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Graphical Abstract Angew. Chem. Int. Ed. 362006

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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:
K. J. T. Noonan, D. P. Gates*
Ambient-Temperature Living Anionic Polymerization of
Phosphaalkenes: Homopolymers and Block Copolymers with
Controlled Chain Lengths
J. Piera, K. Nrhi, J.-E. Bckvall*
Palladium(II)-Catalyzed Aerobic Allylic Oxidative
Carbocyclization of Allene-Substituted Olefins: Immobilization of
an Oxygen-Activating Catalyst
T. J. Taylor, V. I. Bakhmutov, F. P. Gabba**
Hydrocarbon Uptake in the Alkylated Micropores of a Columnar
Supramolecular Solid
J.-P. Leclerc, K. Fagnou*
Palladium-Catalyzed Cross-Coupling Reactions of Diazine
N-Oxides with Aryl Chlorides, Bromides, and Iodides
J. W. Lee, J.-S. Lee, Y.-T. Chang*
Colorimetric Identification of Carbohydrates by a pH
Indicator/pH-Change-Inducer Ensemble
Z.-M. Cui, Q. Liu, W.-G. Song*, L.-J. Wan*
Insights into the Mechanism of Methanol-to-Olefin Conversion
from Zeolites with Systematically Selected Framework Structures
Web Sites
Lipids and Lipidomics
T. Kolter
R. Bruce King
reviewed by D. Scheschkewitz
Encyclopedia of Inorganic Chemistry
Molecular Electronics
M. Wagner*
5916 – 5918
A New Dimension in Multinuclear
Metallocene Complexes
Radial oligocyclopentadienyl metal complexes were synthesized for the first time
by a highly efficient Negishi coupling.
Such compounds open fascinating possibilities for applications on the threshold
between homogeneous and heterogeneous catalysis as well as in molecular
Lantibiotic Biosynthesis
G. Jung*
5919 – 5921
Enzyme-Catalyzed Sulfide Ring Formation
in Lantibiotics
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Building bridges: The crystal structure of
the zinc enzyme NisC was solved recently
by X-ray diffraction. This cyclase singlehandedly catalyzes the formation of several sulfide bridges in the dehydrated
precursor protein NisA of the lantibiotic
nisin. The Highlight discusses the impact
of these results on the field of lantibiotic
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
Taking chemical functionality to a new
level: Blending 2D and 3D nanoscopic
structures with supramolecular concepts
can be used to generate systems for
enhanced recognition and sensing, to
control assembly and disassembly processes, and give the possibility for biomimetic reactions within nanoscopic
Mesoporous Materials
A. B. Descalzo, R. Mart2nez-M34ez,*
F. Sancen5n, K. Hoffmann,
K. Rurack*
5924 – 5948
The Supramolecular Chemistry of
Inorganic–Organic Hybrid Materials
Break it up: Ordinarily, silica gel produces
no separation in a mixture of aromatic
molecules by HPLC; however, solidenhanced DOSY NMR spectroscopy succeeds in this task, although its separation
capabilities concern just the spectral
components. Chromatographic NMR
spectroscopy may thus prove a simple
complement to HPLC in favorable cases.
MAS = magic-angle spinning.
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
G. Pages,* C. Delaurent,
S. Caldarelli
5950 – 5953
Simplified Analysis of Mixtures of Small
Molecules by Chromatographic NMR
AlAl Multiple Bonds
An alkyne analogue with Al: The first
“dialuminyne” of formula Na2[Ar’AlAlAr’]
(see picture; Ar’ = C6H3-2,6-(C6H3-2,6iPr2)2) was synthesized and characterized
by X-ray crystallography. The structure
contains a planar trans-bent C–Al–Al–C
array with an AlAl bond length of
2.428(1) P and a bending angle of
131.71(7)8 at Al.
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NMR Spectroscopy
R. J. Wright, M. Brynda,
P. P. Power*
5953 – 5956
Synthesis and Structure of the
“Dialuminyne” Na2[Ar’AlAlAr’] and
Na2[(Ar’’Al)3]: AlAl Bonding in Al2Na2
and Al3Na2 Clusters
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2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Double up: Photochemical upconversion
by MLCT-sensitized triplet–triplet annihilation is demonstrated (MLCT = metal-toligand charge transfer). Selective visible
excitation of [Ru(dmb)3]2+ (dmb = 4,4’dimethyl-2,2’-bipyridine) in the presence
of anthracene efficiently produces the
[4þ4] cycloaddition product. This transformation traditionally requires ultraviolet
R. R. Islangulov,
F. N. Castellano*
5957 – 5959
Photochemical Upconversion:
Anthracene Dimerization Sensitized to
Visible Light by a RuII Chromophore
Y. H. Jung, K.-B. Lee, Y.-G. Kim,*
5960 – 5963
I. S. Choi*
Fueled up: The protonation of the imino
group of cytosines in double-stranded
DNA, which is required for the formation
of a triplex, can be used to guide the
assembly/disassembly of DNA-conjuga-
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
ted gold nanoparticles. The reversible
switching of the nanoparticles is demonstrated by repeated cycling of pH between
5.0 and 6.5 with the proton as a fuel (see
Proton-Fueled, Reversible Assembly of
Gold Nanoparticles by Controlled Triplex
A change in orientation of adsorbed
oxygen molecules from parallel (top) at
the bare Pt electrode to a mixture of
parallel and end-on modes at a Pt surface
modified by the electrodeposition of
manganese oxide nanoparticles (nanoMnOx/Pt) causes a higher population of
oxygen molecules at the MnOx/Pt surface
(bottom). The modified electrode is thus a
superior electrocatalyst for the reduction
of oxygen (Pt yellow, O white, MnOx
Surface Chemistry
Gold lights the way: A bidentate cyclophane N-heterocyclic carbene ligand has
been used to synthesize a new dinuclear
AuI complex of the formula [Au2L2]2+. The
short Au···Au distance imposed by the
rigid cyclophane ligand leads to a redshifted luminescence profile that enables
the complex to be used as a luminescent
probe for distribution studies in single
living cancer cells.
Gold Luminescent Probes
M. S. El-Deab, T. Ohsaka*
5963 – 5966
Manganese Oxide Nanoparticles
Electrodeposited on Platinum Are
Superior to Platinum for Oxygen
P. J. Barnard, L. E. Wedlock, M. V. Baker,*
S. J. Berners-Price,* D. A. Joyce,
B. W. Skelton, J. H. Steer
5966 – 5970
Luminescence Studies of the Intracellular
Distribution of a Dinuclear Gold(I)
N-Heterocyclic Carbene Complex
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials Science
X. Zhang, D. Li*
5971 – 5974
Metal-Compound-Induced Vesicles as
Efficient Directors for Rapid Synthesis of
Hollow Alloy Spheres
Hollow alloy: Vesicles formed from tetrabutylammonium bromide and metal
compounds act as efficient directors for
the rapid synthesis of a variety of binary,
ternary, and quaternary intermetallic
materials with hollow structures. In this
way, different metals were co-alloyed on
the vesicle surface to produce hollow alloy
spheres containing more than two kinds
of metals.
Hybrid Materials
Fill ’em up: The metal carboxylates MIL100 and MIL-101 act as porous matrices
(see picture; MIL = Materials of Institut
Lavoisier) for drug-delivery systems using
Ibuprofen as a model substrate. Very large
amounts of the drug could be incorporated, up to an unprecedented capacity of
1.4 g of drug per gram of porous solid for
MIL-101, and the total release of Ibuprofen was achieved under physiological
conditions in 3 (MIL-100) and 6 days
P. Horcajada, C. Serre,* M. Vallet-Reg2,
M. Sebban, F. Taulelle,
G. FSrey*
5974 – 5978
Metal–Organic Frameworks as Efficient
Materials for Drug Delivery
Combinatorial Chemistry
T. Arai,* M. Watanabe, A. Fujiwara,
N. Yokoyama, A. Yanagisawa 5978 – 5981
Direct Monitoring of the Asymmetric
Induction of Solid-Phase Catalysis Using
Circular Dichroism: Diamine–CuICatalyzed Asymmetric Henry Reaction
The direct approach: A new highthroughput screening system for analyzing the asymmetric induction in catalytic
enantioselective synthesis couples solidphase reactions with a circular dichroism
detection system (see picture). Thus,
direct monitoring of asymmetric induction without the need for purification or
chromatographic analysis is obtained.
Molecular Mechanics
N. Pour, L. Itzhaki, B. Hoz, E. Altus,
H. Basch, S. Hoz*
5981 – 5983
Auxetics at the Molecular Level: A
Negative Poisson’s Ratio in Molecular
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Negative feedback: Auxetic materials are
materials that, counterintuitively, become
thicker when stretched and thinner when
compressed (negative Poisson’s ratio).
Quantum mechanical computations were
used to identify poly[n]prismanes (n = 3–
6), the first nanomolecular systems that
manifest auxetic behavior at the molecular
level. The magnitude of the negative
Poisson’s ratio in these prismanes ranges
from 7 to 15 %.
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
Discriminating reactions: While no selfaldol reaction is observed in the reaction
shown, catalyst 1 promotes the Michael
addition of aldehydes to nitroalkenes with
the lowest catalyst loading and lowest
stoichiometric ratio of reactant aldehyde
that have been reported so far for this type
of reaction.
C. Palomo,* S. Vera, A. Mielgo,
E. G5mez-Bengoa
5984 – 5987
Highly Efficient Asymmetric Michael
Addition of Aldehydes to Nitroalkenes
Catalyzed by a Simple
Germylidyne Complexes
A. C. Filippou,* N. Weidemann,
A. I. Philippopoulos,
G. Schnakenburg
5987 – 5991
A new activation mode of aryl germanium(II) chlorides at electron-rich metal
centers leads to compounds featuring
metal–germanium triple bonds. Reaction
of 1 with RGeCl affords the hydrido–
germylidene complex 2, which rearranges
thermally to give the germylidyne complex
3 (see scheme; Trip = C6H2-2,4,6-iPr3). In
contrast, the reaction of [Mo(PMe3)6] with
RGeCl yields directly the germylidyne
complex trans-[Cl(PMe3)4MoGeR].
Activation of Aryl Germanium(II)
Chlorides by [Mo(PMe3)6] and
[W(h2-CH2PMe2)H(PMe3)4]: A New Route
to Metal–Germanium Triple Bonds
S. T. Staben, J. J. Kennedy-Smith,
D. Huang, B. K. Corkey, R. L. LaLonde,
F. D. Toste*
5991 – 5994
In control: Gold(I)-catalyzed intramolecular addition of silyl enol ethers to
alkynes and allenes allows for the
diastereoselective synthesis of cyclopentenes with control of the position of the
double bond. The utility of these reactions
Scope broadened: A previously developed
asymmetric Cu-catalyzed allylic substitution can be applied to more substituted
allylic patterns. Two classes of b-disubstituted substrates, cinnamyl derivatives
and aliphatic endocyclic allylic chlorides,
afford excellent regio- and enantioselectivities (see schemes; L* = phosphoramidite ligand).
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
is demonstrated by an efficient total
synthesis of (þ)-lycopladine A that takes
advantage of the orthogonal reactivity of
AuI and Pd0 towards unsaturated iodides
(see scheme).
Gold(I)-Catalyzed Cyclizations of Silyl
Enol Ethers: Application to the Synthesis
of (þ)-Lycopladine A
Asymmetric Catalysis
C. A. Falciola, K. Tissot-Croset,
A. Alexakis*
5995 – 5998
b-Disubstituted Allylic Chlorides:
Substrates for the Cu-Catalyzed
Asymmetric SN2’ Reaction
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Emission-Control Catalysts
As good as new: Perovskite-based catalysts containing Rh and Pt for use in
exhaust-emissions control systems are
developed. These catalysts are found to be
self-regenerating and could thus lead to
the use of lower amounts of precious
metals. The picture shows the TEM image
of Pt grains of catalyst CaTi0.95Pt0.05O3 aged
in an engine exhaust at 900 8C for 100 h.
H. Tanaka,* M. Taniguchi, M. Uenishi,
N. Kajita, I. Tan, Y. Nishihata, J. Mizuki,
K. Narita, M. Kimura,
K. Kaneko
5998 – 6002
Self-Regenerating Rh- and Pt-Based
Perovskite Catalysts for AutomotiveEmissions Control
Synthetic Methods
Z. Gu, S. Ma*
6002 – 6005
Pd(OAc)2-Catalyzed Coupling/Cyclization
of 2,3-Allenoic Acids and Methyl
Propiolate: Observation of Double
1,7-Hydrogen Shifts
On the move: A Pd(OAc)2-catalyzed coupling/cyclization reaction of 2,3-allenoic
acids with methyl propiolate in the
presence of [Sc(OTf)3]/BF3·Et2O
Hydrogen Storage
Give and take: A molecular cluster that
readily takes up and stores two molecules
of H2 also rapidly releases (milliseconds)
the stored H2 by a simple redox process.
This process represents a new method of
hydrogen storage and release from a welldefined molecular material.
S. K. Brayshaw, J. C. Green, N. Hazari,
J. S. McIndoe, F. Marken, P. R. Raithby,
A. S. Weller*
6005 – 6008
Storing and Releasing Hydrogen with a
Redox Switch
Mg/Air Battery Materials
W. Li, C. Li, C. Zhou, H. Ma,
J. Chen*
6009 – 6012
Metallic Magnesium Nano/Mesoscale
Structures: Their Shape-Controlled
Preparation and Mg/Air Battery
(OTf = triflate) leads to a “p-bond migration” in the 1:2 adducts, which may
proceed through double 1,7-hydrogen
Magnesium nano/mesostructures with
spherical, platelike, rodlike, and seaurchin-like shapes are prepared by a
simple and efficient vapor-transport
method. They exhibit excellent electrochemical properties in Mg/air batteries.
The figure shows discharge curves of the
Mg/air batteries made from two samples,
at a constant current of 0.5 mA and a
temperature of 25 8C.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
Solid-State Reactions
Changed in a flash: A photochemically
unreactive crystal of 5-methyl-2-pyridone
with a trimesic acid host is transformed in
the solid state into a reactive phase by
heating or by contact with solvent vapor.
The mechanism was revealed to involve
desolvation and a 1808 turn of one
molecule with respect to the other.
S. Hirano, S. Toyota, F. Toda,* K. Fujii,
H. Uekuasa*
6013 – 6016
Solid-State Phase Transition of an
Inclusion Complex of 5-Methyl-2-pyridone
with 1,3,5-Benzenetricarboxylic Acid
A. Malapelle, Z. Abdallah, G. Doisneau,
J.-M. Beau*
6016 – 6020
Teaching an old molecule new tricks: A
new solution for an expeditious C-sialylation from N-acetylneuraminic acid
involves the use of the peracetylated
derivative 1, a very common starting
material prepared 40 years ago in
Heidelberg, through an anomeric umpolung by samarium diiodide without an
additive, in the presence of a carbonyl
compound. Excellent yields are obtained
for the coupling with cyclic ketones (see
Anomeric Acetates of N-Acetylneuraminic
Acid are Useful C-Sialyl Donors in
Samarium-Mediated Reformatsky
Coupling Reactions
S. S. Sohn, J. W. Bode*
A clean break: An N-heterocyclic carbene
catalyzes the ring-opening of chiral nonracemic formylcyclopropanes, with simultaneous oxidation of the aldehyde function and without the need for stoichiometric reagents. The activated carboxylate
intermediate is trapped by a variety of
nucleophiles, thus leading to chiral esters,
thioesters, or carboxylic acids (see
scheme; DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene, EWG = electronwithdrawing group, Nu = nucleophile.)
6021 – 6024
N-Heterocyclic Carbene Catalyzed CC
Bond Cleavage in Redox Esterifications of
Chiral Formylcyclopropanes
Asymmetric Synthesis
C. C. C. Johansson, N. Bremeyer, S. V. Ley,
D. R. Owen, S. C. Smith,
M. J. Gaunt*
6024 – 6028
A mechanism-guided design process was
used to develop cinchona alkaloids that
are substituted at the C2’ position of the
quinoline moiety. These compounds
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
prove to be excellent organocatalysts for
an enantioselective intramolecular cyclopropanation reaction (see scheme).
Enantioselective Catalytic Intramolecular
Cyclopropanation using Modified
Cinchona Alkaloid Organocatalysts
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Intermolecular Cyclization
Caught in a trap: Intermolecular cyclopropanation reactions of enynes with
alkenes allows the synthesis of complex
cyclic systems with gold(I) catalysts under
mild conditions. Furthermore, gold carbenes are trapped intermolecularly with
alkenes (see scheme; L = ligand), thereby
providing experimental evidence for the
involvement of two different types of
metal carbenes in the skeletal rearrangement of enynes.
S. L5pez, E. Herrero-G5mez,
P. PSrez-Gal3n, C. Nieto-Oberhuber,
A. M. Echavarren*
6029 – 6032
Gold(I)-Catalyzed Intermolecular
Cyclopropanation of Enynes with Alkenes:
Trapping of Two Different Gold Carbenes
Forced to comply: The MnIII6CrIII complex
1 is constructed from two trinuclear
manganese triplesalen complexes and
one [Cr(CN6)]3 ion, and possesses a spin
ground state of St = 21/2. The threefold
symmetry enforced by the triplesalen
ligand precludes a complete cancellation
of the single-site magnetic anisotropies
and minimizes quantum tunneling of the
magnetization. The analysis of the magnetic properties reveals that this complex
is indeed a single-molecule magnet.
Single-Molecule Magnets
T. Glaser,* M. Heidemeier,
T. WeyhermWller, R.-D. Hoffmann,
H. Rupp, P. MWller
6033 – 6037
Property-Oriented Rational Design of
Single-Molecule Magnets: A
C3-Symmetric Mn6Cr Complex based on
Three Molecular Building Blocks with a
Spin Ground State of St = 21/2
Phosphorus Nitrides
M. GXbel, K. Karaghiosoff,
T. M. KlapXtke*
An explosive mixture: The first structural
characterization of a binary molecule of
phosphorus and nitrogen is described.
With the help of a new synthetic strategy,
the phosphorus azide P3N21 is prepared in
pure form, and single crystals are isolated,
enabling a structure determination by
X-ray diffraction (see structure; P orange,
N blue).
6037 – 6040
The First Structural Characterization of a
Binary P–N Molecule: The Highly
Energetic Compound P3N21
Organozinc Compounds
A. Krasovskiy, V. Malakhov, A. Gavryushin,
P. Knochel*
6040 – 6044
Efficient Synthesis of Functionalized
Organozinc Compounds by the Direct
Insertion of Zinc into Organic Iodides and
Insider dealing: A wide range of polyfunctional (hetero)aromatic and aliphatic
zinc reagents can be easily prepared in
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
THF. The compounds are formed by a Zn
insertion reaction mediated by the addition of LiCl (see scheme; All = allyl).
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
Position blocked? Quantitative studies of
polyethylene chain growth in the presence
of water by variable-temperature (VT)
H NMR spectroscopy show, unexpectedly, that water can compete with monomer binding at the vacant coordination
site in cationic diimine palladium(II)
methyl as well as higher alkyl complexes
(see scheme); the latter are prepared
cleanly as water complexes at T < 0 8C.
A. Berkefeld, S. Mecking*
6044 – 6046
Mechanistic Studies of Catalytic
Polyethylene Chain Growth in the
Presence of Water
Radioactive Peptides
F on: Fluorotriorganosilyl-derivatized Tyr3octreotate was labeled with 18F providing
the first practical formulation in 18Fradiochemistry for the labeling of a pep-
tide (see scheme). The very mild reaction
conditions and the fast labeling make this
strategy a valuable tool for the synthesis of
R. Schirrmacher,* G. BradtmXller,
E. Schirrmacher, O. Thews, J. Tillmanns,
T. Siessmeier, H. G. Buchholz,
P. Bartenstein, B. WYngler,
C. M. Niemeyer,
K. Jurkschat*
6047 – 6050
F-Labeling of Peptides by means of an
Organosilicon-Based Fluoride Acceptor
Icosahedral Clusters
A star is born: The Li26 cluster in the new
intermetallic phase Li13Na29Ba19 can be
described on the basis of a tetrahedral
star (left) or four interpenetrating centered icosahedra (right). The M26 cluster is
known from g-brass and was predicted to
be stable for Li in the gas phase.
Li13Na29Ba19 contains the first example of
a homoatomic M26 cluster in the solid
V. Smetana, V. Babizhetskyy,
G. V. Vajenine, A. Simon*
6051 – 6053
Li26 Clusters in the Compound
Homogeneous Catalysis
B. Plietker*
Iron age: An air- and water-resistant
iron(II) catalyst, in the presence of
triphenylphosphane under buffered conditions, allows for the highly regioselective
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
and stereoselective allylation of primary
aromatic amines. A broad substrate range
both in the aniline and in the allyl
carbonate moiety is tolerated.
6053 – 6056
Regioselective Iron-Catalyzed Allylic
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
For more information on
Chemistry—An Asian Journal see
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 5898 – 5908
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