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Graphical Abstract Angew. Chem. Int. Ed. 242004

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Contents
The following Communication is available online (in Wiley InterScience). You can find it, as well as
forthcoming Reviews, Highlights, and Essays, at www.angewandte.org, under Early View.
A. Gutnov,* B. Heller,* C. Fischer, H.-J. Drexler, A. Spannenberg,
B. Sundermann, C. Sundermann:
Cobalt(i)-Catalyzed Asymmetric [2�] Cycloaddition of
Alkynes and Nitriles: Synthesis of Enantiomerically Enriched
Atropoisomers of 2-Arylpyridines
DOI: 10.1002/anie.200454164
Published online: May 26, 2004
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 its 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.
Web Sites
http://www.uni-wuerzburg.de/
mineralogie/crystal/teaching/
teaching.html
Crystallography: Conserving an
Endangered Species.
H.-B. Brgi and T. Weber
Joseph Mizrahi
reviewed by B. Cornils
3098
Books
Developing an Industrial Chemical
Process
3099
Introduction to Cluster Dynamics
3099
Paul-Gerhard Reinhard, Eric Suraud
reviewed by B. Hartke
Modern Carbonyl Olefination
3100
Takeshi Takeda
reviewed by B. Cornils
Another brick in the wall: Organic groups
that contain several alkoxysilane substituents are applied in the synthesis of
hybrid inorganic?organic mesoporous
materials (see scheme). The resulting
materials contain the organic moiety as an
integral part of the wall. Depending on the
functionality of the organic groups and on
the properties of the functionalized
porous material a plethora of potential
applications can be envisioned.
Highlights
Mesoporous Composites
G. Kickelbick*
3102 ? 3104
Hybrid Inorganic?Organic Mesoporous
Materials
3090
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 3090 ? 3096
Angewandte
Chemie
Minireviews
Bioorganic Chemistry
M. K8hn, R. Breinbauer*
3106 ? 3116
The Staudinger Ligation?A Gift to
Chemical Biology
Bioconjugation made easy: The Staudinger ligation between azides and acylmodified phosphanes is probably the
mildest and most chemoselective ligation
reaction. It has found widespread application in chemical biology and can even
be used in the complex environment of a
living cell (see scheme).
Reviews
Coagulation inhibition: Heparin has been
used clinically as an antithrombotic agent
since the 1940s. For decades researchers
have been working on the development of
alternatives with improved pharmacological properties and better-defined modes
of action. The picture shows the synthetic
pentasaccharide fondaparinux in the conformation it adopts when complexed with
antithrombin III.
Antithrombotics
M. Petitou,*
C. A. A. van Boeckel*
3118 ? 3133
A Synthetic Antithrombin III Binding
Pentasaccharide Is Now a Drug!
What Comes Next?
Communications
Getting in tune: A material that undergoes
valence tautomerism was obtained by
tuning the electronic properties of a
cobalt?polyoxolene complex (shown
schematically) which contains a tripositive metal ion acting as an ancillary
counterpart. The tautomerism, which can
be thermally or light induced, is quantitative upon irradiation at 617 nm.
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Angew. Chem. Int. Ed. 2004, 43, 3090 ? 3096
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
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www.angewandte.org
Electron Transfer
C. Carbonera, A. Dei,* J.-F. LAtard,*
C. Sangregorio, L. Sorace
3136 ? 3138
Thermally and Light-Induced Valence
Tautomeric Transition in a Dinuclear
Cobalt?Tetraoxolene Complex
individuals who are personal members of a
national chemical society, or whose institution
already subscribes, or who are retired or selfemployed consultants, print only: Europe
E 248.00/outside Europe US$ 378.00. Postage
and handling charges included. All Wiley-VCH
prices are exclusive VAT.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3091
Contents
Enzyme Screening
R. H. P. DoezA, B. A. Maltman, C. L. Egan,
R. V. Ulijn, S. L. Flitsch*
3138 ? 3141
Profiling Primary Protease Specificity by
Peptide Synthesis on a Solid Support
Reverse screening: A greatly simplified
primary screening of protease specificity
has been achieved by monitoring the
fluorescence during the protease-catalyzed coupling of amino acids instead of
peptide hydrolysis on a solid support (see
picture, AA = amino acid). This approach
paves the way for flexible, rapid, highthroughput identification and characterization of proteases without the need for
expensively labeled peptide arrays.
Charged but not changed: A trinuclear
[NiFe] cluster combining the key structural features and reactivity of [NiFe]
hydrogenases has been prepared (structure shown). Protons oxidize this cluster
to its cation, which has the same structural
parameters as the neutral form and
therefore shows an important key feature
of many oxidoreductases: structural
rigidity during the electron-transfer
processes.
Bioinorganic Chemistry
D. Sellmann, F. Lauderbach,* F. Geipel,
F. W. Heinemann, M. Moll 3141 ? 3144
A Trinuclear [NiFe] Cluster Exhibiting
Structural and Functional Key Features of
[NiFe] Hydrogenases
Oligonucleotide Complexes
A. Bugaut, J.-J. ToulmA,
B. Rayner*
3144 ? 3147
Use of Dynamic Combinatorial Chemistry
for the Identification of Covalently
Appended Residues that Stabilize
Oligonucleotide Complexes
Amplification with kissing: Rapid identification of covalently appended residues
that stabilize oligonucleotide complexes
has been achieved by using a dynamic
combinatorial approach that leads to
amplification of the best ligand (see
schematic representation). Both a DNA
duplex and an RNA loop?loop (kissing)
complex were investigated. Melting-temperature experiments confirmed that the
amplified species stabilize the complexes.
Azide Complexes
Out of line? Theory predicts that [Ti(N3)4]
should exhibit unprecedented linear
TiNNN bond angles as a consequence
of the a-N atoms of the azide groups
acting as tridentate donors into the empty
tetrahedral d0 orbitals of a (㱮v) Group 4
metal atom. The title compounds were
prepared and characterized (see structure). They do not possess linear TiN
NN angles because their coordination
numbers exceed four.
R. Haiges,* J. A. Boatz, S. Schneider,
T. Schroer, M. Yousufuddin,
K. O. Christe*
3148 ? 3152
The Binary Group 4 Azides
[Ti(N3)4], [P(C6H5)4][Ti(N3)5], and
[P(C6H5)4]2[Ti(N3)6] and on Linear
TiNNN Coordination
3092
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 3090 ? 3096
Angewandte
Chemie
Differentiating helices: The direct observation of hydrogen bonds by 3hJN,C? scalar
couplings (see picture) is not only possible for a-helix and b-sheet peptides and
proteins, but for 310-helical peptides as
well. The method also provides information on terminal fraying of helices and
allows the discrimination between a and
310 helices.
Helical Structures
M. Bellanda, M. Rainaldi,
Q. B. Broxterman, B. Kaptein,
F. Formaggio, M. Crisma, S. Mammi,
C. Toniolo*
3152 ? 3155
Direct Observation of Intramolecular
Hydrogen Bonds in Peptide 310 Helices by
3h
JN,C? Scalar Couplings
Vanadium?Alkylidene Complexes
F. Basuli, U. J. Kilgore, X. Hu, K. Meyer,
M. Pink, J. C. Huffman,
D. J. Mindiola*
3156 ? 3159
Kinetically stable, four-coordinate vanadium(iv) neopentylidene complexes
such as [(Nacnac)V糃HtBu(thf)](BPh4)
(Nacnac = [Ar]NC(Me)CHC(Me)N[Ar],
Ar = 2,6-(CHMe2)2C6H3), which was pre-
pared by oxidatively induced a-hydrogen
abstraction from [(Nacnac)V(CH2tBu)2]
with AgBPh4 in THF (see structure),
contain the shortest V糃 bonds known to
date.
Cationic and Neutral Four-Coordinate
Alkylidene Complexes of Vanadium(iv)
Containing Short V糃 Bonds
DNA Synthesis
M. Taki, Y. Kato, M. Miyagishi, Y. Takagi,
K. Taira*
3160 ? 3163
Small-Interfering-RNA Expression in Cells
Based on an Efficiently Constructed
Dumbbell-Shaped DNA
A dumbbell-shaped DNA, expected to be
useful for gene therapy, was synthesized
by using a novel method. The dumbbellshaped vector (see picture) contains a
small interfering RNA (siRNA) coding
sequence, and the vector was used to
investigate the RNA interference (RNAi)
effect inside cells.
Sugar-Based Surfactants
C. Larpent,* A. Laplace,
T. Zemb
Each block carries out a designated task:
Amphiphilic molecules are obtained by
grafting one or several surfactant blocks
with a bulky sugar headgroup onto a
macrocyclic complexing block. This
Angew. Chem. Int. Ed. 2004, 43, 3090 ? 3096
modular approach allows control of the
structure of the aggregates (see scheme)
and formation of micelles insensitive to
the presence of complexed metal ions.
www.angewandte.org
3163 ? 3167
Macrocyclic Sugar-Based Surfactants:
Block Molecules Combining Self-Aggregation and Complexation Properties
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3093
Contents
Natural Products Synthesis
K. Ohmori, K. Mori, Y. Ishikawa,
H. Tsuruta, S. Kuwahara, N. Harada,
K. Suzuki*
3167 ? 3171
Concise Total Synthesis and Structure
Assignment of TAN-1085
Rapid access to the tetracyclic core of
TAN-1085 (1) was possible by exploiting
three efficient processes: a tandem electrocyclic reaction (A), a pinacol cyclization
Mixed-Valence Structures
S. Takaishi,* H. Miyasaka, K.-i. Sugiura
M. Yamashita,* H. Matsuzaki, H. Kishida,
H. Okamoto, H. Tanaka, K. Marumoto,
H. Ito, S. Kuroda, T. Takami 3171 ? 3175
Visualization of Local Valence Structures
in Quasi-One-Dimensional HalogenBridged Complexes [Ni1xPdx(chxn)2Br]Br2
by STM
(B), and a regioselective monobenzoylation of a 1,2-diol (C), which allowed the
first total synthesis of 1.
State secrets: Mott?Hubbard and chargedensity-wave states have been observed in
the quasi-1D bromine-bridged Ni and Pd
complexes [M(chxn)2Br]Br2, respectively,
using STM (see image for the Ni complex,
the arrow denotes the direction of the
chain). The spin soliton was also visualized in real space in the Ni-Pd mixedmetal complexes for the first time. chxn:
(1R,2R)-diaminocyclohexane.
Natural Products Synthesis
Y. Murata, T. Kamino, T. Aoki,
S. Hosokawa,
S. Kobayashi*
3175 ? 3177
Highly Efficient Total Synthesis of
(�)-Citreoviral
Only eight steps were required for the
total synthesis of (�)-citreoviral (3) from
chiral imide 1 in 18 % overall yield. The key
steps included a highly anti-selective aldol
reaction, the stereoselective iodolacton-
RNA Structures
Adenine flips out: A combination of X-ray
crystallography, 2-aminopurine fluorescence labeling, and the use of aminoglycosides as ligands is exploited to
demonstrate conformational transitions
in the RNA domain that ensures accurate
protein synthesis (see picture). The triggering of a conformational change of an
adenine unit in the RNA by ligand binding
can be used as the basis of a screening
method to discover antibiotics.
S. Shandrick, Q. Zhao, Q. Han, B. K. Ayida,
M. Takahashi, G. C. Winters,
K. B. Simonsen, D. Vourloumis,
T. Hermann*
3177 ? 3182
Monitoring Molecular Recognition of the
Ribosomal Decoding Site
3094
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
ization of a g,d-unsaturated b-hydroxyimide, and an intramolecular SN2 reaction
of a tertiary alcohol to form intermediate
2.
Angew. Chem. Int. Ed. 2004, 43, 3090 ? 3096
Angewandte
Chemie
Cluster Compounds
A round peg in a square hole: The unusual
bonding situation within the cluster ion
[{Ti4O}I12]4 (see picture) arises through
the optimization of strong TiTi and TiO
s bonding as well as to the absence of
TiTi multiple (p) bonding and the
avoidance of TiI antibonding interactions.
L. Jongen, A.-V. Mudring, A. M8ller,
G. Meyer*
3183 ? 3185
An Oxygen-Centered Titanium Square
Embedded in a Cuboctahedron of Iodine
in the Salt K4[{Ti4O}I12]
The largest organometallic cluster compound consisting of Al, C, and H only
* , Cp* = C5Me5) is a fascinatingly
(Al50Cp12
simple structure of comparably high
symmetry (see structure). The pentamethylcyclopentadienyl ligands form a
carbon shell similar to the arrangement
found in fullerene structures.
Shell suits: Two shells of Ga12 icosahedra
characterize the arrangement of 24 gallium atoms in the title compound (see
structure). The structure indicates connectivity possibilities of Ga12 units that are
analogous to the topology of the a-boron
modification.
J. Vollet, J. R. Hartig,
H. Schn8ckel*
3186 ? 3189
Al50C120H180 : A Pseudofullerene Shell of 60
Carbon Atoms and 60 Methyl Groups
Protecting a Cluster Core of 50 Aluminum
Atoms
Cluster Compounds
T. Duan, E. Baum, R. Burgert,
H. Schn8ckel*
3190 ? 3192
The Polyhedral Gallium Subhalide
[Ga24Br22]� THF: The First Step on the
Path to a New Modification of Gallium?
Rod?Coil Copolymers
Giant rod?coil amphiphilic block copolymers were prepared by metallocene-catalyzed polymerization. The hydrophilic
coiled block consists of polymethacrylic
acid and the rod component of a hydrophobic cylindrical brush polymer. The high
solubility of the stiff block results in the
micelles being formed with the stiff block
forming the solubilizing corona.
Angew. Chem. Int. Ed. 2004, 43, 3090 ? 3096
Cluster Compounds
M. W. Neiser, S. Muth, U. Kolb,
J. R. Harris, J. Okuda,*
M. Schmidt*
3192 ? 3195
Micelle Formation from Amphiphilic
?Cylindrical Brush??Coil Block Copolymers Prepared by Metallocene Catalysis
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3095
Contents
Asymmetric Synthesis
O. Barun, S. Sommer,
H. Waldmann*
3195 ? 3199
Asymmetric Solid-Phase Synthesis of
6,6-Spiroketals
Structurally simplified spiroketals derived
from natural products often retain the
biological activity of the parent
compound. An asymmetric solid-phase
synthesis with boron-mediated aldol
reactions as key stereodifferentiating
transformations provides 6,6-spiroketals
in just 12 steps in high yield and with high
stereoselectivity (see scheme). The
procedure is suitable for the creation of
compound libraries for use in medicinal
chemistry.
Communications labeled with this symbol have been judged by two referees as being ?very important papers?.
Service
Keywords
3200
Authors
3201
Preview
3203
Corrigendum
*
3096
In the Communication ?Direct Evidence
for Extremely Facile 1,2- and 1,3-GroupMigrations in an FeSi2 System? by H.
Tobita et al. (Angew. Chem. 2004, 116,
223?226; Angew. Chem. Int. Ed. 2004, 43,
221?224, DOI 10.1002/anie.200352519),
the 1H NMR data of complex 4 in the
Experimental Section were given incorrectly. The correct data for 4 are given
below: 1H NMR (300 MHz, [D6]benzene):
d = 0.69 (s, 3H, SiMesMe2), 0.97 (s, 3H,
SiMesMe2), 1.03 (s, 3H, SiMesMe), 1.09
(s, 9H, CMe3), 1.46 (s, 15H, C5Me5), 2.15
(s, 3H, p-Me), 2.23 (s, 3H, p-Me), 2.45 (s,
6H, o-Me), 2.52 (s, 3H, o-Me), 2.64 (s, 3H,
o-Me), 6.78 (s, 2H, m-H), 6.84 (s, 1H,
m-H), 6.88 ppm (s, 1H, m-H).
In the Communication ?HydrogenBonded Helices in the Layered Aluminophosphate (C2H8N)2[Al2(HPO4)(PO4)]? by
J. Yu, R. Xu, et al. (Angew. Chem. 2004,
116, 2453?2456; Angew. Chem. Int. Ed.
2004, 43, 2399?2402, DOI 10.1002/
anie.200353118), on page 2400, left
column, line 27, an oxygen atom was
inadvertently mislabeled. The sentence
should be: P(1) shares two O atoms with
adjacent Al atoms and has one terminal
POH group (P(1)O(12) 1.563(4) W)
and one terminal P糘 group (P(1)糘(1)
1.470(3) W), while P(2) and P(3) each
share three oxygen atoms with adjacent
Al atoms and have one terminal P糘
group (P(2)糘(2) 1.493(3) W, P(3)糘(5)
1.489(3) W).
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 3090 ? 3096
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