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Graphical Abstract Angew. Chem. Int. Ed. 322003

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Contents
The following articles are available online (in Wiley Interscience). You can find them at
www.angewandte.org, under Full Text, Forthcoming Articles.
M. J. Thrippleton, J. Keeler*:
Elimination of Zero-Quantum Interference in Two-Dimensional
NMR Spectra
DOI: 10.1002/anie.200351947
Published online: August 1, 2003
K. Inoue,* K. Kikuchi, M. Ohba, H. Ōkawa:
Structure and Magnetic Properties of a Chiral Two-Dimensional
Ferrimagnet with TC of 38 K
DOI: 10.1002/anie.200351888
Published online: August 1, 2003
M. D. Foster, O. Delgado Friedrichs, R. G. Bell,* F. A. Almeida Paz,
J. Klinowski*:
Structural Evaluation of Systematically Enumerated Hypothetical
Uninodal Zeolites
DOI: 10.1002/anie.200351556
Published online: August 1, 2003
K. Funabashi, M. Jachmann, M. Kanai, M. Shibasaki*:
Multicenter Strategy for the Development of Catalytic Enantioselective Nucleophilic Alkylation of Ketones: Me2Zn Addition to
a-Ketoesters
DOI: 10.1002/anie.200351650
Published online: August 1, 2003
Articles judged by the referees or the editor as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editorial office in final form. As long as there is no page number available these articles should be
cited in the following manner:
Author(s) Angew. Chem. Int. Ed., online publication date, DOI.
News
Organic Chemistry: Jacobsen delivers
Ruzicka Lecture
3714
Catalysis: Corma recognized
3714
Molecular Machines: Mller and Feringa
honored
3714
Books
Bioinformatics and Genome
Analysis
Hans-Werner Mewes, Bertram Weiss,
Henrik Seidel
reviewed by Dietlind L. Gerloff
3715
Industrial Dyes
3716
Klaus Hunger
reviewed by Gnther Seybold
Bacterial combat on dioxins: A bacterial
strain detected in a sediment sample from
a creek contaminated with dioxins in the
Bitterfeld region, Germany, dehalogenates
different polyhalogenated dioxins under
anaerobic conditions by reductive dehalogenation (see scheme). This reaction is
coupled to the generation of energy and to
growth (dehalorespiration).
Highlights
Bacterial Degradation of Dioxin
K.-H. van P-e*
3718 – 3720
Dehalogenation of Polyhalogenated
Dioxins
3706
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 3706 – 3713
Angewandte
Chemie
Minireviews
Carbon monoxide is an important signaling molecule in mammals. It is particularly active in the cardiovascular system
and has been shown to be important in
several areas of medicine, for example, in
suppressing organ graft rejection and in
Metal Carbonyl Pharmaceuticals
reducing the damaging effects of ischemia. The importance of CO provides an
opportunity for bioorganometallic
chemistry to establish a new class of
pharmaceuticals based on metal
carbonyls.
T. R. Johnson, B. E. Mann,* J. E. Clark,
R. Foresti, C. J. Green,
R. Motterlini*
3722 – 3729
Metal Carbonyls: A New Class of
Pharmaceuticals?
Reviews
Dyeing Zeolites: Dye-zeolite antenna systems transporting excitation energy over
large distances are discussed on the basis
of three stages of organization: the
supramolecular organization of dye molecules inside the zeolite channels, the
organization of stopcock molecules plugging the channel entrances, and the
coupling of stopcock-modified antenna
systems to an external device (see picture;
EnT = energy transfer).
Light-Harvesting Antenna Materials
G. Calzaferri,* S. Huber, H. Maas,
C. Minkowski
3732 – 3758
Host–Guest Antenna Materials
Communications
Hysteresis in Fe-CN-Ag/Au Networks
A net change: A fully reversible ligand
substitution involving coordination/
uncoordination of gaseous water and
pyrimidine induces the repetitive allosteric transformation of three interpenetrated nets into a single three-dimensional
net. The transformation does not affect
the crystallinity of the sample but alters
significantly the spin-crossover transition;
the compound shows magnetic and
chromatic bistability (see picture).
For the USA and Canada:
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USA by Publications Expediting Inc. 200 Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2003, 42, 3706 – 3713
V. Niel, A. L. Thompson, M. C. MuEoz,
A. Galet, A. E. Goeta,
J. A. Real*
3760 – 3763
Crystalline-State Reaction with Allosteric
Effect in Spin-Crossover, Interpenetrated
Networks with Magnetic and Optical
Bistability
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Europe E 248.00/Outside Europe US$ 348.00.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3707
Contents
Metallacryptate Magnets
Crypt analysis: The reaction of manganese(ii) chloride with sodium hydroxide,
di-(2-pyridyl)-ketonoxime, and sodium
azide yields a metallacryptate consisting
of 26 manganese centers, namely, four
MnII (see picture; gold spheres) and
22 MnIII ions (green, aqua, and blue
spheres). Results obtained from ac
SQUID magnetic studies indicate that this
molecule displays single-molecule
magnetic behavior.
C. Dendrinou-Samara, M. Alexiou,
C. M. Zaleski, J. W. Kampf, M. L. Kirk,*
D. P. Kessissoglou,*
V. L. Pecoraro*
3763 – 3766
Synthesis and Magnetic Properties of a
Metallacryptate that Behaves as a
Single-Molecule Magnet
Single-Molecule Covalent Chemistry
T. Luchian,* S.-H. Shin,
H. Bayley*
3766 – 3771
Single-Molecule Covalent Chemistry with
Spatially Separated Reactants
Structure-Based Drug Discovery
D. T. Puerta, J. R. Schames,
R. H. Henchman, J. A. McCammon,*
S. M. Cohen*
3772 – 3774
From Model Complexes to Metalloprotein
Inhibition: A Synergistic Approach to
Structure-Based Drug Discovery
Photochemical Asymmetric Synthesis
B. O. Patrick, J. R. Scheffer,*
C. Scott
3775 – 3777
Preorganization of Achiral Molecules for
Asymmetric Synthesis through Crystallization-Induced Immobilization in
Homochiral Conformations
3708
In a recent study, the reversible covalent
chemistry of a simple reaction was monitored at the single-molecule level by
observing the current flowing through a
protein pore, which acted as a nanoreactor. Now, a multistep reaction has
been observed by an improved approach,
in which two of the reactants are separated by the membrane that contains the
pore and diffuse into the reaction zone
(see picture).
A happy marriage: The combination of
synthetic model chemistry with computational conformational analysis has
revealed the binding of an inhibitor to a
medically important metalloenzyme.
[(TpPh,Me)Zn(mbt)] (TpPh,Me = hydrotris(3,5-phenylmethylpyrazolyl)borate,
mbt = 2-methoxybenzenethiol) was used
to template the conformation of a known
inhibitor in the active site of the metalloenzyme, as shown by the green ligand
inside the active site of the protein (the
ZnII ion is shown in purple).
Enantioselective photochemistry: By
forming salts with optically pure amines,
achiral carboxylic acids can be induced to
crystallize in chiral conformations that are
preorganized for enantioselective photochemical reactions. Irradiation of crystals
of the salt shown leads to selective
Norrish type II abstraction of the nearer
(green) g-hydrogen atom, affording a
diastereomerically pure cyclobutanol in
84–98 % enantiomeric excess depending
on the amine used.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 3706 – 3713
Angewandte
Chemie
Three dimensional aromaticity: Polyhedral
boranes with para-O, -NH, -S substituents
should exhibit cylindrical p bonding on
oxidation (see picture), with structural
and reactivity consequences similar to
benzoquinones.
Polyhedral Boranes
Solvothermal techniques allow the crystallization of high nuclearity products that
are otherwise inaccessible by conventional techniques, directly from the reaction mixture. By this method, the reaction
of the triangular species [Fe3O(OAc)6(H2O)3]Cl with benzotriazole (BtaH)
produces an [Fe14] cluster (depicted)
with a very large spin ground state.
Iron Cluster with High Spin
M. M. Balakrishnarajan,
R. Hoffmann*
3777 – 3781
Polyhedral Boranes with Exo Multiple
Bonds: Three-Dimensional Inorganic
Analogues of Quinones
D. M. Low, L. F. Jones, A. Bell,
E. K. Brechin,* T. Mallah, E. RiviPre,
S. J. Teat, E. J. L. McInnes* 3781 – 3784
Solvothermal Synthesis of a
Tetradecametallic FeIII Cluster
Self-Organized Unimolecular Polymers
E. F. Connor, L. K. Sundberg, H.-C. Kim,
J. J. Cornelissen, T. Magbitang, P. M. Rice,
V. Y. Lee, C. J. Hawker, W. Volksen,
J. L. Hedrick,* R. D. Miller* 3785 – 3788
Nanopores created by micellar star polymers in amorphous organic silsequioxane
thermosets produce morphologically
controlled porous materials for semicon-
ductor chip applications (see picture).
Pore size is independent of concentration
and processing conditions, but depends
solely on the size of the polymer molecule.
Templating of Silsesquioxane
Cross-Linking Using Unimolecular
Self-Organizing Polymers
Azasugar Synthesis
A temperature-dependent relay of chirality
is based on the inversion of the nitrogen
lone pair in cyclic azasugars. Elimination
from the conformation preferred at a
Angew. Chem. Int. Ed. 2003, 42, 3706 – 3713
given temperature leads to a cyclic imine,
and in a subsequent nucleophilic attack
the stereochemical information is relayed.
www.angewandte.org
M. A. T. Maughan, I. G. Davies,
T. D. W. Claridge, S. Courtney, P. Hay,
B. G. Davis*
3788 – 3792
Nitrogen Inversion as a Diastereomeric
Relay in Azasugar Synthesis: The First
Synthesis of Adenophorine
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3709
Contents
Asymmetric Hydrogenation
Z. Yinghuai,* K. Carpenter, C. C. Bun,
S. Bahnmueller, C. P. Ke,*
V. S. Srid, L. W. Kee,
M. F. Hawthorne*
3792 – 3795
(R)-Binap-Mediated Asymmetric
Hydrogenation with a Rhodacarborane
Catalyst in Ionic-Liquid Media
Stereoselective Alkylation
T. Ooi, T. Miki, M. Taniguchi, M. Shiraishi,
M. Takeuchi, K. Maruoka*
3796 – 3798
Highly Enantioselective Construction of
Quaternary Stereocenters on b-Keto
Esters by Phase-Transfer Catalytic
Asymmetric Alkylation and Michael
Reaction
Unsymmetrical aryl ketones undergo
asymmetric hydrogenation in ionic-liquid
media in the presence of (R)-binap and a
rhodacarborane catalyst derived from the
suicide precursor 1 (see scheme).
Ketones that are poor substrates for other
methods can be hydrogenated in quantitative yields with very high enantioselectivities (97.3–99.5 % ee). The novel ionic
liquid (N-n-butylpyridinium)+ (closoCB11H12) provides a superior medium for
these reactions.
The designer ammonium salt (S,S)-1
catalyzes highly enantioselective phasetransfer alkylation and Michael reaction of
b-keto esters. This approach provides a
reliable route for the asymmetric synthesis of polyfunctionalized compounds
having chiral quaternary carbon atoms.
High-Valent Rhenium Oxo Chemistry
X. Chen, X. Zhang, P. Chen* 3798 – 3801
Metallaoxetanes and Carbenes from
Diolates in High-Valent Rhenium Oxo
Chemistry: The Importance of the
Coordination Number
ReV diolate complexes cleave to form
either the ReVII trioxo complex or a
rhenium carbene, depending on the
coordination number of the original diolate complex (see picture). The carbene
complexes, detected by using collision
induced mass spectrometry, are the best
experimental indication to date for intermediate “metallaoxetanes”, which would
be the first-formed intermediate in [2þ2]
reactions of olefins with a d0 oxo complex.
This sharp dichotomy in reactivity can be
explained by a qualitative p-strain model.
A very stable biradical, 2, was prepared
from 1 (see picture). The deep-blue/violet
biradical was stable in the air for several
minutes. The sp2-hybridized carbon radi-
cal centers of 2 were confirmed by X-ray
crystallography and its reversible oxidation was characterized by cyclic voltammetry. Mes* = 2,4,6-tBu3C6H2.
Stable Biradicals
H. Sugiyama, S. Ito,
M. Yoshifuji*
3802 – 3804
Synthesis of a 1,3-Diphosphacyclobutane2,4-diyl from Mes*CP
3710
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 3706 – 3713
Angewandte
Chemie
Sophisticated architectures can be built
from oxo-centered carboxylate triangles
linked together by phosphonates. This
suggests that the phosphonate ligands
could function as a means for building
larger entities from carboxylate cages. The
incorporation of a peroxide unit into the
cage structures is also feasible, for example in the hexanuclear cage depicted.
Iron(iii) Phosphonate Cage Complex
E. I. Tolis, M. Helliwell,
S. Langley, J. Raftery,
R. E. P. Winpenny*
3804 – 3808
Synthesis and Characterization of Iron(iii)
Phosphonate Cage Complexes
Alkaloid Total Synthesis
N. Toyooka,* A. Fukutome, H. Shinoda,
H. Nemoto*
3808 – 3810
Forming the tetrasubstituted piperidine
ring with stereocontrol in a Michael-type
conjugate addition is a key step in the first
enantioselective synthesis of the antipode
1 of alkaloid 205 B. The absolute stereochemistry of the natural product could be
determined unambiguously by comparison of the optical rotations.
Total Synthesis of the Antipode of
Alkaloid 205 B
Aerobic Oxidation of Alcohols
D. R. Jensen, M. J. Schultz, J. A. Mueller,
M. S. Sigman*
3810 – 3813
A breath of fresh air: A variety of alcohols
are oxidized using 0.5–0.1 mol % of the
catalyst, and in some cases the oxidation
can simply be carried out open to the air
(see scheme). Mechanistic insight into
the mechanism is provided by a crystal
structure that shows remarkable hydrogen
bonds between the coordinated water and
acetate ligands and an unprecedented
large kinetic isotope effect.
Optimized Heterogeneous Catalysts
A new purpose: Microreactors are commonly used in molecular high-throughput
synthesis. Their use for the formation of
catalysts through the precipitation of
inorganic components is new. The product shows a high degree of nanostructuring (see electron microscopy image),
which is at least partly retained in the
subsequent production steps.
Angew. Chem. Int. Ed. 2003, 42, 3706 – 3713
A Well-Defined Complex for PalladiumCatalyzed Aerobic Oxidation of Alcohols:
Design, Synthesis, and Mechanistic
Considerations
M. Schur, B. Bems, A. Dassenoy,
I. Kassatkine, J. Urban, H. Wilmes,
O. Hinrichsen, M. Muhler,
R. Schlgl*
3815 – 3817
Continuous Coprecipitation of Catalysts in
a Micromixer: Nanostructured Cu/ZnO
Composite for the Synthesis of Methanol
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3711
Contents
Molecular Polymer Wires
Mesoporous materials get wired: Micelles
of the thienyl-substituted ammonium ion
1 in aqueous ammonia solution are
applied as matrices for the formation of
mesoporous silicate particles from tetraethylorthosilicate. After oxidation with
FeCl3 and treatment with HF, polymeric
wires with a bimolecular diameter of 3 nm
and average lengths of 100–200 nm (see
TEM picture) are isolated. The yield of
isolated material was consistently above
10% even in gram-scale reactions.
G. Li, S. Bhosale, T. Wang, Y. Zhang,
H. Zhu, J.-H. Fuhrhop*
3818 – 3821
Gram-Scale Synthesis of SubmicrometerLong Polythiophene Wires in Mesoporous
Silica Matrices
Libraries of Metal Complexes
Z. Grote, R. Scopelliti,
K. Severin*
3821 – 3825
Adaptive Behavior of Dynamic Combinatorial Libraries Generated by Assembly of
Different Building Blocks
Democratic behavior: A strong bias for
the amplification of assemblies, the composition of which reflects the overall
composition of the library, can be
observed in selection processes with
dynamic combinatorial libraries. As a
consequence, it is not necessarily the
assembly with the highest affinity to a
given target (for example, a substrate, see
scheme) that is amplified the most.
From disorder to order and back: Contrary
to all earlier studies on [Fe(2-pic)3]Cl2·
EtOH (pic = picolylamine), an ordered
phase (IP) with two crystallographically
different iron sites was found between
disordered high-spin (HS) and low-spin
(LS) phases. The picture shows the average FeN distances of all three phases.
Order and Disorder
D. Chernyshov, M. Hostettler,
K. W. Trnroos, H.-B. BTrgi* 3825 – 3830
Ordering Phenomena and Phase
Transitions in a Spin-Crossover
Compound—Uncovering the Nature
of the Intermediate Phase of
[Fe(2-pic)3]Cl2·EtOH
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
The publication of Communications labeled with this symbol has been accelerated because of their topical or highly competitive
nature.
3712
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 3706 – 3713
Angewandte
Chemie
Service
Keywords
3832
Authors
3833
Angewandte’s
Sister Journals
Angew. Chem. Int. Ed. 2003, 42, 3706 – 3713
www.angewandte.org
3834 – 3835
Vacancies
3721
Preview
3837
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3713
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