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Graphical Abstract Angew. Chem. Int. Ed. 422006

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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:
N. Borho, Y. Xu*
Lock-and-Key Principle on a Microscopic Scale: The Case of the
Propylene Oxide·Ethanol Complex
A. K. Sahoo, S. Mori, H. Shinokubo,* A. Osuka*
Facile Peripheral Functionalization of Porphyrins through
Pd-Catalyzed [3+2] Annulation with Alkynes
M. Kanno, H. Kono, Y. Fujimura*
Control of p-Electron Rotation in Chiral Aromatic Molecules by
Nonhelical Laser Pulses
M. Abe,* E. Kubo, K. Nozaki, T. Matsuo, T. Hayashi
An Extremely Long-Lived Singlet 4,4-Dimethoxy-3,5-diphenylpyrazolidine-3,5-diyl: A Notable Nitrogen Atom Effect on Intraand Intermolecular Reactivity
E. E. Moushi, T. C. Stamatatos, W. Wernsdorfer, V. Nastopoulos,
G. Christou,* A. J. Tasiopoulos*
A New Family of 3D Coordination Polymers Composed of Mn19
Magnetic Units
W.-Y. Wong,* C.-L. Ho, Z.-Q. Gao, B.-X. Mi, C.-H. Chen,
K.-W. Cheah, Z. Lin
Multifunctional Iridium Complexes Based on Carbazole Modules
as Highly Efficient Electrophosphors
Nobel Prizes 2006: Life, the Universe, and Everything
Controlled Synthesis of Nanoparticles in
Microheterogeneous Systems
Vincenzo Turco Liveri
reviewed by G. B. Sukhorukov
Asymmetric Synthesis
M. Braun,* T. Meier
6952 – 6955
Tsuji–Trost Allylic Alkylation with Ketone
The traditional restriction of the palladium-catalyzed allylation to stabilized
carbanions has been overcome. Recent
studies reveal that preformed “hard”
enolates can serve as nucleophiles, and
routes to novel stereoselective variants of
the Tsuji–Trost method have thus been
High Oxidation States
P. J. Chirik*
6956 – 6959
An FeVI Nitride: There Is Plenty of Room at
the Top!
Movin’ on up: Recent developments in
the coordination chemistry of high-oxidation-state iron nitrido compounds are
highlighted. Special attention is devoted
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
to a newly synthesized FeVI compound
(see scheme), only the second known
example of a hexavalent iron complex.
Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
Green Chemistry
The industrial synthesis of hydrogen peroxide by the anthraquinone process
requires multiple unit operations and
bears several disadvantages, such as the
generation of by-products and significant
energy requirements. Thus, the direct
synthesis of hydrogen peroxide from H2
and O2 (for example, with the aid of a Pd
catalyst, see scheme) is a chemically and
technologically significant alternative.
J. M. Campos-Martin, G. Blanco-Brieva,
J. L. G. Fierro*
6962 – 6984
Hydrogen Peroxide Synthesis: An Outlook
beyond the Anthraquinone Process
Binding or catalysis? Both can be distinguished with a molecularly imprinted
polymer (MIP) by the different patterns of
heat generation. The catalytically active
sites, like in the corresponding enzyme,
generate a steady-state temperature
increase. Thus, enzyme-like catalysis and
antibody-analogue binding are analyzed
simultaneously in a bifunctional MIP for
the first time (see scheme).
Molecular Recognition
K. Lettau, A. Warsinke, M. Katterle,
B. Danielsson,
F. W. Scheller*
6984 – 6990
A Bifunctional Molecularly Imprinted
Polymer (MIP): Analysis of Binding and
Catalysis by a Thermistor
Anthrapyran Natural Products
L. F. Tietze,* K. M. Gericke,
R. R. Singidi
6990 – 6993
The antiherpetic anthrapyran antibiotic
(14S,16R)-AH-1763 IIa (see right-hand
structure) and its (14R,16R) diastereomer
have been prepared in enantioselective
total syntheses. The relative and absolute
stereochemistry of the natural product
was established as (14R,16S), and a
general high-yielding, selective approach
to anthrapyran antibiotics was developed.
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Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
Enantioselective Total Synthesis and
Structure Determination of the
Antiherpetic Anthrapyran Antibiotic
AH-1763 IIa
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individuals who are personal members of a
national chemical society prices are available
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included. All prices are subject to local VAT/
sales tax.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Tailored Nanorods
A. Ghicov, S. Aldabergenova, H. Tsuchyia,
P. Schmuki*
6993 – 6996
TiO2–Nb2O5 Nanotubes with
Electrochemically Tunable Morphologies
Silver Alkoxides and Silyl Oxides
A. Reisinger, D. Himmel,
I. Krossing*
6997 – 7000
AgOC(CF3)3 and AgOSiiPr3—Synthesis
and Characterization of a Donor-Free
Silver(I) Alkoxide and Silyl Oxide
O. FlKgel, J. D. C. CodLe, D. Seebach,
P. H. Seeberger*
7000 – 7003
Microreactor Synthesis of b-Peptides
Made to measure: TiO2–Nb2O5 nanotubes
are grown on a Ti–Nb alloy (Ti45Nb) by
anodization in a fluoride-containing electrolyte (see micrograph), and their lengths
and diameters can be controlled by
adjusting the potential. The low rate of
chemical dissolution of Nb2O5 in the
electrolyte allows the formation of long
nanotubes with regular morphology.
Over 30 years after the first successful
syntheses of CuI alkoxides and silyl oxides,
the first homologous AgI compounds
were synthesized and characterized (see
scheme). AgOC(CF3)3 was furthermore
found to be a promising precursor for
chemical vapor deposition processes and
the deposition of AgF.
Taming the insoluble: The reaction parameters of a b-peptide synthesis were
optimized using only small amounts of
reagents in a silicon microreactor (see
picture). The use of unusually high temperatures (up to 120 8C) reduces the
reaction times. The insertion of a fluorous
benzyl protecting group enhances the
efficiency of the synthesis.
Enantioselective Reactions
A. Kirschner,
U. T. Bornscheuer*
7004 – 7006
Kinetic Resolution of 4-Hydroxy-2-ketones
Catalyzed by a Baeyer–Villiger
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Two with one stroke: The kinetic resolution of racemic 4-hydroxy-2-ketones catalyzed by Baeyer–Villiger monooxygenase
(BVMO) afforded not only the unreacted
enantiomer in good optical purity but also
allows access to optically active 1,2-diols
(see scheme). Thus, this enzymatic
approach provides a range of products in
a single reaction accessible otherwise only
from reactions with ketoreductases and
Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
The smell of money and chemical
weapons: The perplexing metallic odor
from touching iron tools or coins (see
picture) is a type of human body odor
linked to the decomposition of skin peroxides. Fe2+ ion containing rust, drinking
water, and blood all cause a similar
metallic odor. Another “garlic” metallic
odor, that of phosphorus-alloyed iron
under acid attack, is caused by organophosphines, including C–P compounds
which are monitored under the Chemical
Weapons Convention.
D. Glindemann,* A. Dietrich, H.-J. Staerk,
P. Kuschk
7006 – 7009
The Two Odors of Iron when Touched or
Pickled: (Skin) Carbonyl Compounds and
Secondary structures of biopolymers have
a significant influence on their molecular
interactions with surfaces. With the aid of
machine learning through support vector
regression, the retention of oligonucleotides was modeled in ion-pair reversedphase chromatography with high prediction accuracy (see diagram).
NMR dipolar couplings are a sensitive
spectroscopic probe of the structure and
dynamics of biomolecules. It is demonstrated that molecular alignment of
intrinsically disordered proteins depends
critically on electrostatic interactions, is
scaled with the ionic strength of the
solution, and can be predicted by using a
simplified electrostatic model.
NMR Methods
O. Kohlbacher, S. Quinten, M. Sturm,
B. M. Mayr, C. G. Huber*
7009 – 7012
Structure–Activity Relationships in
Chromatography: Retention Prediction of
Oligonucleotides with Support Vector
L. Skora, M.-K. Cho, H.-Y. Kim, S. Becker,
C. O. Fernandez, M. Blackledge,
M. Zweckstetter*
7012 – 7015
Charge-Induced Molecular Alignment of
Intrinsically Disordered Proteins
At the flick of a switch: Two side chains of
a collagen peptide containing (2S,4S)mercaptoproline at two defined positions
are linked with a diiodo azobenzene
derivative. With the trans isomer of the
azobenzene clamp (orange), the peptide
folds into the collagen triple helix (green,
blue, gray), which unfolds upon irradiation at 330 nm. The light-controlled folding/unfolding processes are fully reversible, making this system well-suited for
ultrafast spectroscopic analysis.
Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
U. Kusebauch, S. A. Cadamuro,
H.-J. Musiol, M. O. Lenz, J. Wachtveitl,
L. Moroder,* C. Renner
7015 – 7018
Photocontrolled Folding and Unfolding of
a Collagen Triple Helix
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Supramolecular Chemistry
S. J. Dalgarno, D. B. Bassil, S. A. Tucker,*
J. L. Atwood*
7019 – 7022
Cocrystallization and Encapsulation of a
Fluorophore with Hexameric
Pyrogallol[4]arene Nanocapsules:
Structural and Fluorescence Studies
Metal Phosphate Clusters
R. Murugavel,*
S. Kuppuswamy
7022 – 7026
Octameric and Decameric
Throwing light on encapsulation: The
fluorescent probe molecule 4-[3-(9anthryl)propyl]-N,N-dimethylaniline
(C gray, N blue) crystallizes either exo or
endo to the cavity of pyrogallol[4]arene
hexamers (O red) and displays markedly
different fluorescence emission behavior
as a result. In the exo array, the guest alters
the packing of the hexamer by forming
channels through the extended structure
in the solid state (see picture).
Big Al: The title compounds are not only
among the largest molecular aluminophosphates synthesized thus far, but are
also rare polyhedral cages that contain
AlO4, AlO5, and AlO6 coordination
geometries (see structure; red O, blue Al,
pink P). The cores of these aluminophosphates represent new structural building
units (SBUs) in zeolite chemistry.
Supramolecular Chemistry
U. RKsch, S. Yao, R. Wortmann,*
F. WQrthner*
7026 – 7030
Fluorescent H-Aggregates of Merocyanine
Microporous Materials
T. J. Taylor, V. I. Bakhmutov,
F. P. GabbaR*
7030 – 7033
Hydrocarbon Uptake in the Alkylated
Micropores of a Columnar
Supramolecular Solid
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Unexpected lighting up: A slight rotational twist and rigidification of merocyanine dyes in a face-to-face p-p-stacked
dimer aggregate resulted in an unexpected increase in the fluorescence intensity
and lifetime (see graph). This result
contrasts the common perception that the
fluorescence of H-aggregates is strongly
quenched, but can be rationalized within
the concept of exciton theory.
Neither Doric, Ionic, nor Corinthian!
(HgC6F4)3 interacts with 1,3,5-(Me3SiC
C)3C6H3 to form columns with peripheral
trimethylsilyl groups. These columns selfaggregate into a hexagonal solid containing pores lined by nonpolar methyl groups
(see picture; Hg orange, Si purple, C gray,
F green, H white), which can adsorb
alkanes reversibly.
Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
RNA Structures
Packing a punch: The 2’-hydroxy group
has a strong effect on the structural and
dynamic properties of RNA and DNA, and
governs the hydration of the RNA minor
groove. The conformation of this group
was previously investigated using NOEs
and 2J(C2’,OH2) and 3J(C1’/C3’/H2’,OH2)
couplings at low temperature in water. In
the present study, ab initio calculations
were used to derive appropriate Karpluslike equations for the couplings (see
J. Fohrer, U. Reinscheid, M. Hennig,
T. Carlomagno*
7033 – 7036
Calculation of the Dependence of Homoand Heteronuclear 3J and 2J Scalar
Couplings for the Determination of the
2’-Hydroxy Conformation in RNA
Persistent Radical Cations
One-electron reduction of a diphosphafulvenium dication gives the first stable
diphosphafulvenium monoradical cation
(see scheme). An X-ray crystal structure
analysis, EPR measurements, and DFT
calculations clearly show that reduction
takes place at the exocyclic double bond
and that the excess of electron density is
stabilized by the two electron-withdrawing
phosphonium groups (see SOMO;
P orange, C dark gray, H light gray).
F. Biaso, T. Cantat, N. MLzailles, L. Ricard,
P. Le Floch,* M. Geoffroy* 7036 – 7039
Formation and Structure of a Stable
Monoradical Cation by Reduction of a
Diphosphafulvenium Salt
Lithium-Ion Batteries
Two into one does go: A high-yield
preparation of carbon nanotube (CNT)encapsulated Sn–Sb nanorods that exhibit
excellent lithium storage properties is
described. The perceived growth process
involves a) antimony tin oxide nanoparticles, b) growth of carbon nanotubes
induced by molten Sn–Sb alloy, and
c) capillary encapsulation of molten
Sn–Sb into carbon-nanotube interior (see
Y. Wang, J. Y. Lee*
One-Step, Confined Growth of Bimetallic
Tin–Antimony Nanorods in Carbon
Nanotubes Grown In Situ for Reversible
Li+ Ion Storage
A host of possibilities: Cucurbit[8]uril acts
as a host to mediate in a highly effective
way the formation of charge-transfer
complexes between dendrimers containing accessible p-donor and p-acceptor
units (see scheme). Redox switching of
the self-assembly affords control over the
size of the predominant dendrimer
Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
7039 – 7042
Supramolecular Chemistry
W. Wang, A. E. Kaifer*
7042 – 7046
Electrochemical Switching and Size
Selection in Cucurbit[8]uril-Mediated
Dendrimer Self-Assembly
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
A. U. Nilekar, J. Greeley,
M. Mavrikakis*
7046 – 7049
A Simple Rule of Thumb for Diffusion on
Transition-Metal Surfaces
On the surface: Diffusion on transitionmetal surfaces plays a key role in the
transport of atomic and molecular species
on catalytic surfaces. Density functional
calculations show that there is a simple
linear relation that allows the prediction of
the diffusion barrier from the binding
energy of the diffusing species on the
respective metal surface.
Catalyst Reactivation
C. Temple, A. Jabri, P. Crewdson,
S. Gambarotta,* I. Korobkov,
R. Duchateau*
7050 – 7053
The Question of the Cr Oxidation State in
the {Cr(SNS)} Catalyst for Selective
Ethylene Trimerization: An Unanticipated
Re-Oxidation Pathway
An unprecedented oxidation of chromium(II) by trimethylaluminum which,
despite the reducing environment, forms
a cationic organochromium(III) complex
Gas Separation
H. Guo, G. Zhu,* H. Li, X. Zou, X. Yin,
W. Yang, S. Qiu,* R. Xu
7053 – 7056
Hierarchical Growth of Large-Scale
Ordered Zeolite Silicalite-1 Membranes
with High Permeability and Selectivity for
Recycling CO2
Dinuclear Complexes
G. Feng, D. Natale, R. Prabaharan,
J. C. Mareque-Rivas,*
N. H. Williams*
7056 – 7059
Efficient Phosphodiester Binding and
Cleavage by a ZnII Complex Combining
Hydrogen-Bonding Interactions and
Double Lewis Acid Activation
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
(see picture; SNS = RSCH2CH2N(H)CH2CH2SR, Cy = cyclohexyl,
X = [Me6Al2Cl]), provides a possible
catalyst re-activation pathway.
Another fine mesh you’ve got me into: A
stainless-steel-net-imbedded silicalite-1
membrane (MFI film) is synthesized by a
hydrothermal method. A hierarchical
growth mechanism of the membrane
formation is deduced. The MFI film has
high thermal and mechanical stability,
large-scale order, and exhibits high permeation flux and excellent permeation
selectivity for CO2 (see scheme).
A combined attack: Hydrogen-bonding
interactions with double Lewis acid activation generate a dinuclear ZnII complex
that is exceptionally effective for binding
monoanionic phosphate diesters in water
and for catalyzing phosphodiester transesterifications. The complex catalyzes the
hydrolytic cleavage of RNA-like activated,
artificial substrates and nonactivated,
natural substrates with similar efficiencies.
Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
Super skinny: TaS2 nanowires with a high
aspect ratio (50 000:1; see micrograph)
are synthesized from the elements in a
one-step reaction. The single-crystalline
2H-TaS2 nanowires are superconducting,
with a transition temperature (Tc = 3.4 K)
that is enhanced compared to that of the
bulk material (Tc = 0.8 K).
Wrapped up but still active: A platinum
nanoparticle that is 2.2 nm in diameter
and not coated by any stabilizing agent
can be encapsulated in a hollow carbon
shell 30–40 nm in diameter with a microto nanoporous wall structure (see picture). This encapsulated nanoparticle acts
as an efficient and recyclable heterogeneous catalyst for various liquid-phase
hydrogenation reactions.
C. W. Dunnill, H. K. Edwards, P. D. Brown,
D. H. Gregory*
7060 – 7063
Single-Step Synthesis and SurfaceAssisted Growth of Superconducting
TaS2 Nanowires
Encapsulated Catalysts
S. Ikeda,* S. Ishino, T. Harada,
N. Okamoto, T. Sakata, H. Mori,
S. Kuwabata, T. Torimoto,
M. Matsumura
7063 – 7066
Ligand-Free Platinum Nanoparticles
Encapsulated in a Hollow Porous Carbon
Shell as a Highly Active Heterogeneous
Hydrogenation Catalyst
M. G. Unthank, N. Hussain,
V. K. Aggarwal*
7066 – 7069
Lift your ylides: An asymmetric, epoxyannulation reaction mediated by a vinyl
sulfonium salt converts aminoaldehydes
and -ketones into fused heterocyclic
epoxides. The methodology was extended
to an aziridine-annulation reaction, which
was used to complete the shortest known
formal synthesis of balanol (see scheme,
Ts = toluene-p-sulfonyl, Tf = trifluoromethanesulfonyl).
The Use of Vinyl Sulfonium Salts in the
Stereocontrolled Asymmetric Synthesis of
Epoxide- and Aziridine-Fused
Heterocycles: Application to the Synthesis
of ( )-Balanol
Multicomponent Reactions
E. Thomas, S. Dixon,
R. J. Whitby*
Sequential insertion of 1-lithio-1,1-dihaloalkanes and lithium acetylides into
zirconacyclopentenes and -pentanes
affords complex bicyclo[3.3.0]octenes and
Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
bicyclo[3.3.0]octanes through a novel
rearrangement of a zirconium–alkynyl to a
zirconate—alkenylidene species (see
scheme; Cp = cyclopentadienyl).
7070 – 7072
A Rearrangement to a Zirconium–
Alkenylidene in the Insertion of
Dihalocarbenoids and Acetylides into
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Natural Products
Complete construction: The total synthesis of IKD-8344, a novel 28-membered
ring macrodiolide antibiotic (see structure), was accomplished by employing
Williamson ether synthesis, b-alkoxymethacrylate radical cyclization, and Yamaguchi lactonization reactions. This synthesis is another example of the application of b-alkoxymethacrylate radical cyclization reactions for the stereoselective
construction of complex oxacyclic natural
W. H. Kim, S. K. Hong, S. M. Lim, M.-A. Ju,
S. K. Jung, Y. W. Kim, J. H. Jung,
M. S. Kwon, E. Lee*
7072 – 7075
Total Synthesis of IKD-8344
Surface Chemistry
X. Deng, T. A. Baker,
C. M. Friend*
Going for gold! The synthesis of aziridines
using heterogeneous gold catalysts has an
unanticipated potential. Chemisorbed
atomic oxygen is used to activate ammonia, producing NH bound to the gold
surface (see scheme). Addition of NH
across the double bond of styrene gave
2-phenylaziridine on a single-crystal
Au(111) surface.
7075 – 7078
A Pathway for NH Addition to Styrene
Promoted by Gold
Heterogeneous Catalysis
R. MartVn, M. RodrVguez Rivero,
S. L. Buchwald*
7079 – 7082
Domino Cu-Catalyzed C N Coupling/
Hydroamidation: A Highly Efficient
Synthesis of Nitrogen Heterocycles
Working in tandem: Highly functionalized
pyrroles and pyrazoles can be synthesized
from a domino Cu-catalyzed C N coupling/hydroamidation sequence. The
Oxidative C C Coupling
P. S. Baran,*
M. P. DeMartino
7083 – 7086
Intermolecular Oxidative Enolate
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
scope and the generality of the method is
noteworthy as a wide variety of substituents, either in the alkene or alkyne counterparts, are well tolerated.
No priming necessary: The intermolecular
oxidative heterocoupling of imides and
oxindoles to esters, ketones, and lactones
is shown for the first time to be synthetically viable. Strategic use of the initial
oxidation state of the reactants allows for
the excision of prefunctionalization steps
(halogenation, enol-silane formation) and
allows for the concise synthesis of
unsymmetrical lignans, such as ( )-bursehernin (1).
Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
K. C. Nicolaou,* A. Li,
D. J. Edmonds
7086 – 7090
Total Synthesis of Platensimycin
Beat the superbugs: The newly discovered
antibiotic platensimycin (1) promises to
combat current drug-resistant infections.
The natural product shows potent activity
against Gram-positive bacteria and contains a novel molecular architecture. The
total synthesis of this intriguing natural
product that opens the way to a variety of
otherwise inaccessible analogues has now
been achieved (calculated structure
shown on the right).
Supporting information on the www
(see article for access details).
A video clip is available as Supporting Information
on the www (see article for access details).
Sister Journals
7092 – 7093
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Angew. Chem. Int. Ed. 2006, 45, 6938 – 6947
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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