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Graphical Abstract Angew. Chem. Int. Ed. 92006

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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:
H. Zhang, H. Xia,* G. He, T. B. Wen, L. Gong, G. Jia*
Synthesis and Characterization of Stable Ruthenabenzenes
X. Mo, Y. An, C.-S. Yun, S. M. Yu*
Nanoparticle-Assisted Visualization of Binding Interactions
between Collagen Mimetic Peptide and Collagen Fibers
M. B. Harney, Y. Zhang, L. R. Sita*
Discrete, Multiblock Isotactic?Atactic Stereoblock Polypropene
Microstructures of Differing Block Architectures by
Programmable Stereomodulated Living Ziegler?Natta
Polymerization
Y. Weizmann, Z. Cheglakov, V. Pavlov, I. Willner*
Autonomous Fueled Mechanical Replication of Nucleic Acid
Templates for the Amplified Optical Detection of DNA
B. Botta, F. Caporuscio, D. Subissati, A. Tafi,* M. Botta, A. Filippi,
M. Speranza*
Flattened-Cone 2,8,14,20-Tetrakis(l-valinamido)[4]resorcinarene:
Enantioselective Allosteric Receptors in the Gas Phase
B. Wang, C. Chi, W. Shan, Y. Zhang, N. Ren, W. Yang, Y. Tang*
Chiral MCM-41 Mesostructured Silica Nanofibers
News
Bioorganic Chemistry: K. Sandhoff, H. Kessler, F. Diederich, and K. C. Nicolaou awarded
1346
Books
Handbook of Reagents for Organic
Synthesis
Peter Wipf
reviewed by J. Rademann
1347
Highlights
Carbenes
F. E. Hahn*
1348 ? 1352
Heterocyclic Carbenes
New carbenes open up new vistas. The Pheterocyclic carbene 1 was obtained after
planarization of the P atoms in the
heterocycle with sterically demanding
substituents. The cyclohexyl substituent
in the cyclic alkylaminocarbene 2 can be
locked by proper substitution in the most
sterically demanding conformation such
that a low-coordinate metal center, as in
complex 3, is stabilized.
Minireviews
DNA Structures
Y. Xu, H. Sugiyama*
1354 ? 1362
Photochemical Approach to Probing
Different DNA Structures
1334
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Shedding light on DNA structures: Investigation of local DNA conformational
changes associated with biological events
is essential for understanding the function
of DNA. A modern approach to this is the
use of 5-halouracil as a probe molecule.
Upon irradiation with UV light, a uracil-5yl radical is formed and initiates a
follow-up reaction in the DNA that
depends on the local conformation of the
DNA (see picture).
Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
Angewandte
Chemie
Reviews
A vancomycin mimic: Synthetic macrocycle 1 shows promising antibiotic activity
towards Gram-positive bacterial strands
owing to its ability to bind the (R)-alanyl(R)-alanine terminus of peptoglycans. But
how useful are other amino acid derived
macrocycles?
Macrocycles
S. E. Gibson,* C. Lecci
1364 ? 1377
Amino Acid Derived Macrocycles?An
Area Driven by Synthesis or Application?
Communications
Light moves: Azobenzene liquid-crystalline elastomer (LCE) films with completely
different types of mesogen alignment
have been prepared by in situ photopolymerization. Upon irradiation with UV
light, an LCE film with homogeneous
(parallel) alignment bends toward the
light source, whereas an LCE film with
homeotropic (normal) alignment bends
away from it.
Liquid Crystals
M. Kondo, Y. Yu, T. Ikeda*
1378 ? 1382
How Does the Initial Alignment of
Mesogens Affect the Photoinduced
Bending Behavior of Liquid-Crystalline
Elastomers?
Liquid Crystals
S.-W. Choi, T. Izumi, Y. Hoshino,
Y. Takanishi, K. Ishikawa, J. Watanabe,
H. Takezoe*
1382 ? 1385
Imperative irradiation: A large enantiomeric excess in a liquid-crystal phase can
be induced by circularly polarized light
(CPL) as an external stimulus, and an
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Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
imbalance in the two chiral domains
becomes remarkable in the BX phase (see
pictures), which is similar to the B4 phase
made up by classical bent-core mesogens.
Circular-Polarization-Induced
Enantiomeric Excess in Liquid Crystals of
an Achiral, Bent-Shaped Mesogen
When push comes to shove: A switchable
[2]rotaxane has been developed in which
the binding of a metal ion (e.g. Cd2+, see
scheme) to a bis(picolyl)amine fragment
that acts as one of the stoppers induces a
shift of the macrocyclic component along
the thread from one binding site (green)
to another weaker binding site (orange).
Rotaxanes
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D. S. Marlin, D. Gonz<lez Cabrera,
D. A. Leigh,*
A. M. Z. Slawin
1385 ? 1390
An Allosterically Regulated Molecular
Shuttle
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1335
Angewandte
Chemie
Filling the pores: A zinc-based metal?
organic framework (MOF) can be transformed reversibly from an open (a) to a
dense (b) configuration. The microporous
solid is the first example of a MOF that is
highly selective in the gas-chromatographic separation of alkanes.
Microporous Materials
B. Chen,* C. Liang, J. Yang,
D. S. Contreras, Y. L. Clancy,
E. B. Lobkovsky, O. M. Yaghi,
S. Dai*
1390 ? 1393
A Microporous Metal?Organic
Framework for Gas-Chromatographic
Separation of Alkanes
CC Coupling
P. Braunstein,* O. Siri,* J.-p. Taquet,
Q.-Z. Yang
1393 ? 1397
C-substituted zwitterionic 6p + 6p benzoquinonemonoimines are obtained by a
CC bond formation reaction. A selective,
formal insertion of tetracyanoethylene
(TCNE) or 7,7?,8,8?-tetracyanoquinodimethane (TCNQ) into a CH bond of a
quinonoid ring provides a new, general
synthetic method in quinonoid chemistry.
Chalcogenides
Swapping structures and cations: In an
acid-induced 3D-to-3D transformation at
room temperature, K6Cd4Sn3Se13 is converted into K14xHxCd15Sn12Se46. The
[Cd15Sn12Se46]14 framework, which contains a tunnel network of accessible cages
of labyrinthine complexity (see picture), is
highly robust, acid resistant, and has
excellent ion-exchange properties.
N. Ding, M. G. Kanatzidis*
1397 ? 1401
Acid-Induced Conversions in OpenFramework Semiconductors: From
[Cd4Sn3Se13]6 to [Cd15Sn12Se46]14, a
Remarkable Disassembly/Reassembly
Process
In the red: The synthesis and optical
properties of homologous ladder-type
near-infrared-absorbing chromophores,
namely, two pentarylenebis(dicarboximide)s (green traces; see picture) as well
as a hexarylenebis(dicarboximide) (yellow
trace) have been studied. A strong
bathochromic shift of the absorption
maximum is noted with an increasing
degree of annulation as is evident from
the other traces.
Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
Regioselective Carbon?Carbon Bond
Formation Reactions between TCNE or
TCNQ and a Quinonoid Ring
NIR Dyes
N. G. Pschirer, C. Kohl, F. Nolde, J. Qu,
K. MOllen*
1401 ? 1404
Pentarylene- and
Hexarylenebis(dicarboximide)s: NearInfrared-Absorbing Polyaromatic Dyes
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1337
Contents
Hybrid Nanocomposites
C. J. Bhongale, C.-S. Hsu*
1404 ? 1408
Emission Enhancement by Formation of
Aggregates in Hybrid Chromophoric
Surfactant Amphiphile/Silica
Nanocomposites
Protein Microarrays
A. Watzke, M. KPhn, M. GutierrezRodriguez, R. Wacker, H. SchrPder,
R. Breinbauer, J. Kuhlmann, K. Alexandrov,
C. M. Niemeyer, R. S. Goody,*
H. Waldmann*
1408 ? 1412
In best order: Nanoaggregates of chromophores formed in a controlled fashion
in self-assembled functional hybrid nanocomposites enhance fluorescence (see
scheme). These hybrids minimize the
problem of solid-state quenching and are
thus applicable in the fabrication of
electroluminescence devices.
A sticky situation: A site-specific immobilization of proteins onto a glass surface
may allow the creation of protein microarrays. This approach relies on the Staudinger ligation between azide-modified
proteins and a phosphane-functionalized
glass surface.
Site-Selective Protein Immobilization by
Staudinger Ligation
Asymmetric Catalysis
M. T. Reetz,* Y. Fu,
A. Meiswinkel
1412 ? 1415
Nonlinear Effects in Rh-Catalyzed
Asymmetric Olefin Hydrogenation Using
Mixtures of Chiral Monodentate P Ligands
Well mixed: A 1:1 mixture of two different
binaphthol-derived monophosphonite
ligands (L) is employed in the Rh-catalyzed hydrogenation of prochiral olefins
(see scheme; cod = cyclooctadiene). Var-
iation of the enantiopurity of the ligands
results in unusual nonlinear effects; furthermore, > 92 % ee can be achieved even
if one component is racemic.
Predictable solubilities! Reagents supported on a tetraarylphosphonium group
have solubilities that can be predicted.
The reagents and their by-products can be
readily removed, recovered, and recycled
after reaction by a precipitation/filtration
sequence initiated by the addition of a
low-polarity solvent, such as diethyl ether.
Furthermore, the supported reagents are
robust and exhibit reactivities similar to
their parent compounds.
Supported Catalysts
J.-C. Poupon, A. A. Boezio,
A. B. Charette*
1415 ? 1420
Tetraarylphosphonium Salts as SolubilityControl Groups: PhosphoniumSupported Triphenylphosphine and
Azodicarboxylate Reagents
1338
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2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
Angewandte
Chemie
Back to the elements: The activity of Pt/
K0.95Ta0.92Zr0.08O3 for the photocatalytic
splitting of water into H2 and O2 is greatly
improved by dye sensitization (see picture). Among the organic dyes examined,
the highest photocatalytic activity is
obtained with cyanocobalamin (vitamin B12) as a sensitizer.
Photocatalysis
H. Hagiwara, N. Ono, T. Inoue,
H. Matsumoto, T. Ishihara* 1420 ? 1422
Dye-Sensitizer Effects on a Pt/KTa(Zr)O3
Catalyst for the Photocatalytic Splitting of
Water
Mass Spectrometry
Single charged bioparticles such as viruses, bacteria, and mammalian whole cells
have been successfully desorbed by laserinduced acoustic waves and analyzed with
a quadrupole ion-trap mass spectrometer
(see picture). This approach offers a high
sensitivity of detection and good accuracy
of the mass measurement. The capability
to measure the mass of an entire cell has
broad potential in biomedical applications.
W.-P. Peng, Y.-C. Yang, M.-W. Kang,
Y.-K. Tzeng, Z. Nie, H.-C. Chang,*
W. Chang, C.-H. Chen
1423 ? 1426
Laser-Induced Acoustic Desorption Mass
Spectrometry of Single Bioparticles
Asymmetric Synthesis
J. E. Wilson, G. C. Fu*
A phosphepine catalyst mediates enantioselective [3� cycloadditions of
allenes with a variety of b-substituted a,bunsaturated enones to produce highly
functionalized cyclopentenes that contain
two contiguous stereocenters (see
scheme). Surprisingly, opposite regioisomers are produced as compared to
reactions with b-unsubstituted enones.
1426 ? 1429
Synthesis of Functionalized
Cyclopentenes through Catalytic
Asymmetric [3� Cycloadditions of
Allenes with Enones
Synthetic Methods
Y.-M. Shen, B. Wang, Y. Shi* 1429 ? 1432
Enantioselective Synthesis of 2-Aryl
Cyclopentanones by Asymmetric
Epoxidation and Epoxide Rearrangement
Optically active epoxides are prepared by
the highly enantioselective epoxidation of
benzylidenecyclobutanes using a glucosederived ketone as the catalyst and oxone
as the oxidant. A subsequent Lewis acid
Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
catalyzed rearrangement of the resulting
epoxides with Et2AlCl or LiI provides a-aryl
substituted cyclopentanones in high enantiomeric excess (see scheme; Tol =
tolyl).
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1339
Contents
Asymmetric Reduction
A. V. Malkov,* A. J. P. S. Liddon,
P. RamSrez-LTpez, L. Bendov<, D. Haigh,
P. Koc?ovsky?*
1432 ? 1435
Remote Chiral Induction in the
Organocatalytic Hydrosilylation of
Aromatic Ketones and Ketimines
Lewis basic, metal-free pyridyloxazolines
catalyze the reduction of prochiral aromatic ketones and ketimines with Cl3SiH
in good enantioselectivity (up to 94 % ee).
Arene?arene interactions between the
substrate and the catalyst are likely to play
a role in the enantiodifferentiation process.
Twice poor equals potent: HIV-1 Protease
assembles its own potent inhibitor
through formation of the triazole linkage
from azide- and alkyne-containing fragments that are themselves poor binders.
Thermal [2� Intramolecular
Cycloadditions of Fuller-1,6-enynes
More fused rings for fullerenes: Fuller-1,6enynes are a peculiar class of 1,6-enynes
that involve a highly strained double-bond
component as well as a curved molecular
surface. They undergo an unprecedented
thermal [2� cycloaddition to afford
products with three neighboring fused
rings on one six-membered ring of the C60
core as shown in the scheme.
Computer Chemistry
Origin and generality of the halogen effect
in Diels?Alder reactions were explored
with high-accuracy CBS?QB3 computations. Halogen substitution increases
cycloaddition exergonicities and decreases activation barriers. This effect is
attributed to the energetic preference for
electronegative halogen substituents to
be attached to a more highly alkylated,
and therefore more electropositive,
carbon framework.
Drug Design
M. Whiting, J. Muldoon, Y.-C. Lin,
S. M. Silverman, W. Lindstrom, A. J. Olson,
H. C. Kolb, M. G. Finn, K. B. Sharpless,
J. H. Elder,* V. V. Fokin*
1435 ? 1439
Inhibitors of HIV-1 Protease by Using
In Situ Click Chemistry
Fullerenes
N. MartSn,* M. Altable, S. Filippone,
A. MartSn-Domenech, M. GOell,
M. SolW
1439 ? 1442
S. N. Pieniazek,
K. N. Houk*
1442 ? 1445
The Origin of the Halogen Effect on
Reactivity and Reversibility of Diels?Alder
Cycloadditions Involving Furan
1340
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2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
Angewandte
Chemie
Soft lenses: Reversible antibody?antigen
cross-links at the surface of a hydrogel
microlens allow focal tuning of the
microlens in response to soluble antigens
(see picture; PBS = phosphate-buffered
saline) to form the basis of a label-free
biosensor/bioassay technique, whose
sensitivity can be tuned by controlling the
number of cross-links required to effect a
specific swelling response.
Microlenses
Selective incorporation of CdSe quantum
dots (QDs) in the poly(4-vinylpyridine)
nanodomains of a poly(styrene-b-4-vinylpyridine) diblock copolymer thin film (see
structure) results in much higher conductivity and faster electron tunneling
than in a random distribution of the same
QDs in poly(4-vinylpyridine) homopolymer.
Quantum Dots
The strongest nitrogen base is 1,8-bis(dimethylamino)naphthalene-2,7-diolate
according to experimental data and DFT
calculations. Its proton affinity (PA) is
comparable to those of simple ions such
as OH, NH2, and H. The diaminonaphthalene diolate 2 is protonated at the
neutral amino groups with extremely high
gas-phase and solution proton affinity to
form highly stable H-bonded conjugate
acid 1. DMSO = dimethyl sulfoxide.
J. Kim, N. Singh, L. A. Lyon* 1446 ? 1449
Label-Free Biosensing with Hydrogel
Microlenses
C.-P. Li, K.-H. Wei,*
J. Y. Huang
1449 ? 1453
Enhanced Collective Electron Transport by
CdSe Quantum Dots Confined in the
Poly(4-vinylpyridine) Nanodomains of a
Poly(styrene-b-4-vinylpyridine) Diblock
Copolymer Thin Film
Proton Sponges
V. A. Ozeryanskii,* A. A. Milov,
V. I. Minkin, A. F. Pozharskii 1453 ? 1456
1,8-Bis(dimethylamino)naphthalene-2,7diolate: A Simple Arylamine Nitrogen
Base with Hydride-Ion-Comparable
Proton Affinity
Coordination Modes
Changes in polyhedral shapes around Co
and N atoms in a polyhedral-interconversion reaction coupled to a proton-transfer
process are followed in a theoretical study
through a generalized polyhedral-interconversion coordinate within the framework of the Avnir continuous shape
measures.
D. Casanova, P. Alemany,
S. Alvarez*
1457 ? 1460
Polyhedral Interconversion Coupled with
Proton Transfer between an Ammonium
Cation and the [Co(CO)4] Ion
Electrochemistry
T. Miura, S. Kim, Y. Kitano, M. Tada,
1461 ? 1463
K. Chiba*
Electrolytically generated four-memberedring radical-cation intermediates are
involved in the anodic olefin crossmetathesis of enol ethers and olefins in a
Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
lithium perchlorate/nitromethane electrolyte solution (see scheme). The reaction
mechanism was investigated through
deuterium-labeling studies.
Electrochemical Enol Ether/Olefin CrossMetathesis in a Lithium Perchlorate/
Nitromethane Electrolyte Solution
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1341
Contents
Homogeneous Catalysis
D. Enders,* O. Niemeier,
T. Balensiefer
1463 ? 1467
Asymmetric Intramolecular CrossedBenzoin Reactions by N-Heterocyclic
Carbene Catalysis
Getting cross: Excellent asymmetric
inductions and very good yields are
achieved in the generation of a quaternary
stereocenter in a-hydroxy-substituted tetralones by using chiral N-heterocyclic
carbene catalysts in an enantioselective
intramolecular crossed-benzoin reaction.
The synthesis of the corresponding ahydroxyindanones with good ee values is
also possible by this route.
Allylic Alkylation
B. Plietker*
1469 ? 1473
A Highly Regioselective Salt-Free IronCatalyzed Allylic Alkylation
Ironing out the kinks: A highly regioselective allylic alkylation can be performed
in the presence of catalytic amounts of an
iron(ii) complex and triphenylphosphane (see scheme; EWG = electronwithdrawing group). Allyl carbonates and
Surface Reactions
Over the top: Electrochemically induced
oxygen spillover on a Pt film has been
investigated by photoelectron emission
microscopy. Oxygen ions migrate through
the YSZ substrate to the triple-phase
boundary, where they are converted into
adsorbed oxygen atoms that can oxidize
the carbon layer on the Pt surface (see
scheme; YSZ = yttria-stabilized zirconia).
B. Luer遝n, E. Mutoro, H. Fischer,
S. GOnther, R. Imbihl,
J. Janek*
1473 ? 1476
In Situ Imaging of Electrochemically
Induced Oxygen Spillover on Pt/YSZ
Catalysts
Aluminum Clusters
R. Burgert, H. SchnPckel,* M. Olzmann,
K. H. Bowen, Jr.
1476 ? 1479
The Chlorination of the [Al13] Cluster and
the Stepwise Formation of Its
Intermediate Products, [Al11] , [Al9] , and
[Al7]: A Model Reaction for the Oxidation
of Metals?
pronucleophiles are coupled in high yields
with a high regioselectivity comparable
only with that obtained with Rh catalysts.
The reaction is broadly applicable and
does not require external base.
Watch your step! The individual steps
during the chlorination of [Al13] clusters
via [Al11] , [Al9] , and [Al7] intermediates
(see picture) can be ?visualized? by
means of Fourier transform ion cyclotron
resonance (FT-ICR) mass spectrometry.
The reaction can be interpreted as a model
reaction for the chlorination of bulk
aluminum.
The issues for February 2006 appeared online on the following dates
Issue 5: January 17 � Issue 6: January 23 � Issue 7: January 30 � Issue 8: February 6
1342
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2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
Angewandte
Chemie
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Angew. Chem. Int. Ed. 2006, 45, 1334 ? 1343
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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