вход по аккаунту


Graphical Abstract Angew. Chem. Int. Ed. 292004

код для вставкиСкачать
The following Communications are available online (in Wiley InterScience). You can find them, as
well as forthcoming Reviews, Highlights, and Essays, at, under Early View.
P. Wu, A. K. Feldman, A. K. Nugent,
C. J. Hawker,* A. Scheel, B. Voit, J. Pyun,
J. M. J. Fr&chet, K. B. Sharpless,*
V. V. Fokin*:
Efficiency and Fidelity in a Click-Chemistry
Route to Triazole Dendrimers by the
Copper(i)-Catalyzed Ligation of Azides
and Alkynes
DOI: 10.1002/anie.200454078
Published online: June 30, 2004
K. C. Nicolaou,* S. Vyskocil, T. V. Koftis,
Y. M. A. Yamada, T. Ling, D. Y.-K. Chen,
W. Tang, G. Petrovic, M. O. Frederick, Y. Li,
M. Satake*:
Structural Revision and Total Synthesis of
Azaspiracid-1, Part 1: Intelligence Gathering and Tentative Proposal
DOI: 10.1002/anie.200460695
Published online: June 25, 2004
K. C. Nicolaou,* T. V. Koftis, S. Vyskocil,
G. Petrovic, T. Ling, Y. M. A. Yamada,
W. Tang, M. O. Frederick:
Structural Revision and Total Synthesis of
Azaspiracid-1, Part 2: Definition of the
ABCD Domain and Total Synthesis
DOI: 10.1002/anie.200460696
Published online: June 29, 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.
Meeting Reviews
When Chemistry Met Biology
3750 ? 3751
T. Berg
Inorganic Electrochemistry
Piero Zanello
reviewed by D. Astruc
Organotin Chemistry
Alwyn G. Davies
reviewed by M. Weidenbruch
Multitasking catalysts: Metal catalysis has
been pushed to a new level with the
development of methods that use a single
catalyst for several fundamentally different transformations in a single reaction
flask (see example). Several examples
from the recent literature are highlighted,
including methods in which a single
catalyst mediates two reactions simultaneously. Mes = 2,4,6-trimethylphenyl,
Cy = cyclohexyl.
Multifunctional Catalysis
A. Ajamian, J. L. Gleason*
3754 ? 3760
Two Birds with One Metallic Stone:
Single-Pot Catalysis of Fundamentally
Different Transformations
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 3742 ? 3749
Wrap artists: Hollow polyelectrolyte
microcapsules have promising perspectives in numerous applications, such as
engineering, biotechnology, and medicine. In this Review, the recent advances
in this field are presented, with a focus on
the permeability properties of the capsules as well as on their application as
microreactors. The picture shows a library
of 15 dye-modified capsules of poly(allylamine)/poly(styrene sulfonate).
Materials Science
C. S. Peyratout, L. D<hne*
3762 ? 3783
Tailor-Made Polyelectrolyte Microcapsules: From Multilayers to Smart
Asymmetric Synthesis
B. Breit,* P. Demel,
C. Studte
Selectivity at the flick of a switch: Through
1,3-chirality transfer, a directing/nondirecting leaving group facilitates the stereospecific and stereodivergent construction of quaternary carbon centers by
copper-mediated allylic substitution with
Grignard and organozinc reagents (see
scheme; the use of the corresponding
phosphane oxide leads to selective anti
3786 ? 3789
Stereospecific and Stereodivergent
Construction of Quaternary Carbon
Centers through Switchable Directed/
Nondirected Allylic Substitution
B. Breit,* C. Herber
3790 ? 3792
Can?t have too much of a good thing: A
flexible, iterative strategy based on a
highly selective copper-mediated allylic
substitution makes the preparation of any
desired oligo(deoxypropionate) stereoisomer possible (see scheme; RDG = re-
agent-directing group). This approach
differs from the established enolate-alkylation methodology through the reversed
polarity of the reaction partners and
avoids several problems associated with
the latter method.
Iterative Deoxypropionate Synthesis
Based on a Copper-Mediated Directed
Allylic Substitution
For the USA and Canada:
Edition (ISSN 1433-7851) is published weekly
by Wiley-VCH PO Box 191161, D 69451 Weinheim, Germany. Air freight and mailing in the
USA by Publications Expediting Inc. 200 Meacham Ave., Elmont, NY 11003. Periodicals
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
NJ 07030. Annual subscription price for institutions: Europe E 3430.00/3118.00; outside
Europe US$ 4499.00/4090.00 (valid for print
and electronic/print or electronic delivery); for
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.
Angew. Chem. Int. Ed. 2004, 43, 3742 ? 3749
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Stability Constants
B. Knobloch, R. K. O. Sigel,* B. Lippert,
H. Sigel
3793 ? 3795
Two Metal Ions Coordinated to a Purine
Residue Tolerate Each Other Well
The catalytic sites of ribozymes generally
contain two or more metal ions. Guanine
is the nucleobase most often involved in
binding to metal ions. The repulsion
between two M2+ ions simultaneously
coordinated to guanine in aqueous solution was investigated by using complex 1
(see picture; dien = diethylenetriamine,
R = C2H5) as a model, for which the
stability constants for the binding of Mg2+
and Cu2+ were determined.
Asymmetric Catalysis
A. Gutnov,* B. Heller,* C. Fischer,
H.-J. Drexler, A. Spannenberg,
B. Sundermann,
C. Sundermann
3795 ? 3797
Cobalt(i)-Catalyzed Asymmetric [2�]
Cycloaddition of Alkynes and Nitriles:
Synthesis of Enantiomerically Enriched
Atropoisomers of 2-Arylpyridines
N. MarmK, J.-P. Knemeyer, J. Wolfrum,
M. Sauer*
3798 ? 3801
Highly Sensitive Protease Assay Using
Fluorescence Quenching of Peptide
Probes Based on Photoinduced Electron
A new flavor of chiral induction in the
[2�] cycloaddition yielding pyridines:
Atropoisomers were prepared in the
reaction of alkynes and nitriles in the
Making the cut and then detecting it:
Short fluorophore-labeled peptide substrates (see scheme) show strong fluorescence quenching due to electron
transfer from a tryptophan residue (blue)
to the dye (gray, red). Upon specific
cleavage of the peptide by proteolytic
enzymes, quenching is prevented and the
fluorescence intensity increases. The
3803 ? 3806
Fabrication of Polymer Nanofibers and
Carbon Nanofibers by Using a SaltAssisted Microemulsion Polymerization
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
method can be used to assay proteolytic
enzymes with detection limits in the
picomolar range.
Salt-assisted sphere-to-cylinder micelle
conversion in the microemulsion polymerization process is the crucial step for
the formation of polyacrylonitrile nanofibers (see picture). Iron(iii) chloride is
used as a structure-directing agent and is
coordinated by polyacrylonitrile nanoparticles, which is essential for the formation
of the nanofibers.
Conducting Materials
J. Jang,* J. Bae
presence of 1 mol % chiral CoI catalysts
such as 1 with high yields and up to
93 % ee.
Angew. Chem. Int. Ed. 2004, 43, 3742 ? 3749
Microarray Technology
J. Eppinger,* D. P. Funeriu,* M. Miyake,
L. Denizot, J. Miyake
3806 ? 3810
High-throughput screening of libraries of
potential inhibitors is possible by using an
enzyme microarray method that combines low sample consumption with
accuracy and speed. Information about
Enzyme Microarrays: On-Chip Determination of Inhibition Constants Based on
Affinity-Label Detection of Enzymatic
enzyme inhibition can be obtained ?onchip? by the addition of a fluorescently
tagged affinity label to a microarray of
functional enzymes (see picture).
The intermolecular interactions that lead
to translational and alternate molecular
stacking of 1,3-diene monomers in the
solid state (see example, X = CO2CH2C6H4OCH3) as well as the molecular
symmetry of muconic acid derivatives
have been utilized in controlling the
stereoregularity of polymers. This crystal
engineering approach has enabled the
four kinds of stereoregular diene polymers
to be synthesized in a solid-state
A thrust in the right direction: Two different disk-shaped ligands (a tris-monodentate and a hexa-monodentate ligand) and
three Ag+ ions have been used as bearings
and balls, respectively, in the construction
of a molecular thrust ball bearing (see
schematic representation). Rotation
occurs through a combination of intramolecular, reversible multipoint ligand
S. Nagahama, T. Tanaka,
A. Matsumoto*
3811 ? 3814
Supramolecular Control over the
Stereochemistry of Diene Polymers
Molecular Devices
S. Hiraoka, K. Hirata,
M. Shionoya*
3814 ? 3818
A Molecular Ball Bearing Mediated by
Multiligand Exchange in Concert
exchange and flip motions that act in
Biologically Active Compounds
G. Yang, J. Schmieg, M. Tsuji,
R. W. Franck*
3818 ? 3822
Which source provides the better drug?
The fully synthetic C-glycoside 1 (Y = CH2)
is about 1000 times more potent against
malaria in mice than the corresponding Oglycoside (Y = O), which is derived from a
Angew. Chem. Int. Ed. 2004, 43, 3742 ? 3749
natural product and itself known to show
remarkable activity against a wide range of
diseases. The results of comparative biological assays emphasize the potential of
C-glycosides as therapeutic agents.
The C-Glycoside Analogue of the
Immunostimulant a-Galactosylceramide
(KRN7000): Synthesis and Striking
Enhancement of Activity
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Cluster Compounds
Difficult to determine, the molecular
structure of the ionic cluster
[Ag26In18S36Cl6(dppm)10(thf)4]2+[InCl4(thf) ]2 (see picture, dppm = bis(diphenylphosphanyl)methane) was independently resolved by theoretical (density
functional theory) and experimental
(single-crystal XRD, FTMS) methods. The
cluster was synthesized by the reaction of
AgOOCPh and InCl3 with S(SiMe3)2 in the
presence of the bidentate phosphane
R. Ahlrichs, A. EichhPfer, D. Fenske,*
O. Hampe, M. M. Kappes, P. Nava,
J. Olkowska-Oetzel
3823 ? 3827
Synthesis and Structure of
?A Combined Approach of Theory
and Experiment
X. Sun, Y. Li*
Carbon spheres are used as templates to
prepare semiconductor hollow spheres of
Ga2O3 (depicted) and GaN. The thickness
and uniformity of the final products are
predetermined by the thickness of the
active layer of the carbon spheres. The
diameter of the spheres can be adjusted in
the range of 100 nm to 1.5 mm, which
covers the band gaps in the spectral
regime from UV to near infrared.
3827 ? 3831
Ga2O3 and GaN Semiconductor Hollow
Cage Compounds
U. N. Nehete, G. Anantharaman,
V. Chandrasekhar, R. Murugavel,
M. G. Walawalkar, H. W. Roesky,*
D. Vidovic, J. Magull, K. Samwer,
B. Sass
3832 ? 3835
Polyhedral Ferrous and Ferric Siloxanes
The synthesis, isolation, and single-crystal
X-ray structures of the first polyhedral
ferrous and ferric siloxanes (see scheme)
Molecular Electronics
E. Tran, M. A. Rampi,*
G. M. Whitesides*
3835 ? 3839
Electron Transfer in a Hg-SAM//SAM-Hg
Junction Mediated by Redox Centers
suggest that similar synthetic strategies
will allow the preparation of other transition-metal siloxane frameworks.
Current affairs: The electron-transport
properties of a metal?molecule?metal
junction based on two contacting redoxactive self-assembled monolayers of
[Ru(NH3)5(NC5H4-4-CH2NHCO(CH2)10SH](PF6)2 (see picture) is described. The
junction becomes conductive when the
electrode potentials are adjusted to the
formal potential of the redox centers and
shows diode- and transistor-like characteristics analogous to those of solid-state
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 3742 ? 3749
Mesoporous Materials
J. E. Lim, C. B. Shim, J. M. Kim,* B. Y. Lee,*
J. E. Yie
3839 ? 3842
Electron-deficient silicon atoms, which are
generated on a silica surface by evacuation above 900 K, are attacked by Grignard
reagents (see picture). This reactivity
provides a novel route for the surface
modification of mesoporous silicas as the
organic groups are strongly bound to the
surface through the formation of SiC
bonds. The pore structures of the mesoporous silicas are not destroyed by the
Dehydroxylation Route to Surface
Modification of Mesoporous Silicas
by Using Grignard Reagents
Main-Group-Metal Clusters
U. N. Nehete, V. Chandrasekhar,
G. Anantharaman, H. W. Roesky,*
D. Vidovic, J. Magull
3842 ? 3844
The hexatin(ii) cage containing siloxane
ligands is obtained by the addition of
Sn[N(SiMe3)2]2 to a suspension of
RSi(OH)3 in a hexane/THF mixture (see
scheme). The X-ray crystal structure analysis of compound 1 reveals a central
{(SnO)6} motif enclosed by two outer
{R2Si2O3} siloxane ligands.
Molecular {(SnO)6} Trapped by Two
{R2Si2O3} Fragments: X-ray Single-Crystal
Structure of [(SnO)6(R2Si2O3)2]
Ionic Liquids
N. D. Clement, K. J. Cavell*
Reactive Couples: Imidazolium salts react
with alkenes under mild conditions in the
presence of a Ni0-based catalyst to produce 2-alkyl imidazolium salts (see
scheme, cod = 1,5-cyclooctadiene). The
mechanism involves oxidative addition of
an imidazolium CH bond to M0 to give a
(carbene)MH intermediate and finally
bond formation between the carbene and
an alkyl ligand through reductive elimination.
Fits like a glove! The dicopper(ii) complex
1 of a bistren cage containing ditolyl
spacers binds dicarboxylate anions in
aqueous solutions. The inclusion is highly
selective on the basis of the distance
between the COO groups. For example,
terephthalate (see picture) is discriminated from isophthalate and phthalate.
Angew. Chem. Int. Ed. 2004, 43, 3742 ? 3749
3845 ? 3847
Transition-Metal-Catalyzed Reactions
Involving Imidazolium Salt/N-Heterocyclic Carbene Couples as Substrates
Anion Sensors
M. Boiocchi, M. Bonizzoni, L. Fabbrizzi,*
G. Piovani, A. Taglietti
3847 ? 3852
A Dimetallic Cage with a Long Ellipsoidal
Cavity for the Fluorescent Detection of
Dicarboxylate Anions in Water
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Metal Hydride Complexes
High thermal stability is a characteristic
feature of the depicted amido indium
hydride complex (In red; hydride yellow),
which is amongst the first to be synthesized and characterized. The stability
arises from steric shielding of the InH
bond, which frustrates the formation of
the intermolecular InHIn bridges.
R. J. Baker, C. Jones,* P. C. Junk,
M. Kloth
3852 ? 3855
Kinetic Control over the Thermal Stability
of the InH Bond: Synthesis and Characterization of Amido Indium Hydride
Communications labeled with this symbol have been judged by two referees as being ?very important papers?.
Sister Journals
3858 ? 3859
In the Communication ?Continuous Glucose Sensing with a Fluorescent Thin-Film
Hydrogel? by B. Singaram et al. (Angew.
Chem. Int. Ed. 2003, 42, 5857?5859,
DOI 10.1002/anie.200352405) on page
5859, the top right paragraph says ?operate under physiological conditions (37 8C,
0.1 mm ionic strength, pH 7.4)?. Instead it
should read ?operate under physiological
conditions (37 8C, 0.1 m ionic strength,
pH 7.4)?.
In the Communication ?The Circumambulation of a Phosphirane: Taking 9Phenyl-9-phosphabicyclo[6.1.0]nona-2,4,6triene for a ?Walk?? by K. Lammertsma
et al. (Angew. Chem. Int. Ed. 2004, 43,
714 ? 717, DOI 10.1002/anie.200351855),
the 1H NMR chemical shift of compound
3P of 3.65 ppm should be 2.65 ppm and
the 31P NMR chemical shift at 179 ppm
should be reversed in sign. The first
reference reporting the conversion of 3P
to 7P should also have been cited: T. J.
Katz, C. R. Nicholson, C. A. Reilly, J. Am.
Chem. Soc. 1966, 88, 3832 ? 3842.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 3742 ? 3749
In the Communication ?Diffusion-Limited, Aggregation-Based, Mesoscopic
Assembly of Roughened Core-Shell
Bimetallic Nanoparticles into Fractal Networks at the Air?Water Interface? by Y. Jin
and S. Dong (Angew. Chem. Int. Ed. 2002,
41, 1040?1044), the title is incorrect. The
correct title is: ?Diffusion-Limited, Aggregation-Based, Mesoscopic Assembly of
Surface-Roughened Shell-Type Bimetallic
Nanoparticles into Fractal Networks at the
Air?Water Interface?. The interior-hol-
lowed structure of the unit bimetallic
nanoparticles was clearly revealed in a
related publication (Y. D. Jin, S. J. Dong, J.
Phys. Chem. B 2003, 107, 12902?12905).
The authors apologize for this oversight.
In the Communication ?Size-dependent
Magnetic Properties of Colloidal Mn3O4
and MnO Nanoparticles? by J. T. Park
et al. (Angew. Chem. Int. Ed. 2004,
43, 1115 ? 1117, DOI 10.1002/
anie.200352400), the following important
reference for the preparation of soluble,
monodisperse MnO and Mn3O4 is missing: M. Yin, S. O?Brien, J. Am. Chem. Soc.
2003, 125, 10 180 ? 10 181. This work
appeared online (August 5, 2003) during
the review process and eluded the
authors? attention.
Angew. Chem. Int. Ed. 2004, 43, 3742 ? 3749
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Без категории
Размер файла
677 Кб
abstract, int, angel, 292004, chem, graphical
Пожаловаться на содержимое документа