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Graphical Abstract Angew. Chem. Int. Ed. 402003

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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, Early View.
A. Mller,* S. K. Das, S. Talismanov, S. Roy, E. Beckmann, H. B%gge,
M. Schmidtmann, A. Merca, A. Berkle, L. Allouche, Y. Zhou,
L. Zhang:
Trapping Cations in Specific Positions in Tuneable “Artificial Cell”
Channels: New Nanochemistry Perspectives
DOI: 10.1002/anie.200352358
Published online: October 8, 2003
S. Arndt, T. P. Spaniol, J. Okuda*:
Homogeneous Ethylene-Polymerization Catalysts Based on Alkyl
Cations of the Rare-Earth Metals: Are Dicationic Mono(alkyl)
Complexes the Active Species?
DOI: 10.1002/anie.200352532
Published online: October 8, 2003
R. Fasel,* M. Parschau, K.-H. Ernst*:
Chirality Transfer from Single Molecules into Self-Assembled
Monolayers
DOI: 10.1002/anie.200352232
Published online: October 6, 2003
L. E. Cheruzel, M. S. Pometun, M. R. Cecil, M. S. Mashuta,
R. J. Wittebort, R. M. Buchanan*:
Structures and Solid-State Dynamics of One-Dimensional Water
Chains Stabilized by Imidazole Channels
DOI: 10.1002/anie.200352157
Published online: October 6, 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
Spotlight on RSC Award Winners
4850
Books
Solvent-free Organic Synthesis
4851
Koichi Tanaka
reviewed by G. Kaupp
High Pressure Chemistry
4852
Rudi van Eldik, Frank-Gerrit Kl%rner
reviewed by L. M. Harwood
Alkaloids
4852
Manfred Hesse
reviewed by F. von Nussbaum
Hot stuff: The Suzuki reaction of arylboronic derivatives with aryl halides is the
most important method for generating
aryl–aryl coupling products. Now such
couplings have become easier and cleaner
in hot water without the need of a
transition-metal catalyst (see scheme).
Highlights
Aryl–Aryl Coupling Reactions
C.-J. Li*
4856 – 4858
Suzuki Reaction Takes a “Naked Hot
Bath”: Coupling in High-Temperature
Water without Transition Metals
4840
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 4840 – 4847
Angewandte
Chemie
Minireviews
Interfacial Host–Guest Complexes
G. Cooke*
4860 – 4870
Electrochemical and Photochemical
Control of Host–Guest Complexation at
Surfaces
Solid progress: The transfer of responsive
supramolecular systems from the solution to the solid state by immobilizing
their components onto surfaces is an
attractive method for developing systems
with molecular electronics and device
applications (see scheme). The ability to
coherently interface these systems with
the outside world may pave the way for
their implementation as novel components within the emerging advanced
materials and nanotechnology industries.
Reviews
Thermodynamic Organic Complexes
Statistically shown: Complexes of
enzymes and catalytic antibodies with
their substrates and cyclodextrins, synthetic hosts, and albumins with organic
molecules all have similar association
constants (Ka) of 101–106 m 1. Antibody–
antigen and enzyme–inhibitor complexes
achieve tighter binding (Ka = 104–1012 m 1)
and enzyme–transition-state binding is
much stronger (Ka = 1010–1020 m 1). The
origins of these differences, the role of
enthalpy/entropy compensation, and the
relationships between the size of the
buried solvent-accessible surface areas of
the guest and binding affinities are analyzed.
K. N. Houk,* A. G. Leach, S. P. Kim,
X. Zhang
4872 – 4897
Binding Affinities of Host–Guest, Protein–
Ligand, and Protein–Transition-State
Complexes
Communications
Selectively cleaved: Under appropriate
experimental conditions, electrospray
ionization mass spectrometry produces
fragment ions that directly indicate noncovalent protein–heme interaction sites in
native Cytochrome c (see picture). The
proposed mechanism involves asymmetric charge partitioning in gaseous protein
dimer ions, which causes electron transfer
and subsequent backbone-cleavage.
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Angew. Chem. Int. Ed. 2003, 42, 4840 – 4847
MS Shows Tertiary Structure
K. Breuker,*
F. W. McLafferty
4900 – 4904
Native Electron Capture Dissociation for
the Structural Characterization of
Noncovalent Interactions in Native
Cytochrome c
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4841
Contents
Water Clusters
T. KLddermann, F. Schulte, M. Huelsekopf,
R. Ludwig*
4904 – 4908
Formation of Water Clusters in a
Hydrophobic Solvent
Titanium Dioxide Photocatalysts
S. Sakthivel, H. Kisch*
4908 – 4911
Daylight Photocatalysis by CarbonModified Titanium Dioxide
Lanthanum Copper Chalcogenides
S. Strobel, T. Schleid*
4911 – 4913
La2CuS4 : A Lanthanum Copper Sulfide
with Discrete Anion Triples [S3Cu···S
S···CuS3]12 Based on La4[Cu2S6(S2)]
And not a drop to drink: Hydrogenbonded water clusters could be detected
in CCl4 by IR spectroscopy. The comparison between measured and calculated
Green titana: Carbon-doped titanium
dioxide, supported onto filter paper, photocatalyzes the gas-phase degradation of
the atmospheric pollutants benzene (a),
acetaldehyde (b) and carbon monoxide (c) in diffuse indoor visible light (see
picture).
A unique structure: In the crystalline state
the lanthanum copper sulfide La2CuS4
comprises discrete anion triples. These
are composed of almost planar triangular
[CuS3]5 units, which consist of Cu+ and
S2 ions linked through a S S -dumbbell
to form the [S3Cu···S S···CuS3]12 anion
(see picture).
Force-Induced Affinity Changes
M. K. Beyer*
Small action, large effect: The proton
affinity has been defined as a function of
an external mechanical force and its
applicability as a chemical concept is
explored (see scheme). It is shown that
forces in the sub-nN to nN range change
the proton affinity of small model molecules by values ranging from kT up to
several 10 kJ mol 1, which suggests that
these affinity changes are chemically significant.
4913 – 4915
Coupling of Mechanical and Chemical
Energy: Proton Affinity as a Function of
External Force
4842
frequencies along with the characteristic
temperature behavior of band intensities
suggests that cyclic clusters are formed
up to the tetramer (see picture).
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 4840 – 4847
Angewandte
Chemie
Synthesis of Modified Proteins
Z. Machova, R. von Eggelkraut-Gottanka,
N. Wehofsky, F. Bordusa,
A. G. Beck-Sickinger*
4916 – 4918
Enzymatic synthesis and expressed protein ligation were combined in a method
for protein synthesis in which protein
thioesters with specific leaving groups
could be used by protease V8 from
Staphylococcus aureus to catalyze the
formation of peptide bonds. This method
was applied to the synthesis of
fluorescence-labeled (Fl) analogues of
proneuropeptide Y (proNPY; see
scheme). CBD = chitin binding domain.
Expressed Enzymatic Ligation for the
Semisynthesis of Chemically Modified
Proteins
A Chain of Dendrimers
H.-F. Chow,* C.-F. Leung, W. Li,
K.-W. Wong, L. Xi
4919 – 4923
Molecular jewelry! Up to 880 dendrimer
beads can be joined together with Pt
complexes to make a long “necklace” of
dendrimers (see picture). The polymerization of dendrimers that contain reac-
tive functional subunits on the dendrimer
surface opens a new route to a novel class
of dendronized polymers of high molecular weights and in good yields.
A novel catalytic role for transition-metal
cations in the homogeneous conversion
of the nitrogen oxides NO2, NO, or N2O
and CO into N2 and CO2 is demonstrated
by thermodynamic and kinetic studies of
gas-phase reactions of 29 transition-metal
cations and some of their oxides (see
scheme). Fe+, Os+, and Ir+ ions are shown
to be most effective. The chemistry identified may have practical applications in
new designs of catalytic converters.
Closing the door to nucleophilic attack on
one face of the substrate by using a bulky
substituent (see schematic formula) was
the key to obtaining high enantiomeric
excesses in the reduction of methyl
ketones by catecholborane with promotion by zinc complexes of new chiral
iminooxazoline (IMOX) ligands. The
modular nature, simple design, and possibility to produce tailored IMOX ligands
could be advantages in designing the next
generation of these chiral ligands.
Angew. Chem. Int. Ed. 2003, 42, 4840 – 4847
www.angewandte.org
Synthesis and Characterization of
Dendritic Necklaces: A Class of
Outer-Sphere–Outer-Sphere Connected
Dendronized Organoplatinum Polymers
Catalyzed Reduction of N Oxides
V. Blagojevic, M. J. Y. Jarvis, E. Flaim,
G. K. Koyanagi, V. V. Lavrov,
D. K. Bohme*
4923 – 4927
Gas-Phase Reduction of Oxides of
Nitrogen with CO Catalyzed by Atomic
Transition-Metal Cations
Enantioselective Alcohol Synthesis
M. Locatelli, P. G. Cozzi*
4928 – 4930
Effective Modular Iminooxazoline (IMOX)
Ligands for Asymmetric Catalysis:
[Zn(IMOX)]-Promoted Enantioselective
Reduction of Ketones by Catecholborane
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4843
Contents
Membrane Transport
A. V. Koulov, T. N. Lambert, R. Shukla,
M. Jain, J. M. Boon, B. D. Smith,*
H. Li, D. N. Sheppard,* J.-B. Joos,
J. P. Clare, A. P. Davis*
4931 – 4933
Chloride Transport Across Vesicle and Cell
Membranes by Steroid-Based Receptors
Crossing the barriers: Membrane transport, a well-established phenomenon for
neutral cation receptors such as valinomycin, has been demonstrated for the
anion-binding “cholapods”. The cholapods promote chloride efflux from vesicles by an antiport mechanism and
mediate anion flow through live cells
grown as epithelia (see schematic representation).
DNA Hybridization Detection
D. Zhou, K. Sinniah, C. Abell,*
T. Rayment*
4934 – 4937
Label-Free Detection of DNA Hybridization at the Nanoscale: A Highly Sensitive
and Selective Approach Using AtomicForce Microscopy
Less than 10 21 mol of label-free probe
DNA with high sequence specificity can be
quantitatively detected on a surface by
using AFM to create nanofeatures of
single-stranded DNA and monitor the
topographic changes upon exposure to a
complimentary DNA (see scheme).
Stopping the rot! The selective oxidation
of benzene to phenol with hydrogen
peroxide is achieved by using a new
zeolite catalyst (TS-1B), obtained by the
modification of titanium silicalite with
NH4HF2 and H2O2 (see scheme). The new
catalyst, used in presence of a particular
cosolvent (sulfolane) protects the produced phenol from overoxidation and
dramatically enhances the selectivity of
the reaction.
Oxidation of Benzene to Phenol
L. Balducci, D. Bianchi,* R. Bortolo,
R. D’Aloisio, M. Ricci, R. Tassinari,
R. Ungarelli
4937 – 4940
Direct Oxidation of Benzene to Phenol
with Hydrogen Peroxide over a Modified
Titanium Silicalite
Phosphininium Compounds
A. Moores, L. Ricard,
P. Le Floch*
A tetravalent phosphorus atom in an
aromatic system! A 1-methylphosphininium tetrachlorogallate is synthesized
and fully characterized (see structure).
This compound has aromatic properties
like those of phosphinine, pyridine, and
pyridinium salts. These features were
asserted and quantified by DFT calculations. This phosphininium salt reacts
easily with an alkyne to yield a phosphabarellenium salt through a Diels–Alder
reaction.
4940 – 4944
A 1-Methyl-Phosphininium Compound:
Synthesis, X-Ray Crystal Structure, and
DFT Calculations
4844
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 4840 – 4847
Angewandte
Chemie
Electrochemistry on a Few Molecules
C. Amatore,* F. GrQn,
E. Maisonhaute
The behavior of a limited number of
molecules is expected to show a profound
stochastic character and therefore to significantly differ from the usual chemical
kinetic laws. This dichotomy is investigated theoretically within an electrochemical framework by considering the
specific example of the oxidation of a
PAMAM redox dendrimer caped by
64 ruthenium bis-terpyridine centers (see
picture). Thus the maximum number of
adsorbed molecules at which the observation of the intrinsic stochastic nature of
the phenomenon should remain observable can be evaluated, either by itself, or
when instrumental distortions are
involved.
4944 – 4947
Electrochemistry within a Limited
Number of Molecules: Delineating the
Fringe Between Stochastic and Statistical
Behavior
DNA Lesions
A stable analogue (cFapydGuo) of the
major oxidative DNA lesion FapydGuo
was prepared. The direct comparison of
the pairing properties of the oxidative
lesion b-8-oxodGuo and b-cFapydGuo
(see formulae) revealed significant differences in base pairing, indicative of unexpected mutagenic differences.
M. Ober, U. Linne, J. Gierlich,
T. Carell*
4947 – 4951
The Two Main DNA Lesions 8-Oxo-7,8dihydroguanine and 2,6-Diamino-5-formamido-4-hydroxypyrimidine Exhibit
Strongly Different Pairing Properties
Ruthenium Pterin Radical Complex
T. Kojima,* T. Sakamoto, Y. Matsuda,
K. Ohkubo, S. Fukuzumi
4951 – 4954
A Ruthenium Pterin Complex Showing
Proton-Coupled Electron Transfer:
Synthesis and Characterization
Coupled to coenzymes: Ruthenium(ii)
complexes having a pterin as a ligand,
which is a redox-active heteroaromatic
coenzyme, are synthesized and characterized to reveal that the complexes
showed reversible proton-dependent
Angew. Chem. Int. Ed. 2003, 42, 4840 – 4847
redox behavior (see scheme). The pterin
ligand undergoes proton-coupled electron
transfer to form a ruthenium(ii)-coordinated monohydropterin radical upon oneelectron reduction.
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4845
Contents
Asymmetric Michael Addition
N. Halland, T. Hansen,
K. A. Jørgensen*
4955 – 4957
Organocatalytic Asymmetric Michael
Reaction of Cyclic 1,3-Dicarbonyl Compounds and a,b-Unsaturated
Ketones—A Highly Atom-Economic
Catalytic One-Step Formation of Optically
Active Warfarin Anticoagulant
A broad range of Michael adducts 3 were
obtained by the organocatalytic asymmetric Michael addition of cyclic 1,3dicarbonyl compounds 1 to a,b-unsaturated ketones 2. The reaction allows a one-
step synthesis of the optically active anticoagulant warfarin and several analogues
3 on a kilogram scale in up to 99 % yield
with 88 % ee (> 99.9 % ee after a single
recrystallization).
Reduction through cleavage: The reduction of a tetravalent thorium–bisdiaryloxide complex 1 with [K(naphthalenide)]
leads to the cleavage of dinitrogen and
partial hydrogenation via the probable
formation of a zero-valent thorium–amide
synthon (2; see scheme).
Low-Valent Thorium Complexes
I. Korobkov, S. Gambarotta,*
G. P. A. Yap
4958 – 4961
Amide from Dinitrogen by In Situ
Cleavage and Partial Hydrogenation
Promoted by a Transient Zero-Valent
Thorium Synthon
Natural Product Synthesis
A. W. G. Burgett, Q. Li, Q. Wei,
P. G. Harran*
4961 – 4966
A Concise and Flexible Total Synthesis of
( )-Diazonamide A
Porphyrin–C60 Conjugates
D. Bonifazi, M. Scholl, F. Song,
L. Echegoyen,* G. Accorsi, N. Armaroli,*
F. Diederich*
4966 – 4970
Exceptional Redox and Photophysical
Properties of a Triply Fused Diporphyrin–
C60 Conjugate: Novel Scaffolds for
Multicharge Storage in Molecular Scale
Electronics
4846
The remarkable action of an IIII species on
a tripeptide containing acyclic tyrosine/
tryptophan is the key step in a total
synthesis of ( )-diazonamide A. The
completed preparation of this new antimitotic is concise, multiply convergent,
and amenable to diversification of intermediates.
Up to fifteen electrons are reversibly
accommodated in a triply fused porphyrin
dimer conjugated to two [60]fullerene
moieties. Its photophysical properties
differ completely from those of the many
known porphyrin–fullerene dyads: Photoexcitation of the C60 moieties results in
quantitative sensitization of the low-lying
(about 1 eV) and very short lived lowest
singlet level of the porphyrin sheet (see
scheme).
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 4840 – 4847
Angewandte
Chemie
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.
Service
Keywords
4972
Authors
4973
Angewandte’s
Sister Journals
Preview
4974 – 4975
4977
Corrigendum
*
In the communication “6-Amino-3-Pyridinols: Towards Diffusion-Controlled ChainBreaking Antioxidants” by D. A. Pratt, L.
Valgimigli, G. F. Pedulli, N. A. Porter and
co-workers (Angew. Chem. 2003, 115,
4506–4509; Angew. Chem. Int. Ed. 2003,
Angew. Chem. Int. Ed. 2003, 42, 4840 – 4847
42, 4370–4373), on page 4370 there is an
error in the sentence “Calculations predicted that incorporation of two nitrogen
atoms at the 3- and 5-positions of the
phenolic ring significantly raises the IP
and greatly improves the stability of the
www.angewandte.org
compound in air while only minimally
lowering the O H BDE.[4]” the word
“lowering” should be “increasing”. The
authors apologize for this error.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4847
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