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Graphical Abstract Angew. Chem. Int. Ed. 52006

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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:
J. Deschamp, O. Chuzel, J. Hannedouche, O. Riant*
Highly Diastereo- and Enantioselective Copper-Catalyzed
Tandem Conjugated Reduction/Aldol Reaction to Ketones
J. W. Bode,* R. M. Fox, K. D. Baucom
Chemoselective Amide Ligations by Decarboxylative
Condensations of N-Alkylhydroxylamines and a-Keto Acids
A. Oleksi, A. G. Blanco, R. Boer, I. Us*n, J. Aymam,, A. Rodger,
M. J. Hannon,* M. Coll*
Molecular Recognition of a Three-Way DNA Junction by a
Metallosupramolecular Helicate
J. E. Banham, C. R. Timmel, R. J. M. Abbott, S. M. Lea,*
G. Jeschke*
A New Tool for Characterization of Weak Protein–Protein
Interactions: Evidence from DEER for the Trimerization of a
von Willebrand Factor A Domain in Solution
B. H. Lipshutz,* B. A. Frieman, A. E. Tomaso, Jr.
Copper-in-Charcoal (Cu/C): Heterogeneous, Copper-Catalyzed
Asymmetric Hydrosilylations
J. T. Shaw,* J. M. Mitchell
A Structurally Diverse Library of Polycyclic Lactams Resulting
from the Systematic Placement of Proximal Functional Groups
Obituary
Henry Taube (1915–2005): Electron Transfer
P. C. Ford, E. I. Solomon
692
Books
Optical Spectroscopy in Chemistry and
Life Sciences
Werner Schmidt
reviewed by M. Volk
694
Carbon Nanotubes
M. Meyyappan
reviewed by D. M. Guldi
695
Sugar in the gas tank?! Biomass is the
only practical source of renewable liquid
fuel (see picture). In research worldwide,
new technologies are being developed for
the generation of liquid fuels from
renewable resources. One example is the
reduction of polyols, such as sorbitol,
which can be obtained from carbohydrates, into alkanes in an aqueous-phase
reforming process.
Highlights
Biofuels
J. O. Metzger*
696 – 698
Production of Liquid Hydrocarbons from
Biomass
Phosphorus Modifications
A. Pfitzner*
Phosphorus Remains Exciting!
680
699 – 700
A peep down the pipe: Although phosphorus has been known for about
350 years, it still offers scope for discovery. Thus success has now been achieved
in the elucidation of the crystal structure
of fibrous phosphorus in which the polymeric phosphorus tubes are present as
parallel tubes (see structure) contrary to
Hittorf’s phosphorous in which these
tubes are linked cross-wise. In addition,
polymers with the translational unit [P12]
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
have been isolated from their copper
iodide adducts.
Angew. Chem. Int. Ed. 2006, 45, 680 – 689
Angewandte
Chemie
Reviews
From conception to application: Combinatorial and high-throughput experimentation technologies make important contributions to research in the area of
polymeric sensor materials that are based
on homo- and copolymers, formulated
materials, engineered structures with
desired morphologies, and molecular
recognition materials (see picture).
Materials Research
702 – 723
R. A. Potyrailo*
Polymeric Sensor Materials: Toward an
Alliance of Combinatorial and Rational
Design Tools?
Communications
Close to original: A DNA-like doublestranded polymer is synthesized by ringopening metathesis polymerization of a
bisnorbornene derivative containing a
rigid ferrocene spacer. The polymer forms
helices (see picture), supercoils, and
ladders, which are observable by scanning
tunneling microscopy.
DNA-like Polymers
The incorporation of a single gold nanoparticle into a rationally designed DNA
nanostructure and the use of the nanoparticle-bearing DNA nanostructure for
the templated self-assembly of periodical
nanoparticle arrays is presented. This
approach allows the opportunity to control the interparticle spacings and hierarchical architectures of nanoparticles.
Nanostructures
H.-C. Yang, S.-Y. Lin, H.-C. Yang, C.-L. Lin,
L. Tsai, S.-L. Huang, I. W.-P. Chen,
C.-H. Chen, B.-Y. Jin, T.-Y. Luh* 726 – 730
Molecular Architecture towards Helical
Double-Stranded Polymers
J. Sharma, R. Chhabra, Y. Liu, Y. Ke,
H. Yan*
730 – 735
DNA-Templated Self-Assembly of TwoDimensional and Periodical Gold
Nanoparticle Arrays
DNA Nanostructures
Decorated tiles: Self-assembling DNA
nanostructures can be used to form
addressable, size-controlled nanoarrays
with a variety of programmed patterns.
Arrays of DNA cross-shaped tiles were
decorated with pixels of individual protein
molecules. The letters “D”, “N”, and “A”
on self-assembled 4 N 4 arrays (< 80-nm
square, see picture) were prepared by a
minimal-depth strategy.
Finite-Size, Fully Addressable DNA Tile
Lattices Formed by Hierarchical Assembly
Procedures
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Angew. Chem. Int. Ed. 2006, 45, 680 – 689
S. H. Park, C. Pistol, S. J. Ahn, J. H. Reif,
A. R. Lebeck, C. Dwyer,*
T. H. LaBean*
735 – 739
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
681
Angewandte
Chemie
Habit forming: Amphiphilic lipopeptide 1
forms a stable monolayer with an antiparallel b-sheet conformation. This
monolayer interacts with calcium ions and
can be used as a biomimetic mineralization template for the formation of a new
crystal habit of calcite (see SEM image).
The nucleation of different crystal faces
can be achieved depending on the ability
of the template to adapt to the organic
phase.
Biomineralization
S. Cavalli, D. C. Popescu, E. E. Tellers,
M. R. J. Vos, B. P. Pichon, M. Overhand,
H. Rapaport, N. A. J. M. Sommerdijk,*
A. Kros*
739 – 744
Self-Organizing b-Sheet Lipopeptide
Monolayers as Template for the
Mineralization of CaCO3
Host–Guest Systems
D. Fiedler, R. G. Bergman,*
K. N. Raymond*
745 – 748
Stabilization of Reactive Organometallic
Intermediates Inside a Self-Assembled
Nanoscale Host
Trapped in a cage: A supramolecular
metal–ligand assembly is utilized to stabilize two reactive organometallic intermediates in aqueous solution. While
these organometallic complexes decompose in organic solution within hours and
in the presence of water within minutes,
binding into the supramolecular cage
renders them inert for several weeks.
Despite their stabilization, the guest
molecules are still able to react stoichiometrically with CO.
Nanostructures
To cap it all off: Colloidally stable hydrophilic 1D CdTe nanostructures (see picture) have been easily prepared under
aqueous conditions in the presence of
capping thiol ligands. The present methodology shows a strong dependence on
the concentration of the precursors and
the molecular structure of the ligand.
H. Zhang, D. Wang,*
H. MPhwald
Ligand-Selective Aqueous Synthesis of
One-Dimensional CdTe Nanostructures
Self-assembly of 1,n’-disubstituted ferrocene cyclopeptides leads to the first
model of b barrels, a ubiquitous structural
motif in proteins. The b-barrel model has
eight b strands arranged almost parallel
to the axis of the channel with an internal
pore diameter of 8 Q.
Angew. Chem. Int. Ed. 2006, 45, 680 – 689
748 – 751
Macrocycles
S. Chowdhury, D. A. R. Sanders,
751 – 754
G. Schatte, H.-B. Kraatz*
Discovery of a Pseudo b Barrel: Synthesis
and Formation by Tiling of Ferrocene
Cyclopeptides
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
683
Contents
Charge Separation
T. Hasobe, S. Fukuzumi,*
P. V. Kamat*
755 – 759
Stacked-Cup Carbon Nanotubes for
Photoelectrochemical Solar Cells
Seeing the light: Stacked-cup carbon
nanotubes (SCCNTs) have been electrophoretically deposited on conducting
glass electrodes from a suspension in
THF by using a dc field (see picture).
These SCCNT films undergo charge
separation and deliver photocurrent on
irradiation with visible light. The photon
conversion efficiency of 17 % observed
with the SCCNT system is two orders of
magnitude greater than those obtained
with carbon nanotubes.
Enzyme Catalysis
H. Deng, S. L. Cobb, A. R. McEwan,
R. P. McGlinchey, J. H. Naismith,
D. O’Hagan,* D. A. Robinson,
J. B. Spencer
759 – 762
The Fluorinase from Streptomyces cattleya
Is Also a Chlorinase
Choices choices: The fluorinase enzyme
from Streptomyces cattleya (catalyzes the
formation of a CF bond from fluoride
ions) also has the capacity to utilize a
chloride ion although it has a clear
preference for the fluoride ion. The
enzyme mediates a nucleophilic chlorination reaction, which is an unusual
mechanism for enzymatic chlorination.
Double substitution: The first selective
and widely applicable method for a stepwise alkylation of 1,1-dichloro-1-alkenes
involving a cross-coupling double substitution using Pd-catalysis has been devel-
oped. This method provides an efficient
and highly selective route for the synthesis
of E or Z trisubstituted alkenes. dpephos = bis(o-diphenylphosphanylphenylether).
Cross-Coupling
Z. Tan, E.-i. Negishi*
762 – 765
Widely Applicable Pd-Catalyzed transSelective Monoalkylation of Unactivated
1,1-Dichloro-1-alkenes and Pd-Catalyzed
Second Substitution for the Selective
Synthesis of E or Z Trisubstituted Alkenes
Liquid Chromatography
V. A. Soloshonok*
766 – 769
Remarkable Amplification of the SelfDisproportionation of Enantiomers on
Achiral-Phase Chromatography Columns
684
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A phase they’re going through: The
enantiomers of chiral compounds containing a trifluoromethyl group directly
bonded to a stereogenic carbon center are
prone to self-disproportionation on columns of achiral silica gel (see picture).
Thus, all fluorine-containing chiral
reagents and drugs, as well as literature
data on the stereochemical outcome of
asymmetric transformations involving
fluorine-containing compounds, should
be reevaluated.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 680 – 689
Angewandte
Chemie
Synthetic Methods
H. Tanaka, D. Takahashi,
T. Takahashi*
770 – 773
Stereoselective Synthesis of Oligo-a(2,8)3-deoxy-d-manno-2-octulosonic Acid
Derivatives
Iodoalkoxylation (see scheme) of a glycal
with an acyclic saccharide precursor leads
to an efficient stereoselective synthesis of
di- and tri-a(2,8)-3-deoxy-d-manno-2octulosonic acid (KDO; see picture). The
glycal forms a-linked 3-iodo-KDO derivatives. The opening of the pyran ring
improves the reactivity of the C8 hydroxy
group. NIS = N-iodosuccimide, Tf =
triflate, M.S. = molecular sieves
Colloids
On suspension: While slightly hydrophobic silica particles can stabilize emulsions
by forming dense, close-packed monolayers at the droplet surface that act as a
steric barrier against coalescence,
strongly repulsive particles can stabilize
emulsions as a result of spontaneous
particle accumulation in a dense monolayer bridging the emulsion droplets that
are sparsely covered with particles (see
microscopy images).
Reaction of the high-spin iron(ii) alkyl
complex [{PhB(CH2PiPr2)3}FeMe] with
phenylsilane or mesitylsilane affords
unusual diamagnetic silane adducts of the
iron(ii) hydride [{PhB(CH2PiPr2)3}FeH].
An h3 bonding mode in these silane
adducts has been established by NMR
spectroscopy, X-ray crystallography, and
DFT methods. Rapid interconversion of
T. S. Horozov,* B. P. Binks
Particle-Stabilized Emulsions: A Bilayer or
a Bridging Monolayer?
Silanes
C. M. Thomas, J. C. Peters*
776 – 780
An h3-H2SiR2 Adduct of
[{PhB(CH2PiPr2)3}FeIIH]
the hydride positions in solution via a
silylene intermediate is proposed.
Keeping order: Mesoporous crystalline
iron oxide thin films were prepared by
using special block copolymer templates.
The optimized templating properties and
temperature stability of the porogens
allowed a crystal-to-crystal phase transition (from goethite to hematite) within the
walls of the porous scaffold without disruption of the mesostructure.
Angew. Chem. Int. Ed. 2006, 45, 680 – 689
773 – 776
Mesoporous Materials
T. Brezesinski, M. Groenewolt,
781 – 784
M. Antonietti, B. Smarsly*
Crystal-to-Crystal Phase Transition in SelfAssembled Mesoporous Iron Oxide Films
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
685
Contents
Biotechnology
Coat of arms: Combining colloidal particles, whose surfaces have been coated
with a polyelectrolyte multilayer by means
of the layer-by-layer (lbl) technology, with
virus surface display systems enables a
variety of biological functions to be added
to the particles (see picture). The proteins
displayed on the colloidal surface can be
monitored by using modern sorting and
analytical techniques.
M. Fischlechner, L. Toellner, P. Messner,
R. Grabherr, E. Donath*
784 – 789
Virus-Engineered Colloidal Particles—A
Surface Display System
Total Synthesis
J. Yamaguchi, M. Toyoshima, M. Shoji,
H. Kakeya, H. Osada,
Y. Hayashi*
789 – 793
Concise Enantio- and Diastereoselective
Total Syntheses of Fumagillol, RK-805,
FR65814, Ovalicin, and
5-Demethylovalicin
l-Proline-mediated a-aminoxylation is a
key step in the enantio- and diastereoselective total syntheses of fumagillin,
ovalicin, and related compounds (see
scheme). These compounds contain a
CC Coupling
The unsalted variety: The direct coupling
reaction of alcohols with active methylenes, alkoxyketones, or indoles catalyzed
by InCl3 proceeds without the formation of
metal salts (see scheme). As H2O is the
only by-product of this system, the alkylated products are easily isolated in pure
form, and the reaction is suitable for largescale synthesis.
M. Yasuda, T. Somyo,
A. Baba*
793 – 796
Direct Carbon–Carbon Bond Formation
from Alcohols and Active Methylenes,
Alkoxyketones, or Indoles Catalyzed by
Indium Trichloride
Foldamers
J.-L. Hou, H.-P. Yi, X.-B. Shao, C. Li,
Z.-Q. Wu, X.-K. Jiang, L.-Z. Wu, C.-H. Tung,
Z.-T. Li*
796 – 800
Helicity Induction in Hydrogen-BondingDriven Zinc Porphyrin Foldamers by
Chiral C60-Incorporating Histidines
686
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cyclohexane ring, two epoxides, and five
or six contiguous stereogenic centers, and
they display anti-angiogenesis or immunosuppressive properties.
High chiral amplification is exhibited by a
new series of zinc porphyrin appended,
hydrogen-bonded foldamers on binding
with C60-incorporating chiral histidines as
a result of the cooperation of two discrete
noncovalent interactions: zinc porphyrin/
imidazole coordination and zinc porphyrin/C60 p–p stacking (see picture).
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 680 – 689
Angewandte
Chemie
Synthetic Methods
How would you reduce an aryl OH group?
Traditionally, a palladium catalyst, a mild
source of hydride, and a triflate derivative
are used in solution. A more modern
alternative is presented that is not only
economical but heterogeneous as well.
Nickel-on-graphite (Ni/Cg) is introduced
as a very inexpensive catalyst that reduces
aryl tosylates and mesylates with excellent
functional group tolerance.
B. H. Lipshutz,* B. A. Frieman, T. Butler,
V. Kogan
800 – 803
Heterogeneous Catalysis with
Nickel-on-Graphite (Ni/Cg): Reduction of
Aryl Tosylates and Mesylates
Iron Phosphonates
Turning over a new leaf: In the title iron
phosphonate compounds, triangles and
hexagons fuse together to generate a
maple leaf lattice (see polyhedral representation; green Fe, purple P). This lattice
is a new type of topologically frustrated
antiferromagnetic network. Exotic forms
of magnetic behavior are often encountered in such frustrated materials.
D. Cave, F. C. Coomer, E. Molinos,
H.-H. Klauss, P. T. Wood*
803 – 806
Compounds with the “Maple Leaf”
Lattice: Synthesis, Structure, and
Magnetism of
Mx[Fe(O2CCH2)2NCH2PO3]6·n H2O
Electrostatic glue: Chiral anionic molecular squares are generated by linking four
spiro-biscatecholate ligands with boron
centers. Through ionic interactions and
hydrogen bonding, substituted ammonium ions facilitate the stacking of the
anionic squares into infinite nanotubes
(see picture; green B, black C, blue N,
red O).
Supramolecular Chemistry
B. F. Abrahams, D. J. Price,
R. Robson*
806 – 810
Tetraanionic Organoborate Squares Glued
Together by Cations To Generate
Nanotubular Stacks
Cyclizations
Y. Morimoto,* Y. Nishikawa, C. Ueba,
T. Tanaka
810 – 812
Against the rules: The switching of the
usual 5-exo cyclizations of epoxide substrates to the 6-endo mode, which goes
against Baldwin’s rule, is demonstrated by
treating bishomoepoxy alcohols with triisopropylsilyl triflate (TIPSOTf) in nitro-
Nanoreactors: Metal nanoparticles must
be stabilized with carrier systems against
aggregation if they are to have applications in catalysis. One such system, a
thermosensitive network of poly(N-isopropylacrylamide) that surrounds a polystyrene core, enables control over the
catalytic activity of the nanoparticles
through a phase transition and leads
Angew. Chem. Int. Ed. 2006, 45, 680 – 689
methane (see scheme). This method is
different to those previously reported in
which elaborate modifications of the
epoxide substrate are required to attain 6endo cyclization.
Reagent-Controlled Switching of 5-exo to
6-endo Cyclizations in Epoxide Openings
Nanoparticles
Y. Lu, Y. Mei, M. Drechsler,
M. Ballauff*
to applications as a controllable
nanoreactor.
813 – 816
Thermosensitive Core–Shell Particles as
Carriers for Ag Nanoparticles: Modulating
the Catalytic Activity by a Phase Transition
in Networks
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
687
Contents
Sugar Helices
D. Fischer, E. Loos, A. Geyer*
816 – 819
Oligo-(1!2)-a-d-glucopyranosyl-(1!2)b-d-fructofuranosides Form Tight Sugar
Coils
Supramolecular Chemistry
W. Pisula, M. Kastler, D. Wasserfallen,
J. W. F. Robertson, F. Nolde, C. Kohl,
K. MYllen*
819 – 823
Pronounced Supramolecular Order in
Discotic Donor–Acceptor Mixtures
Substituent Effects
F. M. Bickelhaupt,* H. L. Hermann,
823 – 826
G. Boche*
a-Stabilization of Carbanions: Fluorine Is
More Effective than the Heavier Halogens
Sphingolactones
V. Wascholowski, A. Giannis*
827 – 830
Sphingolactones: Selective and
Irreversible Inhibitors of Neutral
Sphingomyelinase
The cyanobacterial oligosaccharides [a-dGlc(1!2)]n-b-d-Fru (n 9) form righthanded helices with a tetrasaccharide
repeat, a diameter of 12 Q, and a pitch of
5 Q. The vicinal a-(1!2)-glycosidic linkages stabilize this compact helix with a
significant energy barrier of unwinding.
Kojiheptaose (n = 7) with a fructofuranose
terminus is the smallest biopolymer with
an unfolding barrier observable by NMR
spectroscopy.
Mixing a hexa-peri-hexabenzocoronene
(HBC) derivative and a perylene- or terrylenediimide results in the formation of
complex helical arrangements in the
columnar superstructures. Weak donor–
acceptor interactions between the electron-rich HBC and the electron-poor
rylene dye lead to strictly alternating and
long-range-ordered stacks. The mixtures
display homeotropic orientation on surfaces (picture shows an image from an
optical microscope).
Ready steady go! The basicity of the
carbanions CH2X decreases continuously in the series X = F, Cl, Br, I. However,
contrary to the common assumption, this
occurs not because of the increasing astabilization of CH2X : F stabilizes CH2X
more effectively than Cl, Br, and I (see
picture). This apparent contradiction
results from the usually ignored stabilization of the corresponding acids CH3X by
X.
Ceramide analogues which act as potent
inhibitors of the neutral sphingomyelinase
(N-SMase) without needing to contain
reactive epoxy groups are the sphingolactones (see picture for an example).
Sphingolactones are useful chemical tools
for exploring the biological significance of
ceramide and N-SMase in, for example,
apoptosis and inflammatory processes.
The issues for January 2006 appeared online on the following dates
Issue 1: December 14. · Issue 2: December 21. · Issue 3: January 5. · Issue 4: January 11
688
www.angewandte.org
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 680 – 689
Angewandte
Chemie
Service
Keywords
832
Authors
833
Sources
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For more information on
ChemMedChem see
www.chemmedchem.org
Corrigendum
*
The correct correspondence address for the authors of this Communication is:
State Key Laboratory of Structural Chemistry
Fujian Institute of Research on the Structure of Matter
and Graduate School of the Chinese Academy of Sciences
Fuzhou, Fujian 350002 (P. R. China)
Lanthanide–Transition-Metal Sandwich
Framework Comprising {Cu3} Cluster
Pillars and Layered Networks of {Er36}
Wheels
J.-W. Cheng, J. Zhang, S.-T. Zheng,
M.-B. Zhang, G.-Y. Yang*
73–77
Angew. Chem. Int. Ed. 2006, 45
DOI 10.1002/anie.200502917
Angew. Chem. Int. Ed. 2006, 45, 680 – 689
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
689
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