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Graphical Abstract Angew. Chem. Int. Ed. 52003

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From Mendel to the Postgenomic Era
A. Marx
Organometallics in Synthesis
Manfred Schlosser
N. Krause
Global Environmental Change
Ronald E. Hester, Roy M. Harrison
J. Hahn
Peptide Bond Isomerization
J. Fangh‰nel*
The search for the answer to the question
posed in the title has been helped by
results by Eisenmesser et al. on the
cyclophilin 18-catalyzed peptidyl±prolyl
cis/trans isomerization. Here their results
are discussed in connection with previously published data about the catalytic
mechanism of this enzyme class. For
several of the amino acid side chains (see
picture) present in the active center of the
enzyme it could be shown that they are
involved in substrate binding or in formation of the transition state.
490 ± 492
Enzymatic Catalysis of the Peptidyl±Prolyl
Bond Rotation: Are Transition State Formation and Enzyme Dynamics Directly
cyclophilin ¥ enzyme catalysis ¥ molecular
dynamics ¥ PPIase ¥ proteins
Protein Microarray Methods
D. S. Wilson, S. Nock*
494 ± 500
Recent Developments in Protein Microarray Technology
drug development ¥ immunoassays ¥
multiplexed analysis ¥ proteomics ¥
Small and fast: The miniaturization and
parallelization of protein microarrays has
made it possible to measure simultaneously the interactions between proteins
and numerous analytes in a small biological sample. These microarrays consist
of numerous, about 50±200 mm, spots
with surface-bound proteins (see picture).
This will enable the throughput of proteomic analysis to be increased dramatically.
100 Years of Arynes
H. H. Wenk, M. Winkler,
W. Sander*
502 ± 527
One Century of Aryne Chemistry
arynes ¥ cyclization ¥ enediynes ¥ matrix
isolation ¥ quantum chemistry
One century the after postulation of the
first aryne (didehydrobenzofuran 1) as a
reactive intermediate, research activities
in this area are more prevalent than ever
before. The discovery of the endiyne
cytostatics in particular has promoted a
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renaissance of aryne chemistry. Despite
considerable progress during the last few
years many questions still remain unanswered and, therefore, interest in aryne
chemistry–parent systems 2±4–is expected to continue far into the future.
Angew. Chem. Int. Ed. 2003, 42, No. 5
Chains of Metal Atoms
C. Tejel, M. A. Ciriano,* B. E. Villarroya,
J. A. LÛpez, F. J. Lahoz,
L. A. Oro*
529 ± 532
Electrons in chains: A novel metallic chain
made up of six iridium atoms (see
picture) with an average oxidation state of
þ 1.33 has been found in the complex
(Opy ¼ 2-pyridonate, H ¼ head, T ¼ tail).
This complex provides a new link in the
electronic sequence connecting dinuclear
IrI and IrII complexes.
Water shortage: The structures of the
three-dimensional coordination polymers
[{M2(Cu3(iminodiacetate)6)}¥8 H2O]n
(M ¼ La (1), Nd (2), and Eu (3)) contain
water molecules that are located within
channels throughout the lattice structure
(see picture). Investigation of their thermal stability shows that the frameworks
remained intact when the guest water
molecules were removed. Rehydration of
the La and Eu species leads to polymers
with only five lattice water molecules per
polymer unit, which corresponds to a
change in the bonding characteristics of
the water molecules.
The prevention of cell death by the antiapoptotic protein Bcl-xL has been linked
to a number of cancers. Bcl-xl binds to the
A Hexanuclear Iridium Chain
chain structures ¥ electronic structure ¥
iridium ¥ metal±metal interactions ¥ N,O
Nanoporous Coordination Polymers
Y.-P. Ren, L.-S. Long,* B.-W. Mao,
Y.-Z. Yuan, R.-B. Huang,
L.-S. Zheng
532 ± 535
Nanoporous Lanthanide±Copper(ii) Coordination Polymers: Syntheses and
Crystal Structures of [{M2(Cu3(iminodiacetate)6)}¥8 H2O]n (M ¼ La, Nd, Eu)
copper ¥ lanthanides ¥ nanostructures ¥
polymers ¥ structure elucidation
BH3 domain of the proapoptotic protein
Bak, thus preventing programmed cell
death. A competitive assay and docking
studies have shown that the polyamide
scaffold 1, which was synthesized based
on a rational structure-based design,
interferes with the Bak BH3/Bcl-xl complexation.
Protein-Protein Interactions
J. T. Ernst, J. Becerril, H. S. Park, H. Yin,
A. D. Hamilton*
535 ± 539
Design and Application of an a-HelixMimetic Scaffold Based on an Oligoamide-Foldamer Strategy: Antagonism of
the Bak BH3/Bcl-xL Complex
amides ¥ helical structures ¥
peptidomimetics ¥ protein models ¥
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Angew. Chem. Int. Ed. 2003, 42, 478 ± 484
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Theory of Pyramidal Boron
K. T. Giju, A. K. Phukan,
E. D. Jemmis*
Discovery of new pyramids: Theoretical
studies have characterized CBSiH5,
BSi2H5, CBGeH5, and CBSnH5, all of which
have a tricoordinate pyramidal boron
atom as minima on their respective
potential energy surfaces (see picture).
The extent of pyramidalization, as well as
the energy for inversion through the
planar structure, is dependent on the
substituents of the boron atom.
539 ± 542
Stabilization of Tricoordinate Pyramidal
Boron: Theoretical Studies on CBSiH5,
BSi2H5, CBGeH5, and CBSnH5
boron ¥ computer chemistry ¥ density
functional calculations ¥ small ring
Narrow windows and large supercavities
comprise the novel nanoporous coordination organometallic structure RPM-1,
which has a two-fold interpenetrating 3D
network containing unique open channels
(see picture). RPM-1 exhibits a high
sorption capacity for large hydrocarbons
and superior size/shape selectivity for the
photolysis of ortho-methyl dibenzyl ketone
(o-MeDBK; 100 % cage effect). A completely reversible structural transformation takes place between RPM-1 and a
nonporous 1D compound, which allows a
full recovery of the o-MeDBK derived
products (100 % mass balance).
Ship-in-Bottle Photochemistry
L. Pan, H. Liu, X. Lei, X. Huang,
D. H. Olson, N. J. Turro,
J. Li*
542 ± 546
RPM-1: A Recyclable Nanoporous Material Suitable for Ship-In-Bottle Synthesis
and Large Hydrocarbon Sorption
cobalt ¥ coordination polymers ¥ hostguest systems ¥ photochemistry ¥ zeolite
Chiral Metallahelicates
J. A. Johnson, J. W. Kampf,
V. L. Pecoraro*
Both l- or d-norvaline hydroxamic acids
undergo one-step reactions with acetate,
chloride, and CuII ions to form self-assembled metallahelicates that contain
20 chiral carbon and four chiral metal
centers. Enantiopure complexes of over
three nanometers in length, and composed of either P- or M-type doublestranded helical oligomers (see scheme),
have been isolated.
546 ± 549
The Preparation of a Double Metallahelicate Containing 28 Copper Atoms
copper ¥ helical structures ¥ macrocycles ¥
self-assembly ¥ supramolecular chemistry
Lewis Acids in Total Synthesis
A. K. Miller, D. Trauner*
549 ± 552
Total Synthesis of ( )-Photodeoxytridachione through a Lewis Acid Catalyzed
cyclization ¥ cycloaddition ¥ homogeneous
catalysis ¥ Lewis acids ¥ total synthesis
Concerted or stepwise: The concise total
synthesis of the molluscan polypropionate photodeoxytridachione (3) features a
Lewis acid catalyzed cyclization of tetra-
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enoic ester 1 to form bicylo[3.1.0]hexene 2
as a key step. The stereochemistry of the
cyclization can be rationalized in terms of
a stepwise or a concerted mechanism.
Angew. Chem. Int. Ed. 2003, 42, No. 5
Osmium±Palladium Clusters
Palladium-filled sandwiches: The reaction
between the [Os10(m6-C)(CO)24]2 ion and
[Pd(NCMe)4](BF4)2 yields the osmium±
palladium mixed-metal cluster,
which has the highest nuclearity known
for such clusters, and has been shown by
single-crystal X-ray analysis to be a ™metal
sandwich∫ with two Os9 units connected
by a triangular Pd3 subcluster (see picture); five reversible cathodic waves have
been observed through cyclic voltammetry.
Silica coats for butterfly wings: The oxidation of silane with hydrogen peroxide is
conducted on the surface of delicately
K.-F. Yung, W.-T. Wong*
553 ± 555
[{N(PPh3)2}2{Os18Pd3(m6-C)2(CO)42}]: An
Osmium±Palladium Mixed-Metal HighNuclearity Carbonyl Cluster
cluster compounds ¥ electrochemistry ¥
osmium ¥ palladium ¥ redox chemistry
structured biological specimens (templates), to produce a thin silica coating
that leaves the underlying structure unharmed. Removal of the template by
calcination leaves a precise replica of the
original specimen (see SEM image of a
silica replica obtained from a fly wing).
The method is also proposed as a novel
means of conservation for sensitive archaeological specimens.
Patterned polymer brushes can be produced on the micrometer and nanometer
scale by a combination of self-assembly
and lithography. Self-assembled monolayers of biphenyl thiols were structured
by chemical lithography. The patterns
were amplified by surface-initiated polymerization.
Biomimetic Structures Through CVD
G. Cook, P. L. Timms,
C. Gˆltner-Spickermann*
557 ± 559
Exact Replication of Biological Structures
by Chemical Vapor Deposition of Silica
biomimetics ¥ coating ¥ CVD ¥ replication ¥
Patterned Polymer Brushes
U. Schmelmer, R. Jordan,* W. Geyer,
W. Eck, A. Gˆlzh‰user,* M. Grunze,
A. Ulman
559 ± 563
Surface-Initiated Polymerization on SelfAssembled Monolayers: Amplification of
Patterns on the Micrometer and Nanometer Scale
azo compounds ¥ lithography ¥
polymerization ¥ polymers ¥ self-assembly
Angew. Chem. Int. Ed. 2003, 42, 478 ± 484
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Radical Anion Complexes
P. Ghosh, A. Begum, D. Herebian,
E. Bothe, K. Hildenbrand, T. Weyherm¸ller,
K. Wieghardt*
563 ± 567
Coordinated o-Dithio- and
o-Iminothiobenzosemiquinonate(1) p
Radicals in [MII(bpy)(LC)](PF6) Complexes
Reversible ligand-centered one-electron
oxidation of square-planar neutral com-
plexes of palladium(ii) and platinum(ii)
[M(bpy)(L)] (bpy ¼ bipyridine, L: see picture) leads to the paramagnetic complexes [M(bpy)(LC)]þ . Thus, the existence
of S,S-coordinated o-dithiobenzosemiquinonate(1) p radical ions has
been proven unequivocally.
electronic structure ¥ palladium ¥
platinum ¥ radical ligands ¥ S ligands
Polymerization Mechanism Determined
J. Wiesecke, M. Rehahn*
567 ± 570
[2.2]Paracyclophanes with Defined Substitution Pattern–Key Compounds for the
Mechanistic Understanding of the Gilch
Reaction to Poly(p-phenylene vinylene)s
cyclophanes ¥ Gilch reaction ¥ radical
reactions ¥ reaction mechanisms
Structures of Polyboron Fluorides
J. A. J. Pardoe, N. C. Norman,
P. L. Timms,* S. Parsons,* I. Mackie,
C. R. Pulham,
D. W. H. Rankin
571 ± 573
The Surprising Structures of B8F12 and
boron ¥ bridging ligands ¥ cluster
compounds ¥ fluorides ¥ X-ray diffraction
Radical reassessment: [2.2]Paracyclophanes D and E have been identified as
the main side-products of the Gilch
reaction leading to poly(p-phenylene
vinylene)s (PPV B). The constitution of the
cyclic dimers allows the conclusion to be
drawn that the PPV formation occurs by
free-radical polymerization of C, initiated
by diradicals A. Anionic chain growth,
often discussed as an alternative to the
radical process, can be excluded.
Unstable, reactive, and yellow: Compound
B8F12, assumed for 30 years to have a
diborane-like structure B2(BF2)6, has now
been shown also to contain a short,
central BB bond. Across the BB bond
are two bridging BF2 groups, which are
bent out of the plane by long-range,
intramolecular F¥¥¥B interactions. The
B-(m-BF2) bonds are long and, surprisingly, asymmetric, but calculations confirm
that this structure is intrinsic to the
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Angew. Chem. Int. Ed. 2003, 42, No. 5
Amide/Hydride Transformation
M. G. Klimpel, P. Sirsch, W. Scherer,
R. Anwander*
574 ± 577
Unsolvated hydride derivatives [Me2Si(2-Me-C9H5)2LnH] (Ln ¼ Y, Ho) are available from ansa-lanthanidocene complexes
by utilizing a novel [N(SiHMe2)2]/[H]
transformation inititated by diisobutylalu-
minumhydride (DIBAH; see scheme;
R ¼ SiHMe2). The molecular structure of
the THF adduct reveals a ™flyover∫ dimer
of composition [{Y(thf)}2{m2-[(h5-2-MeC9H5)SiMe2(h5-2-Me-C9H5)]}2(m2-H)2].
DIBAH-Mediated Amide/Hydride Transformation in ansa-Lanthanidocene(iii)
BIBAH ¥ holmium ¥ hydrides ¥
metallocenes ¥ silylamide ¥ yttrium
Photocatalytic Oxidation
J.-M. Zen,* S.-L. Liou, A. S. Kumar,
M.-S. Hsia
577 ± 579
An Efficient and Selective Photocatalytic
System for the Oxidation of Sulfides to
A heterogenous nafion membrane containing lead ruthenate pyrochlore (Pyc)
and [Ru(bpy)3]2þ (designated as
j NPycxRu(bpy) j ) photochemically catalyzes the selective oxidation of organic
sulfide to sulfoxide in the presence of O2
through formation of H2O2 as an intermediate (see scheme, R ¼ Ph, PhCOCH3,
heterogeneous catalysis ¥ membranes ¥
photochemistry ¥ ruthenium ¥
Stereoselective Alkylation
T. Ooi, E. Tayama,
K. Maruoka*
Virtually complete chirality transfer has
been realized in the N-terminal alkylation
of small, Schiff-base activated peptides
under mild phase-transfer conditions, in
which finely tuned chiral quaternary am-
Communications labeled with
this symbol have been judged
by two referees as being ™very
important papers∫.
Angew. Chem. Int. Ed. 2003, 42, 478 ± 484
monium salts are used as catalysts.
Repeated extension and alkylation of the
N-terminal position can lead selectively to
nonnatural oligopeptides (see picture).
The publication of
Communications labeled with
this symbol has been
accelerated because of their
topical or highly competitive
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579 ± 582
Highly Stereoselective N-Terminal Functionalization of Small Peptides by Chiral
Phase-Transfer Catalysis
alkylation ¥ asymmetric catalysis ¥
peptides ¥ phase-transfer catalysis ¥
synthetic methods
Supporting information for
articles labeled with this symbol
can be found at or
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