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Graphical Abstract Angew. Chem. Int. Ed. 472005

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Contents
The following Communications have been judged by at least two referees to be “very
important papers” and will be published online at www.angewandte.org soon:
C. Drago, L. Caggiano, R. F. W. Jackson*
Vanadium-Catalyzed Sulfur Oxidation/Kinetic Resolution in the
Synthesis of Enantiomerically Pure Alkyl Aryl Sulfoxides
X. Rocquefelte,* S. E. Boulfelfel, M. B. Yahia, J. Bauer, J.-Y.
Saillard,* 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
S. Klaus, H. Neumann, A. Zapf, D. Str0bing, S. H0bner, 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
N. Mart5n,* 6. Mart5n-Domenech, S. Filippone, M. Altable,
L. Echegoyen,* C. M. Cardona
Retrocycloaddition Reactions of Pyrrolidinofullerenes
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
Obituary
Leopold Horner (1911–2005):
Nestor of Preparative Organic Chemistry
H. Kunz
7664
C. O. Kappe, M. Larhed
7666
Meeting Reviews
All the Rave in Microwaves
Highlights
Natural Product Synthesis
C. Escolano*
7670 – 7673
Stephacidin B, The Avrainvillamide
Dimer: A Formidable Synthetic Challenge
Rising to the challenge: Stephacidin B is
an antitumor antibiotic isolated from the
fungi Aspergillus ochraceus (see picture).
Recently, two elegant approaches to the
enantioselective synthesis of this dimeric
N-hydroxyindole alkaloid were reported
that pave the way to a series of medicinally
attractive stephacidin analogues.
Minireviews
Organosulfur Reagents
S. R. Dubbaka, P. Vogel*
7674 – 7684
Organosulfur Compounds: Electrophilic
Reagents in Transition-Metal-Catalyzed
Carbon–Carbon Bond-Forming Reactions
7652
Inexpensive and easily prepared organosulfur compounds, such as sulfonyl chlorides, thiol esters, thioethers, sulfonium
ions, sulfoxides, sulfoximines, sulfones,
sulfonates and sulfonamides, are good
electrophilic partners in C C cross-coupling reactions and arylations catalyzed by
transition metals (see scheme).
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
Angewandte
Chemie
Reviews
Nanotechnology
A swell idea: Research on hydrogel nanoparticles confirms the huge application
potential of soft nanomaterials. Such
nanoparticles can be made to swell and
contract in response to changes in their
environment. They could find uses as
bioresponsive sensors, drug-delivery systems, implantable biomaterials, biotesting, and targetable chemotherapy agents.
The picture shows HeLa cells containing
core–shell nanoparticles as fluorescent
markers.
S. Nayak, L. A. Lyon*
7686 – 7708
Soft Nanotechnology with Soft
Nanoparticles
Communications
Joining the cubes: The linking of lithium
{Li4O4} cubanes by the bifunctional organometalloligand [(h4-quinone)Rh(cod)]
(cod = cyclooctadiene) results in an
unprecedented doubly bridged motif. The
dimeric assembly features cubane units
that are connected by a transition-metal
complex and that incorporate a quinone
oxygen atom at one of the corners.
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
S. U. Son, J. A. Reingold, S. B. Kim,
G. B. Carpenter,
D. A. Sweigart*
7710 – 7715
Lithium Alkoxide {Li4O4} Cubanes Bridged
by Rhodium–Quinonoid
Organometalloligands
Synthetic Methods
Enantioselective propargylic substitution
reactions of propargylic alcohols with
acetone catalyzed by a diruthenium complex gives the propargylic alkylated products in good yields with up to 82 % ee. A
p–p interaction of phenyl rings between
the ligand and allenylidene moieties is
considered to play a crucial role in
achieving such a high selectivity (see
scheme; Cp*=pentamethylcyclopentadiene).
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ANGEWANDTE CHEMIE International
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USA by Publications Expediting Inc. 200
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Cubanes
Y. Inada, Y. Nishibayashi,*
S. Uemura
7715 – 7717
Ruthenium-Catalyzed Asymmetric
Propargylic Substitution Reactions of
Propargylic Alcohols with Acetone
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7653
Angewandte
Chemie
Palladium Catalysis
S. Kamijo,* Y. Sasaki, C. Kanazawa,
T. SchMßeler, Y. Yamamoto* 7718 – 7721
Ringing the changes for organopalladium
catalysts. A new nucleophilic reactivity of
organopalladium species has been
revealed. The reaction between aryl isocyanates and terminal alkynes in the
An uncommon interaction characterizes
the NiI–NiI zwitterionic complex presented here. The m-Ph moiety of the tetraphenylborate ligand coordinates synfacially to the two Ni centers (see picture)
and provides two pairs of electrons
through an h2(C2,C3):h2(C5,C6) interaction that is strengthened as a result of the
electrostatic attractions between the
anion and the formally cationic Ni2 fragment.
When S is SO much better: Conjugate
vaccines that contain S-glycosides induce
carbohydrate-specific antibodies that
cross react with the corresponding Oglycosides and vice versa. Four distinct
systems have been examined, in each of
which the antigen-specific response to Sglycosides is either comparable or superior to the response to O-glycosides.
An analogue with P: Reaction of the
“dithallene” (TlArDipp2)2 (1; ArDipp2 = C6H32,6-(C6H2-2,6-iPr2)2) with P4 afforded
Tl2[P4(ArDipp2)2] (2), a thallium complexed
diaryltetraphosphabutadienediide. The
negative charge in the anion of 2 is
delocalized over the P4 array to afford an
average P P bond order of approximately
1.33.
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
presence of a palladium catalyst produces
oxindoles through the intramolecular
vinylpalladation of isocyanates (see
scheme; dppe = 1,2-bis(diphenylphosphanyl)ethane).
Oxindole Synthesis through
Intramolecular Nucleophilic Addition of
Vinylpalladiums to Aryl Isocyanates
Cationic Ni2 Fragment
Y. Chen, C. Sui-Seng,
D. Zargarian*
7721 – 7725
Tetraphenylborate as a Novel Bridging
Ligand in a Zwitterionic Nickel(i) Dimer
Immunochemistry
D. R. Bundle,* J. R. Rich, S. Jacques,
H. N. Yu, M. Nitz, C.-C. Ling 7725 – 7729
Thiooligosaccharide Conjugate Vaccines
Evoke Antibodies Specific for Native
Antigens
1,3-Butadiene Analogues
A. R. Fox, R. J. Wright, E. Rivard,
P. P. Power*
7729 – 7733
Tl2[Aryl2P4]: A Thallium Complexed
Diaryltetraphosphabutadienediide and its
Two-Electron Oxidation to a
Diaryltetraphosphabicyclobutane, Aryl2P4
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7655
Contents
Site-Ordered Solids
P. M. Mallinson, M. M. B. Allix,
J. B. Claridge, R. M. Ibberson,
D. M. Iddles, T. Price,
M. J. Rosseinsky*
7733 – 7736
Ba8CoNb6O24 : A d0 Dielectric Oxide Host
Containing Ordered d7 Cation Layers
1.88 nm Apart
High-Pressure Crystallography
N. Casati,* P. Macchi,
A. Sironi*
7736 – 7739
Staggered to Eclipsed Conformational
Rearrangement of [Co2(CO)6(PPh3)2] in
the Solid State: An X-ray Diffraction Study
at High Pressure and Low Temperature
Rearrangement Reactions
D. Armesto,* M. J. Ortiz,*
A. R. Agarrabeitia,
N. El-Boulifi
7739 – 7741
The Effects of Triplet Sensitizers’ Energies
on the Photoreactivity of b,g-Unsaturated
Methyl Ketones
Molecular Wheels
Z.-H. Ni, H.-Z. Kou,* L.-F. Zhang, C. Ge,
A.-L. Cui, R.-J. Wang, Y. Li,
O. Sato*
7742 – 7745
[MnIII(salen)]6[FeIII(bpmb)(CN)2]6·7 H2O:
A Cyanide-Bridged Nanosized Molecular
Wheel
7656
www.angewandte.org
Following orders: The cobalt and niobium
ions in Ba8CoNb6O24 are completely
ordered in the seven-layer repeat of hexagonal and cubic stacking. Such siteordered solids may find application as
microwave dielectric resonators, for
example, in mobile telecommunications.
In the structure shown, {CoO6} and
{NbO6} units are red and blue octahedra,
respectively, and barium cations are black
spheres.
Under pressure: characterization of the
high-pressure phase of crystalline
[Co2(CO)6(PPh3)2] has provided the first
structural evidence for the transformation
from a staggered to eclipsed arrangement
of the equatorial carbonyl ligands in a
dimeric transition-metal complex (see
picture). A comparison with the same
phenomenon observed at low temperature (though arrested in the very early
stages) is presented.
Triplet determines reactivity: b,g-Unsaturated ketones 1 do not undergo the oxa-dip-methane (ODPM) rearrangement in the
presence of acetophenone or 3-methoxyacetophenone as a triplet sensitizer. However, they afford the ODPM products 2
when using triplet sensitizers with triplet
energies slightly higher than those of the
alkene triplets. When the triplet energies
of the sensitizers are slightly lower than
those of the alkene groups in 1, ODPM
rearrangement occurs along with 1,3-acyl
migration to form enones 3 (see scheme).
Heterometallic wheel: A cyanide-bridged
heterometallic dodecanuclear complex
featuring a nanosized molecular wheel
has been synthesized based on magnetically anisotropic [Mn(salen)]+ and [Fe(bpmb)(CN)2] building blocks. Magnetic
studies reveal that the complex exhibits
overall ferromagnetic intramolecular coupling (see picture) and frequency-dependent ac magnetic susceptibility.
H2bpmb = 1,2-bis(pyridine-2-carboxamido)-4-methylbenzene.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
Angewandte
Chemie
Cores for thought: Structural and spectroscopic studies show that the
{Cu2(S2)2}2+ core of [Cu2(tmeda)2(m-S2)2](OTf)2 (tmeda = N,N,N’,N’-tetramethylethylenediamine; OTf = trifluoromethanesulfonate) is best described as a bis(mdisulfido(C1 ))dicopper(ii) complex
rather than a bis(m-disulfido(2 ))dicopper(iii) complex. This complex
represents a new motif in the copper–
sulfur chemistry of biologically relevant,
synthetic model systems.
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
J. T. York, E. C. Brown,
W. B. Tolman*
7745 – 7748
Characterization of a Complex
Comprising a {Cu2(S2)2}2+ Core:
Bis(m-S22 )dicopper(iii) or
Bis(m-S2C )dicopper(ii)?
An unconventional hydrate promoter,
tBuNH2 , forms a double hydrate upon
reacting with CH4 (see picture). This
double hydrate shows different storage
capacities for CH4 depending on the
concentration of tBuNH2. Based on this
phenomenon, a tuning concept for determining the optimum initial concentration
of tBuNH2 is proposed.
Gas Storage
Covering the bases: Nucleobases and
aromatic carboxylic acids possessing
complementary functional groups have
been used in the synthesis of molecular
adducts with exotic architectures. The
architectures obtained with cytosine as
the nucleobase lead to the production of
several different supramolecular structures (see picture).
Supramolecular Chemistry
Popping corks: The protonated urea ions
(C black, N/O green) that cork the pores
of a polyoxomolybdate capsule (Mo blue,
O red) can be reversibly removed allowing
the entry of Ca2+ ions (pink) into the
capsule. This process resembles the
functioning of gated calcium channels in
cell membranes.
Stepping up: Density functional calculations indicate that small molecules, such
as propylene oxide, chemisorb in an
enantiospecific manner on intrinsically
chiral, stepped Cu surfaces. As an example, the preferential adsorption configurations for the (S)- (right) and (R)amino(fluoro)methoxy species (left) on
Cu(874)S are shown.
Bioinorganic Chemistry
D.-Y. Kim, J.-w. Lee, Y.-T. Seo,
J. A. Ripmeester, H. Lee*
7749 – 7752
Structural Transition and Tuning of tertButylamine Hydrate
S. R. Perumalla, E. Suresh,
V. R. Pedireddi*
7752 – 7757
Nucleobases in Molecular Recognition:
Molecular Adducts of Adenine and
Cytosine with COOH Functional Groups
Supramolecular Chemistry
A. MMller,* L. Toma, H. BVgge, C. SchWffer,
A. Stammler
7757 – 7761
Porous Capsules Allow Pore Opening and
Closing That Results in Cation Uptake
Surface Chirality
B. Bhatia, D. S. Sholl*
7761 – 7764
Enantiospecific Chemisorption of Small
Molecules on Intrinsically Chiral Cu
Surfaces
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7657
Contents
Catalyst Design
G. Klein, N. Humbert, J. Gradinaru,
A. Ivanova, F. Gilardoni, U. E. Rusbandi,
T. R. Ward*
7764 – 7767
Tailoring the Active Site of Chemzymes by
Using a Chemogenetic-Optimization
Procedure: Towards Substrate-Specific
Artificial Hydrogenases Based on the
Biotin–Avidin Technology
Directed Assembly
G. Zhang, D. Wang,*
H. MVhwald
7767 – 7770
Decoration of Microspheres with Gold
Nanodots—Giving Colloidal Spheres
Valences
The combination of chemical- with
genetic-optimization strategies (i.e. chemogenetic) allows the production of artificial hydrogenases based on the biotin–
avidin technology. In the spirit of
enzymes, second-coordination-sphere
Giving directions: Microspheres are
decorated with a defined number of Au
nanodots by using O2-plasma-etched colloidal crystals as masks for the deposition
of Au vapor (see picture). The Au nanodots deposited on the spheres might be
considered as nanoscale analogues of sphybridized atomic orbitals, which may be
used to spatially direct the association of
spheres to generate hierarchical “supraparticles”.
Nanotechnology
Positive feedback: Relatively large gaps
can be reproducibly fabricated by utilizing
the change in impedance arising from the
high electric field between the electrodes
in a feedback-controlled electrodeposition
system. Furthermore, the gap size can be
finely tuned down to around 1 nm by
simply controlling subsequent deposition
time (see SEM images).
Q. Qing, F. Chen, P. Li, W. Tang, Z. Wu,
Z. Liu*
7771 – 7775
Finely Tuning Metallic Nanogap Size with
Electrodeposition by Utilizing HighFrequency Impedance in Feedback
Protein Structures
N. A. Lakomek, C. FarYs, S. Becker,
T. Carlomagno, J. Meiler,*
C. Griesinger*
7776 – 7778
Side-Chain Orientation and HydrogenBonding Imprint Supra-tc Motion on the
Protein Backbone of Ubiquitin
7658
www.angewandte.org
interactions between the host protein
(streptavidin) and the substrate (an
olefin) allow fine-tuning of the selectivity
to produce either R or S hydrogenation
products.
Order parameters derived from residual
dipolar couplings between NH groups
reveal motion of protein backbones on a
time scale slower than the correlation
time tC. Less-mobile amides (blue and
green) in ubiquitin, for example, are Hbonded and belong to residues with side
chains pointing towards the hydrophobic
core while more mobile ones (yellow,
orange, and red) have solvent-exposed
side chains and fewer H bonds.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
Angewandte
Chemie
Lighting up: The conformation of the
DNA-binding domain of the basic helixloop-helix protein MyoD can be controlled
through an azobenzene cross-linker in
response to light flashes. The DNA binding specificity of alkylated MyoD can be
modulated through the isomerization of
the cross-linker to the cis conformer, which
leads to significantly enhanced sequence
selectivity.
Close and yet fluorescent: Derivatives of
Pigment Yellow 101 can exhibit small
intermolecular distances in the solid-state
crystal structures. Nevertheless, these
compounds show strong solid-state fluorescence. X-ray structure determinations
and elaborate quantum-chemical calculations indicate that the unexpected fluorescence is a property of the individual
molecules which is retained in the crystal.
(Excited state energies are plotted along a
CNN bending mode.)
Ambidextrous ligands satisfy both Ag and
Fe. The three-dimensional polymeric ions
[Ag3Fe2(ECN)12]4 (E = S, Se) form networks in which {Fe(1,3-m-NCE)2Ag} units
are linked to form 80-membered
{Fe10Ag10}(ECNC)20 rings. The mixedvalent compound (Pr4N)4[Ag3Fe2(SeCN)12]
is the first crystallographically characterized homoleptic selenocyanato complex
of iron.
Two GaCl3 adducts of 4-bis(trimethylsilyl)amino-1,2,4,3,5-triazadiphosphole
were formed in simple high-yielding reactions. The adducts were fully characterized (see structure of the monoadduct)
and shown to be stable at ambient
temperature. The structure, bonding, and
NMR spectra of the triazadiphosphole
adducts are discussed on the basis of
MO, NBO, and DFT calculations.
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
DNA Binding
L. Guerrero, O. S. Smart, C. J. Weston,
D. C. Burns, G. A. Woolley,
R. K. Allemann*
7778 – 7782
Photochemical Regulation of DNABinding Specificity of MyoD
Solid-State Fluorescence
A. Dreuw,* J. PlVtner, L. Lorenz,
J. Wachtveitl, J. E. Djanhan, J. BrMning,
T. Metz, M. Bolte,
M. U. Schmidt*
7783 – 7786
Molecular Mechanism of the Solid-State
Fluorescence Behavior of the Organic
Pigment Yellow 101 and Its Derivatives
Mixed-Valent Compounds
S. Gerber, H. GrVger, J. Ensling, P. GMtlich,
H. Krautscheid*
7787 – 7790
(Pr4N)4[Ag3Fe2(ECN)12]—Anionic Network
Structures with Mutual Interpenetration
P,N Heterocycles
S. Herler, P. Mayer,
J. Schmedt auf der GMnne, A. Schulz,*
A. Villinger, J. J. Weigand
7790 – 7793
A Triazadiphosphole
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7659
Contents
Cyclizations
A. Zulys, M. Dochnahl, D. Hollmann,
K. LVhnwitz, J.-S. Herrmann,
P. W. Roesky,* S. Blechert* 7794 – 7798
Intramolecular Hydroamination of
Functionalized Alkenes and Alkynes with a
Homogenous Zinc Catalyst
Coordination Modes
W. W. Seidel,* M. Schaffrath,
T. Pape
7798 – 7800
Can Acetylenedithiolate Act as a
Tetradentate Bridging Ligand?
Simple and versatile: A new zinc complex
catalyzes the intramolecular hydroamination of nonactivated alkynes and alkenes
(see example in scheme; {(iPr)2ATI} = Nisopropyl-2-(isopropylamino)troponimin-
Tetradentate and ambidentate: Because
the four-atom acetylenedithiolate has
donor electron density on all sides of the
dianion, it can link and electronically
couple different metal ions. The bendback angles of the sulfur atoms in the h2C,C’-acetylenedithiolate complex
[Tp’W(CO)2(h2-C2S2)] are sufficiently
flexible to allow for a chelation of both
sulfur donors to the {(h5-C5H5)Ru(PPh3)}
fragment (see structure).
Isomerizations
M. Kreich, P. Claus*
ato). The catalyst is relatively robust,
exhibits excellent activities, and tolerates
various functional groups such as ethers,
thioethers, and amides.
7800 – 7804
Direct Conversion of Linoleic Acid over
Silver Catalysts in the Presence of H2 : An
Unusual Way towards Conjugated Linoleic
Acids
A silver lining: The isomerization of conjugated double bonds over silver catalysts
in the presence of hydrogen are unusual
and hitherto unknown. Silver catalysts
control the selectivity of the extremely
difficult isomerization of linoleic acid
towards the physiologically important 9cis,11-trans- and 10-trans,12-cis-unsaturated isomers, which are anticarcinogenic
and antiarteriosclerotic agents (see
scheme, CLA = conjugated linoleic acids).
Service
Keywords
7806
Authors
7807
Vacancies
Preview
7660
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
A71
7809
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
Angewandte
Chemie
Corrigendum
*
On page 6171 of this Communication, the sentence that begins on line 12 of the last
paragraph should read “Reductive ring opening was achieved with borane–trimethylamine complex in the presence of triflic acid to give …”. On page 6172 in footnote (d) to
Scheme 4, “TFA” should be changed to “triflic acid”.
Highly Diastereoselective Alkylation of
Aziridine-2-carboxylate Esters:
Enantioselective Synthesis of LFA-1
Antagonist BIRT-377
A. P. Patwardhan, V. R. Pulgam, Y. Zhang,
W. D. Wulff*
6169–6172
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200500923
Angew. Chem. Int. Ed. 2005, 44, 7652 – 7661
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7661
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