC coupling.
Ruthenium-Catalyzed Reactions—A
Treasure Trove of Atom-Economic
24-Carat bacteria: A bacteria/nanoparticle
composite device is operated by applying
a bias of 10 V across a bacterial bridge,
which is coated with gold nanoparticles
and spans two gold electrodes, and
measuring the current (see image). A
change in humidity from 0 to 20 % causes
swelling of the bacteria membrane which
results in a 40-fold decrease of the current
although the interparticle distance
increases less than 0.2 nm.
V. Berry, R. F. Saraf*
6668 – 6673
Self-Assembly of Nanoparticles on Live
Bacterium: An Avenue to Fabricate
Electronic Devices
Framework Materials
C.-L. Chen, A. M. Goforth, M. D. Smith,
C.-Y. Su, H.-C. zur Loye*
6673 – 6677
Shrinkage factor: The ligand ppca (4(pyridin-4-yl)pyridine-2-carboxylic acid)
has enabled the synthesis of a new 3D
framework material, [{[Co2(ppca)2(H2O)(V4O12)0.5]·3.62 H2O}n], which exhibits socalled “dynamic structural changes”.
Temperature changes lead to the reversible removal of guest molecules and/or
ligands (e.g. H2O) bound to the framework with a concomitant reversible structure change (see scheme).
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Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
[Co2(ppca)2(H2O)(V4O12)0.5]: A Framework
Material Exhibiting Reversible Shrinkage
and Expansion through a Single-Crystalto-Single-Crystal Transformation Involving
a Change in the Cobalt Coordination
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Iron aggregates are arranged into a closepacked structure through coordination
bonds to give a material that displays a
structural and magnetic hierarchy. The
tripodal proligand nitrilotripropionic acid
(H3ntp = N(CH2CH2COOH)3) successfully traps {Fe13} aggregates, thus producing a lattice that displays three levels of
organization (see picture of its 3D packing
arrangement; Fe green; O red; N blue;
C black; H white).
Hierarchical Structures
Quick on the uptake: A 20-mer DNA
oligomer modified with 5-[(6-guanidiniohexylcarbamoyl)methyl]-2’-deoxyuridine
(Tg) shows efficient cellular uptake (blue
arrow) in HeLa cells without any other
reagents. The fluorescence microscopy
image reveals FAM-labeled DNA oligomer
(green) and stained nuclei (blue).
FAM = 6-carboxyfluorescein.
Nucleic Acids
Hierarchical Assembly of {Fe13} OxygenBridged Clusters into a Close-Packed
T. Ohmichi, M. Kuwahara, N. Sasaki,
M. Hasegawa, T. Nishikata, H. Sawai,
N. Sugimoto*
6682 – 6685
Nucleic Acid with Guanidinium
Modification Exhibits Efficient Cellular
Protein Interactions
Controlling blood loss: The synthesis of a
series of arylamide oligomers 1, which
interact with heparin is described. The
heparin–small molecule interaction inhibits the heparin’s ability to activate
antithrombin. These arylamide oligomers
are the first example of low-molecularweight antagonists that inhibit the anticoagulant function of heparin.
S. Choi, D. J. Clements, V. Pophristic,
I. Ivanov, S. Vemparala, J. S. Bennett,
M. L. Klein, J. D. Winkler,
W. F. DeGrado*
6685 – 6689
The Design and Evaluation of HeparinBinding Foldamers
Correlated bond rotations within biconcave molecules that comprise a semirigid
C3-symmetric core and pendant m-terphenyl groups (see figure) assist
mechanical coupling between the two
vertices such that structural changes on
one side of the molecule are effectively
transmitted to the other side. Self-assembly of one such compound affords a
nonporous solid from which entrapped
guests can completely escape in the
absence of channels that connect interstitial voids.
Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
M. Murugesu, R. ClQrac, W. Wernsdorfer,
C. E. Anson, A. K. Powell*
6678 – 6682
Host–Guest Systems
J. A. Riddle, J. C. Bollinger,
D. Lee*
6689 – 6693
Escape from a Nonporous Solid:
Mechanically Coupled Biconcave
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DNA Nanostructures
Y. He, Y. Tian, Y. Chen, Z. Deng,
A. E. Ribbe, C. Mao*
6694 – 6696
Sequence Symmetry as a Tool for
Designing DNA Nanostructures
Grand designs: DNA sequence symmetry
is explored as a tool for designing DNA
nanostructures. The resulting symmetric
DNA motifs can self-assemble into two-
Lipid Bilayers
S. Majd, M. Mayer*
6697 – 6700
Hydrogel Stamping of Arrays of
Supported Lipid Bilayers with Various
Lipid Compositions for the Screening of
Drug–Membrane and Protein–Membrane
dimensional arrays as wide as 1 mm (see
picture). The DNA arrays can be used as
templates to fabricate nanostructures of
other materials, such as gold.
Stamping on fat: Agarose gel stamps were
used to create 100 membrane arrays
(see picture) by using only picomolar
amounts of lipids. This constitutes a rapid
and straightforward method for the fabrication of functional membrane arrays with
a variety of lipid compositions which can
be used for screening assays, for example,
for drug–membrane interactions.
Asymmetric Catalysis
M. S. Taylor, N. Tokunaga,
E. N. Jacobsen*
6700 – 6704
Enantioselective Thiourea-Catalyzed AcylMannich Reactions of Isoquinolines
Inexpensive aromatic feedstocks are substrates for highly enantioselective acylative Mannich reactions catalyzed by a
thiourea chiral hydrogen-bond donor 1.
This methodology provides access to
useful 1-substituted dihydroisoquinolines
Gene Therapy
K. C. Wood, S. R. Little, R. Langer,*
P. T. Hammond*
6704 – 6708
A Family of Hierarchically Self-Assembling
Linear-Dendritic Hybrid Polymers for
Highly Efficient Targeted Gene Delivery
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
(see scheme; TrocCl = 2,2,2-trichloroethyl
chloroformate, TBS = tert-butyldimethylsilyl), which serve as precursors to enantioenriched 1-substituted tetrahydroisoquinolines.
Modular materials composed of concentric functional “shells” with independently
tuneable properties are prepared from the
self-assembly of DNA and linear-dendritic
hybrid polymers (see scheme;
PAMAM = poly(amidoamine), PEG =
poly(ethylene glycol)). These ligand-targeted systems demonstrate serum stability, low toxicity, and transfection efficiencies that exceed those of the most efficient
commercially available polymer poly(ethylenimine).
Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
What a radical target! Two key hydrogenatom adducts of 1-methylcytosine have
been prepared by the targeted chemical
generation of cytosine radicals. Femtosecond collisional transfer of electrons to
gas-phase tautomers of protonated 1methylcytosine using molecular electron
donors (dimethyl disulfide and trimethylamine) produces stable radical adducts
with the hydrogen atoms positioned at N3
and C5 of the cytosine ring, respectively.
With high quality and in high yield: The
synthesis presented here affords CdSe
and CdTe semiconductor nanocrystals
without the need of a precursor injection.
It allows the detailed control of the size
and shape of the nanocrystals, as can be
seen from the tetrahedral CdSe nanocrystals that have been prepared (TEM
image). The method is suitable for
industrial-scale preparations.
Antipodal relationship: A convergent synthetic pathway leading to 4-hydroxy-2pyridinones was involved in the synthesis
of apiosporamide (1) and YM-215343 (2).
Both have an antipodal relationship to the
natural metabolites, whose relative and
absolute configurations have been established. Activated b-alanine enolate
equivalents derived from b-lactams were
the key to the synthesis.
Between the sheets: The structure of the
titanosilicate Ti-YNU-1 reveals a much
larger spacing along the c axis between
the MWW sheets than its lamellar precursor and 3D Ti-MWW (see picture).
Formation of twelve-membered rings
would explain this cell expansion, which
results in increased steric accessibility
and may explain the higher catalytic
activity of Ti-YNU-1 relative to other
Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
C. Yao, M. L. Cuadrado-Peinado,
M. PolTšek, F. Tureček*
6708 – 6711
Specific Generation of 1-Methylcytosine
Radicals in the Gas Phase
Y. A. Yang, H. Wu, K. R. Williams,
Y. C. Cao*
6712 – 6715
Synthesis of CdSe and CdTe Nanocrystals
without Precursor Injection
Assignment of Configuration
D. R. Williams,* D. C. Kammler,
A. F. Donnell,
W. R. F. Goundry
6715 – 6718
Total Synthesis of (þ)-Apiosporamide:
Assignment of Relative and Absolute
Zeolite Structures
J. Ruan, P. Wu, B. Slater,
O. Terasaki*
6719 – 6723
Structure Elucidation of the Highly Active
Titanosilicate Catalyst Ti-YNU-1
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Anticancer Genes
B. S. Reddy, R. Banerjee*
6723 – 6727
17b-Estradiol-Associated StealthLiposomal Delivery of Anticancer Gene to
Breast Cancer Cells
Killing by stealth: The highly specific
mutual affinity of estrogen receptor and
17b-estradiol (ES) allows apoptotic genes
to be targeted at primary human breast
adenocarcinoma cells through the use of
Template Synthesis
stealth liposomes. Cells are transfected
with a cationic lipoplex containing a
targeting lipid (see picture; DPPE = 1,2dipalmitoyl-Sn-glycero-phosphatidylethanolamine, PEG = poly(ethylene glycol)).
Double agent: Controlled sulfonation of
polystyrene hollow spheres gives hydrophilic layers with sulfonic acid groups that
allow the formation of a wide variety of
functional composites. In this way,
double-shelled hollow spheres have been
prepared in one step by using such
sulfonated polystyrene hollow spheres as
templates (see TEM image of titania
M. Yang, J. Ma, C. Zhang, Z. Yang,*
Y. Lu*
6727 – 6730
General Synthetic Route toward
Functional Hollow Spheres with DoubleShelled Structures
J.-P. Biron, A. L. Parkes, R. Pascal,*
J. D. Sutherland*
6731 – 6734
Expeditious, Potentially Primordial,
Aminoacylation of Nucleotides
In the beginning: Mixed carboxylic phosphoric anhydrides 3, formed from 3’nucleotides 1 and amino acid N-carboxyanhydrides 2, undergo competing
rearrangement to 2’-aminoacyl esters 4
and cyclization to 2’,3’-cyclic phosphates
5. The intramolecular aminoacyl transfer
is faster than the cyclization despite the
ease with which 2’,3’-cyclic phosphates
are formed through any other form of
phosphate activation.
Domino-cyclization of two phosphinidene
molecules: Methylation of the nucleophilic phosphinidene 1 with MeOTf (OTf =
triflate) affords the unusual phosphonium
cage 2, which implies the formation of the
novel phosphenium ion 3 as a reactive
Phosphorus Cage Compounds
M. Driess,* N. Muresan, K. Merz,
M. PVch
6734 – 6737
Formation of a Bowl-Shaped, Pentacyclic
Phosphonium Cage by Methylation of a
Nucleophilic Phosphinidene
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
Coordination Chemistry of Silicon
M. Driess,* N. Muresan,
K. Merz
6738 – 6741
A Novel Type of Pentacoordinate Silicon
Complexes and Unusual Ligand Coupling
by Intramolecular Electron Transfer
Even the electropositive element silicon
initiates electron-transfer processes in
amido-bis(enolate) complexes: This is
shown by the reactions of halides RSiX3
with HN[CH2C(O)tBu]2 in the presence of
a base. While small substituents (R = H,
Cl, Br, Ph) furnish the dinuclear pentacoordinate complexes 1, the bulkier tBu3Si
group favors formation of the dinuclear
tetracoordinate complex 2.
P.-h. Szu, X. He, L. Zhao,
H.-w. Liu*
The proteins DesI and DesII are proposed
to catalyze a C4 deoxygenation reaction to
give the key intermediate 1 in the biosynthesis of d-desosamine. Biochemical
characterization of purified DesII showed
that it is a member of the S-adenosylmethionine (SAM) family of radical enzymes.
The involvement of a SAM radical in the
reaction with DesII identifies a new strategy for deoxygenation reactions of sugars.
Biosynthesis of TDP-d-Desosamine:
Identification of a Strategy for C4
Matrix-isolation IR, electronic-absorption,
and Au L3-edge EXAFS (extended X-ray
absorption fine structure) data have provided the first experimental evidence that
the ground-state structure of AuCl3 is not
D3h symmetric (trigonal-planar), but
rather has a Jahn–Teller-distorted Tshaped geometry (see picture).
Matrix Isolation
Combining kinetic, structural, and computational studies on complex dynamic
feedback systems may lead to the field of
“systems chemistry”. The approach is
exemplified by the analysis of a simple
organic self-replicating system that has
the potential to express both homochiral
autocatalysis and heterochiral cross-catalysis (see picture).
Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
6742 – 6746
I. J. Blackmore, A. J. Bridgeman, N. Harris,
M. A. Holdaway, J. F. Rooms,
E. L. Thompson,
N. A. Young*
6746 – 6750
Experimental Evidence for a Jahn–Teller
Distortion in AuCl3
M. Kindermann, I. Stahl, M. Reimold,
W. M. Pankau,
G. von Kiedrowski*
6750 – 6755
Systems Chemistry: Kinetic and
Computational Analysis of a Nearly
Exponential Organic Replicator
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Alkane Metathesis
E. Le Roux, M. Taoufik,* C. CopQret,
A. de Mallmann, J. Thivolle-Cazat,
J.-M. Basset,* B. M. Maunders,
G. J. Sunley
6755 – 6758
Development of Tungsten-Based
Heterogeneous Alkane Metathesis
Catalysts Through a Structure–Activity
More active and selective catalysts of
alkane metathesis (see scheme) that are
based on well-defined tungsten carbyne
and hydride complexes supported on
alumina have been developed through a
structure–activity relationship. The
improvement of activity on changing from
Ta in 2 to W in 1 and the product selectivity
show that olefin metathesis is probably
the key process in CC bond formation in
the alkane metathesis reaction.
A dramatic enhancement of the reactivity
of the C4- and C8-hydroxy groups of sialic
acid has been demonstrated by 1,5-lactam
bridging. Sialyl-a(2!4)sialoside and
sialyl-a(2!8)sialoside were made avail-
able in high yields through direct sialylation (see scheme). Furthermore, the
glycan parts of the new gangliosides
Hp-s6 and HLG-2 were synthesized for
the first time.
Showdown at the OK corrole: The direct
borylation of corroles under iridium catalysis through CH activation proceeds
with perfect regioselectivity and excellent
yields. 2-Borylated corroles allow an easy
access (two steps) to directly linked
corrole–porphyrin conjugates and other
functionalized corroles (see scheme).
H. Ando,* Y. Koike, S. Koizumi, H. Ishida,
M. Kiso*
6759 – 6763
1,5-Lactamized Sialyl Acceptors for
Various Disialoside Syntheses: Novel
Method for the Synthesis of Glycan
Portions of Hp-s6 and HLG-2
Corrole Derivatives
S. Hiroto, I. Hisaki, H. Shinokubo,*
A. Osuka*
6763 – 6766
Synthesis of Corrole Derivatives through
Regioselective Ir-Catalyzed Direct
Protein Relaxivity
Z. Zhang, M. T. Greenfield, M. Spiller,
T. J. McMurry, R. B. Lauffer,
P. Caravan*
6766 – 6769
Multilocus Binding Increases the
Relaxivity of Protein-Bound MRI Contrast
Spinning around: The sensitivity of MRI
contrast agents can be increased through
multilocus binding. This restricts the
internal motion and therefore increases
the relaxivity of a bound protein multimer
(see picture; A) relative to a single binding
group (B), whose flexibility and internal
motion limits the relaxivity gain. Proteintargeting groups (TG) can be used to
anchor the multimer.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
Influential neighbors: 1,2-Chirality transfer provides the basis for a novel asymmetric synthesis of cyclopropanes by
irradiation of enantiomerically pure alkyl
phenyl ketones bearing a leaving group X
in the a position. The photochemically
excited carbonyl group is able to distinguish between the diastereotopic positions g and g’ in terms of a desymmetrization. In some cases the configuration
is influenced by the temperature.
Addition of Bi prevents deactivation of
Pd–Sb catalysts in the acetoxylation of
toluene. The presence of Bi hinders the
formation of an inactive Pdd state and
the blockage of the active Pd sites by
carbon species from coke deposits (see
the photoelectron spectrum). The modified catalyst displays extremely high
selectivity for benzyl acetate ( 95 %) at
higher toluene conversions.
Heterogeneous Catalysis
Reduction on the spot: Planarly adsorbed
thiolated porphyrin molecules (purple)
incorporated in an insulating alkanethiol
monolayer (blue) function as nanoelectrodes for the local reduction of metals
(gray). This approach was applied for the
in situ synthesis of nanoparticles of a
predetermined size.
Nanoparticle Deposition
J. Radnik,* A. Benhmid, V. N. Kalevaru,
M.-M. Pohl, A. Martin, B. LXcke,
U. Dingerdissen
6771 – 6774
Deactivation of Pd Acetoxylation
Catalysts: Direct Observations by XPS
T. Hirsch, M. Zharnikov, A. Shaporenko,
J. Stahl, D. Weiss, O. S. Wolfbeis,
V. M. Mirsky*
6775 – 6778
Size-Controlled Electrochemical Synthesis
of Metal Nanoparticles on
Monomolecular Templates
Asymmetric Synthesis
P. Wessig,* O. MXhling
6778 – 6781
1,2-Chirality Transfer in the Synthesis of
The issues for October 2005 appeared online on the following dates
Issue 37: September 14 · Issue 38: September 20 · Issue 39: September 30 · Issue 40: October 7
Sister Journals
Angew. Chem. Int. Ed. 2005, 44, 6602 – 6611
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6784 – 6785
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