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Graphical Abstract Angew. Chem. Int. Ed. 482003

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Contents
The following articles are available online (in Wiley InterScience). You can find them at
www.angewandte.org, under Full Text, Early View.
K. Koszinowski, D. Schrder, H. Schwarz*:
Coupling of Methane and Ammonia by
Dinuclear Bimetallic Platinum?CoinageMetal Cations PtM+
DOI: 10.1002/anie.200352817
Published online: December 5, 2003
C. Lemire, R. Meyer, Sh. Shaikhutdinov,
H.-J. Freund*:
Do Quantum Size Effects Control CO
Adsorption on Gold Nanoparticles?
DOI: 10.1002/anie.200352538
Published online: December 2, 2003
L. Zhao, S. K. Pal, T. Xia, A. H. Zewail*:
Dynamics of Ordered Water in Interfacial
Enzyme Recognition: Bovine Pancreatic
Phospholipase A2
DOI: 10.1002/anie.200352961
Published online: December 8, 2003
Articles judged by the referees or the editor as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editorial office in final form. As long as there is no page number available these articles should be
cited in the following manner:
Author(s) Angew. Chem. Int. Ed., online publication date, DOI.
News
Materials Science: German Future Award
for Merck Team
5922
Biophysical Chemistry: C. Griesinger
Recognized
5922
Biochemistry: H. Waldmann Receives
Bergmann Medal
5922
Rosette M. Roat-Malone
reviewed by F. Meyer
Jerome A. Berson
reviewed by S. J. Weininger
Imagine? if the biomachinery of nature
accepted every uncoded amino acid sitespecifically as desired. Spectacular
advances in breaking the genetic code to
expand the set of amino acids available for
protein biosynthesis are highlighted, and
examples of the post-translational chemical modification of proteins containing
these nonnatural amino acids are presented (see scheme).
Books
Bioinorganic Chemistry
5924
Chemical Discovery and the Logicians?
Program
5924
Highlights
Protein Design
J. H. van Maarseveen,*
J. W. Back
5926 ? 5928
Re-Engineering the Genetic Code:
Combining Molecular Biology and
Organic Chemistry
Nanotechnology
M. Burghard*
5929 ? 5930
Carbon Nanotubes by Quantitative SolidState Conversion of an Organometallic
Precursor
5912
Optimization of synthesis methods for
carbon nanotubes is an essential requirement for realizing their potential applications in field-emission devices, (bio)sensors, or as electrical interconnections in
microchips. Procedures directly yielding
clean nanotubes from a single molecular
precursor (see picture) are highly desired
and are expected to provide important
clues to the general mechanism of nanotube formation.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 5912 ? 5919
Angewandte
Chemie
Reviews
A radical view of oxygenation: As revealed
by recent research, radical intermediates
are almost ubiquitous during metalassisted oxo-functionalizations of organic
substrates (see picture). This review
covers examples from the areas as diverse
as homogeneous and heterogeneous
chemistry, as well as metalloenzyme systems.
Oxygenation
C. Limberg*
5932 ? 5954
The Role of Radicals in Metal-Assisted
Oxygenation Reactions
Communications
Plasma chemistry
N. SchiefenhAvel, H.-J. Himmel,
M. Binnewies*
5956 ? 5957
Microwave magic: GC?MS analysis and
quantum chemical calculations were used
to show that N2(SiCl3)4 was a product of
the reaction of SiCl4 with N2 activated with
a gas plasma generated by microwaves.
N2(SiCl3)4 is the first known perhalogenated silyl hydrazine (see scheme: N blue,
Si gray, Cl green).
N2(SiCl3)4?A Tetrakissilylhydrazine as an
Unexpected Product of the Reaction
between N2 and SiCl4
Asymmetric Synthesis
K. MuFiz,* M. Nieger,
H. MansikkamGki
A mechanistic puzzle in the field of
osmium(viii)-mediated functionalization
of olefins: How do the diaminations of
olefins to give osmaimidazolidines with a
stereogenic osmium center proceed (see
scheme: C: gray, N: green, red: O, Os:
pink)?
5958 ? 5961
Stereochemically Defined Osmium
Centers from Asymmetric Diamination
of Olefins: Mechanistic Implications
for Osmium-Mediated Acrylate
Functionalization
Modeling Metalloproteins
P. Spuhler,
M. C. Holthausen*
The core of the problem: The selective
hydroxylation of benzylic CH bonds by a
[Cu2O2]2+ core is a nonsynchronous concerted process (see scheme). This is the
result of density functional calculations on
the mechanistic scenario of the monooxygenase reactivity of a bis(m-oxo)dicopper(iii) complex.
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(valid for print and electronic/print or electronic
Angew. Chem. Int. Ed. 2003, 42, 5912 ? 5919
www.angewandte.org
5961 ? 5965
Mechanism of the Aliphatic Hydroxylation
Mediated by a Bis(m-oxo)dicopper(iii)
Complex
delivery); for individuals who are personal
members of a national chemical society, or
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are retired or self-employed consultants, print
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5913
Contents
Poly(acetylene)s
J. O. Krause, M. T. Zarka, U. Anders,
R. Weberskirch, O. Nuyken,*
M. R. Buchmeiser*
5965 ? 5969
Simple Synthesis of Poly(acetylene) Latex
Particles in Aqueous Media
The metathesis catalyst 1 allows the first
living cyclopolymerization of 1,6-heptadiynes. With the chiral 4-(ethoxycarbonyl)4-(1S,2R,5S)-(■)-menthoxycarbonyl-1,6heptadiyne highly tactic polymers with an
alternating cis?trans structure and a stereoregularity of greater than 95 % are
obtained. Fixation of 1 on poly(2-oxazoline) block copolymers provides access to
poly(acetylene)s under aqueous conditions by micellar catalysis.
A semiautomated high-throughput
system has been developed to express
and purify proteins and assay their catalytic activity. The screen can be used to
evolve activity, selectivity, and expression
levels of proteins directly or in combination with selections. To illustrate its
potential, the system was applied to the
directed evolution of catalytic antibodies
with aldolase activity.
Stacking the deck: A series of aromatic
fluorinated nucleosides (the electrostatic
surface potentials are depicted) was used
to probe electrostatic effects in the stacking of DNA bases in water. Although
increasing fluorine substitution (from
zero through five) generally increases
stacking ability, a new tetrafluorinated
analogue is, surprisingly, the strongest
helix stabilizer, while the pentafluorinated
base is the weakest.
Screening for Protein Catalysts
J. Gildersleeve, A. Varvak, S. Atwell,
D. Evans, P. G. Schultz*
5971 ? 5973
Development of a High-Throughput
Screen for Protein Catalysts: Application
to the Directed Evolution of Antibody
Aldolases
DNA Structures
J. S. Lai, J. Qu, E. T. Kool*
5973 ? 5977
Fluorinated DNA Bases as Probes of
Electrostatic Effects in DNA Base Stacking
Cage Compounds
F. K. Larsen,* J. Overgaard, S. Parsons,
E. Rentschler, A. A. Smith, G. A. Timco,*
R. E. P. Winpenny*
5978 ? 5981
Horseshoes, Rings, and Distorted Rings:
Studies of Cyclic Chromium-Fluoride
Cages
5914
Running rings around ammonium: Use of
amine templates leads to a rich structural
chemistry for heterometallic cyclic compounds. For example, use of two diethylammonium cations leads to the formation of the {Cr10Cu2} cage, which is
stabilized by NHиииF bonds (see picture).
The results suggest a new method for
making sophisticated polymetallic architectures.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 5912 ? 5919
Angewandte
Chemie
Organolanthanides with amido-tethered
N-heterocyclic carbenes: a new bidentate
ligand that tethers an N-heterocyclic carbene group to a trivalent lanthanide
complex (samarium, depicted,
N?? = N(SiMe3)2 ; or yttrium) affords the
first organolanthanide amido?carbene
complexes and an opportunity to explore
the strength and reactivity of the early
metal?N-heterocyclic carbene fragment.
Organolanthanide Complexes
P. L. Arnold,* S. A. Mungur, A. J. Blake,
C. Wilson
5981 ? 5984
Anionic Amido N-Heterocyclic Carbenes:
Synthesis of Covalently Tethered
Lanthanide?Carbene Complexes
Sensors
M. Matsushita,* K. Yoshida,
N. Yamamoto, P. Wirsching, R. A. Lerner,
K. D. Janda*
5984 ? 5987
Blue lights the way! The rapid evaluation
of enantiomeric excess in the highthroughput screening of libraries has been
a hurdle to the discovery of effective
catalysts. A blue-fluorescent monoclonal
antibody (mAb) addresses this problem;
mAb 19G2 is used as a fluorescent sensor
(see picture) to evaluate a panel of
Cinchona alkaloid derivatives in the synthesis of asymmetric amino acids by
phase-transfer catalysis.
High-Throughput Screening by Using a
Blue-Fluorescent Antibody Sensor
Natural Product Synthesis
B. M. Trost,* D. B. Horne,
M. J. Woltering
A potential general approach to potent
N-heterocyclic glycosidase inhibitors is
illustrated by the first total synthesis of
(■)-broussonetine G (1). The key transformation of the synthesis relies on two
successive palladium-catalyzed asymmetric allylic alkylations of butadiene monoxide with a nitrogen nucleophile to
construct the pyrrolidine core.
Sterically protected tri- and hexanuclear
platinum clusters were used as building
blocks for the high-yield synthesis of a
first-generation dendrimer (see picture;
tBu groups are omitted for clarity), which
is chemically and thermally stable, and in
which the cluster units are separated by
conjugated 1,3,5-triethynylphenyl groups.
Angew. Chem. Int. Ed. 2003, 42, 5912 ? 5919
www.angewandte.org
5987 ? 5990
Palladium-Catalyzed DYKAT of Vinyl
Epoxides: Enantioselective Total
Synthesis and Assignment of the
Configuration of (■)-Broussonetine G
Pt Dendrimer Synthesis
A. Albinati, P. Leoni,* L. Marchetti,
S. Rizzato
5990 ? 5993
Assembling Metal Clusters with Covalent
Linkers: Synthesis and Structure of a
Quasi-Planar Pt18 Dendrimer Containing
Five Clusters Connected by s-Alkynyl
Spacers
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5915
Contents
Pd-Catalyzed C?C Coupling
D. Gelman, S. L. Buchwald* 5993 ? 5996
Efficient Palladium-Catalyzed Coupling
of Aryl Chlorides and Tosylates with
Terminal Alkynes: Use of a Copper
Cocatalyst Inhibits the Reaction
Less catalyst, lower temperature, and
greater generality are the advantages of
the new general protocol over those
previously described for the palladiumcatalyzed coupling of aryl chlorides and
alkynes (see scheme). Better results are
obtained without a copper cocatalyst,
which has been found to inhibit product
formation in the coupling reaction of aryl
chlorides with terminal alkynes.
An entirely substrate-controlled total synthesis of three members of the thapsigargin family (e.g. trilobolide) is achieved
starting from (S)-carvone. The synthesis is
linear in nature but is achieved in high
yield (> 90 % per step). The route permits
late-stage divergence, providing access to
a range of natural products and structural
analogues.
Natural Products
S. F. Oliver, K. HAgenauer, O. Simic,
A. Antonello, M. D. Smith,
S. V. Ley*
5996 ? 6000
A Route to the Thapsigargins from
(S)-Carvone Providing a SubstrateControlled Total Synthesis of Trilobolide,
Nortrilobolide, and Thapsivillosin F
Supported Catalysts
A. Hu, H. L. Ngo, W. Lin*
Catalytic building blocks: Chiral porous
zirconium phosphonates containing Rubinap moieties are synthesized by a
molecular building-block approach, and
characterized by a variety of techniques.
These hybrid solids are used for enantioselective heterogeneous asymmetric
hydrogenation of b-keto esters with
ee values of up to 95 % (see picture).
Ready tunability of such a molecular
building-block approach promises to lead
to useful heterogeneous asymmetric catalysts.
6000 ? 6003
Chiral, Porous, Hybrid Solids for Highly
Enantioselective Heterogeneous
Asymmetric Hydrogenation of
b-Keto Esters
Molecular Wheels
H.-J. Zhai, A. N. Alexandrova, K. A. Birch,
A. I. Boldyrev, L.-S. Wang*
6004 ? 6008
Hepta- and Octacoordinate Boron in
Molecular Wheels of Eight- and NineAtom Boron Clusters: Observation and
Confirmation
5916
Two types of aromaticity: Experimental
and theoretical evidence shows that eightand nine-atom boron clusters are perfectly
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
planar molecular wheels, with a hepta- or
octacoordinated central boron atom,
respectively (see picture, B green). The
radii of the miniature molecular wheels
are found to be 1.8 and 2.0 U. Analyses of
their chemical bonding reveal that they
possess double (s and p) aromaticity,
which is responsible for the wheel structures and the extreme coordination environments.
Angew. Chem. Int. Ed. 2003, 42, 5912 ? 5919
Angewandte
Chemie
Asymmetric Oxidative Coupling
J. Gao,* J. H. Reibenspies,
A. E. Martell
6008 ? 6012
Structurally Defined Catalysts for
Enantioselective Oxidative Coupling
Reactions
Copper(ii)-based complex catalysts (see
crystal structures) were prepared and
characterized by X-ray crystallography.
They were shown to be active catalysts for
asymmetric oxidative coupling of 2-naphthol with high enantioselectivity.
Natural Product Synthesis
Good health! Although not initially present in red wine, acutissimin A (see picture) and other flavano-ellagitannins are
formed during aging in oak barrels by a
diastereoselective nonenzymatic condensation reaction between flavan-3-ols
present in grapes and ellagitannin vescalagin from oak. Acutissimin A is a DNA
topoisomerase inhibitor that is 250-fold
more potent in vitro than the clinically
used anicancer drug etoposide.
In a supermolecular system, the sum of
properties is more than that of the
individual components. The combination
Angew. Chem. Int. Ed. 2003, 42, 5912 ? 5919
S. Quideau,* M. Jourdes, C. Saucier,
Y. Glories, P. Pardon,
C. Baudry
6012 ? 6014
DNA Topoisomerase Inhibitor Acutissimin A and Other Flavano-Ellagitannins in
Red Wine
of rod and disc shaped groups (see
picture) in the right ratio allows the design
of a material with nematic and several
layered (smectic) phases. Shape-induced
nanophase segregation of rods and discs
leads to the formation of distinct sublayers.
Liquid Crystals
Taking the temperature: The electronic
properties of DNA largely depend on the
orientation of the p stacking. Based on
the discrete clusters of interstrand fourbase p stacks in Z-form DNA, a molecular
thermometer that exploits the differences
in the p stackings of B- and Z-DNA has
been designed (see picture).
Molecular Devices
www.angewandte.org
P. H. J. Kouwer,
G. H. Mehl*
6015 ? 6018
Multiple Levels of Order in Linked Disc?
Rod Liquid Crystals
R. Tashiro, H. Sugiyama*
6018 ? 6020
A Nanothermometer Based on the
Different p Stackings of B- and Z-DNA
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5917
Contents
Helical Polymers
S. Hecht,* A. Khan
6021 ? 6024
Intramolecular Cross-Linking of Helical
Folds: An Approach to Organic Nanotubes
The tubular secondary structure of a
folded helical polymer?a poly(m-phenyleneethynylene) derivative carrying multiple cinnamate moieties?is stabilized by
intramolecular cross-linking through topochemically controlled photodimeriza-
tions (see schematic representation). This
approach should enable the generation of
organic nanotubes with controlled
dimensions and surface functionality that
constitute attractive building blocks for
functional nanostructures.
Communications labeled with this symbol have been judged by two referees as being ?very important papers?.
The publication of Communications labeled with this symbol has been accelerated because of their topical or highly competitive
nature.
Service
Keywords
6028
Authors
6029
Angewandte?s
Sister Journals
5918
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
6026 ? 6027
Index
6031
Preview
6157
Angew. Chem. Int. Ed. 2003, 42, 5912 ? 5919
Angewandte
Chemie
Corrigenda
*
In the Communication ?Ligand and Metal
Effects on the Formation of Main-Group
Polyhedral Clusters? by M. P. Coles, A. E.
H. Wheatley et al. (Angew. Chem. Int. Ed.
2003, 42, 5593 ? 5596), Figure 2 refers to
compound 11 and not to compound 9.
In the Communication ?A Stable Salt of
the Tris(ethene)silver Cation: Structure
and Characterization of [Ag(h2-C2H4)3]+[Al{OC(CF3)3}4]? by I. Krossing and
A. Reisinger (Angew. Chem. Int. Ed. 2003,
42, 5725 ? 5728) the last entry in column 2
(correct version: 1610 (vw; a1?)) and the
penultimate entry in column 3 of Table 1
(correct version: 1575 (3 km mol1, e?)[a] )
were erroneously switched during the
editing process.
Angew. Chem. Int. Ed. 2003, 42, 5912 ? 5919
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5919
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