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Graphical Abstract Angew. Chem. Int. Ed. 322004

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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.
J. M. J. Paulusse, R. P. Sijbesma*:
Reversible Mechanochemistry of a PdII Coordination Polymer
DOI: 10.1002/anie.200460040
Published online: July 28, 2004
N. Pinna,* G. Neri, M. Antonietti, M. Niederberger*:
Nonaqueous Synthesis of Nanocrystalline Semiconducting
Metal Oxides for Gas Sensing
DOI: 10.1002/anie.200460610
Published online: July 28, 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.
Orville L. Chapman (1932–2004): Organic Chemistry and Education
R. J. McMahon
Experimental Design for Combinatorial
and High Throughput Materials
James N. Cawse
reviewed by U. S. Schubert
Organosilanes in Radical
Chryssostomos Chatgilialoglu
reviewed by D. L. J. Clive
A catalytic option: Tertiary amines are
converted into the corresponding aamino nitriles in the presence of hydrated
ruthenium trichloride (5 mol %), sodium
cyanide (1.2 equiv), and molecular oxygen
(see scheme). This is a valuable alternative to the Strecker synthesis of a-amino
nitriles and can be used to prepare N-aryl
glycine derivatives and unsymmetrical
Synthesis of a-Amino Nitriles
M. North*
4126 – 4128
Oxidative Synthesis of a-Amino Nitriles
from Tertiary Amines
Imaging Agents
M. Green*
Dots in cells: Recent advances in the use
of functionalized semiconductor quantum
dots in bioimaging, from cancer studies to
blood-flow monitoring, are described. The
image shows a mouse fibroplast labeled
with two different sizes (and therefore two
different colors) of CdSe/ZnS quantum
4129 – 4131
Semiconductor Quantum Dots as
Biological Imaging Agents
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 4114 – 4121
P. Chen, S. I. Gorelsky, S. Ghosh,
4132 – 4140
E. I. Solomon*
N2O Reduction by the m4-Sulfide-Bridged
Tetranuclear CuZ Cluster Active Site
A spectrum of unusual features: N2O
reduction is accomplished in biology by
an active site consisting of a m4-sulfidebridged tetranuclear copper cluster (the
CuZ center), which has many unusual
spectroscopic features. Recent studies
have led to electronic-structure descriptions of resting CuZ, its catalytically relevant form, and elucidated the role of CuZ
in N2O activation and reduction (see
Alkene Oxygenation
A rational improvement of rhodium/iridium-catalyzed olefin oxygenation by
dioxygen or hydrogen peroxide requires
more detailed insight into underlying
mechanisms and ligand effects (see
scheme). In this Review, results from
model studies are related to known catalytic systems, and differences between
rhodium/iridium- and palladium-catalyzed olefin oxidation are discussed.
B. de Bruin,* P. H. M. Budzelaar,
A. W. Gal
4142 – 4157
Functional Models for Rhodium-Mediated
Olefin-Oxygenation Catalysis
CP and CAs Bonds
M. Finze, E. Bernhardt, H. Willner,*
C. W. Lehmann
4160 – 4163
[(CF3)3BCP] and [(CF3)3BCAs]:
Thermally Stable Phosphaethynyl and
Arsaethynyl Complexes
Make mine a triple: The tetraphenyl
phosphonium salts of [(CF3)3BCX]
(X = P, As) are stable even well above
room temperature. The synthesis of these
first phospha- and arsaethynyl complexes
of boron from (CF3)3BCO is carried out in
two steps (see scheme). The complex
[(CF3)3BCAs] is the first stable anionic
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Angew. Chem. Int. Ed. 2004, 43, 4114 – 4121
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Classical feeding experiments indicate
involvement of nonribosomal peptide,
polyketide, and isoprenoid biosynthesis in
the formation of the myxobacterial antibiotic leupyrrin (1). The resulting structural elements are modified further (e.g.
by a semipinacol-like rearrangement and
oxidative formation of a methylene
bridge) to yield the unique leupyrrin
H. B. Bode, S. C. Wenzel, H. Irschik,
G. HLfle, R. MMller*
4163 – 4167
Unusual Biosynthesis of Leupyrrins in the
Myxobacterium Sorangium cellulosum
Cluster Compounds
M. Pley, M. S. Wickleder*
4168 – 4170
The Cluster Ion [Pt12O8(SO4)12]4
Scanning Electrochemical Microscopy
C. Zhao, G. Wittstock*
4170 – 4172
An SECM Detection Scheme with
Improved Sensitivity and Lateral Resolution: Detection of Galactosidase Activity
with Signal Amplification by Glucose
Platinum dumbbells: The reaction of
platinum nitrate with concentrated sulfuric acid at 350 8C leads to the deep red
oxide–sulfate (NH4)Pt3O2(SO4)3, in which
six [Pt2]6+ dumbbells are linked by oxide
ions and sulfate groups to the novel
cluster anion [Pt12O8(SO4)12]4 (see picture). The structure of the core of this
anion matches exactly the recent prediction for dodecanuclear complexes built
from six metal dumbbells.
An enzymatic amplification cycle is used
in a novel detection scheme for scanning
electrochemical microscopy (SECM). An
immobilized enzyme system comprising
galactosidase and PQQ-dependent
glucose dehydrogenase was imaged by
SECM with high sensitivity and high
lateral resolution.
PQQ = pyrroloquinolinequinone.
Protein Folding
M. Mutter,* A. Chandravarkar, C. Boyat,
J. Lopez, S. Dos Santos, B. Mandal,
R. Mimna, K. Murat, L. Patiny, L. SaucOde,
4172 – 4178
G. Tuchscherer
Switch Peptides In Statu Nascendi:
Induction of Conformational Transitions
Relevant to Degenerative Diseases
S on
S on
S off
A novel concept for triggering conformational transitions, and thus changes in
structure and function, in peptides with a
switching element S provides intriguing
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
perspectives for studying molecular processes (see scheme) that play a key role,
for example, in early events of Alzheimer’s
Angew. Chem. Int. Ed. 2004, 43, 4114 – 4121
Gas-Phase Reactions
A motion breaking with tradition: The cis–
trans isomerization of nonpolar conjugated p systems does not proceed simply
by the 1808 twist of a C¼C bond (“onebond flip”, OBF), but by the rotation of a
central CH group out of the plane (“hula
twist”, HT). The hula-twist motion does
not require any external constraint but is
driven by an internal force: the slope on
the way through a conical intersection.
W. Fuß,* C. Kosmidis, W. E. Schmid,
S. A. Trushin
4178 – 4182
The Photochemical cis–trans Isomerization of Free Stilbene Molecules Follows a
Hula-Twist Pathway
Divide and conquer: A novel approach
was used to separate solvent effects from
the intrinsic interactions involved in the
association of biological complexes (see
figure). The enthalpy of solvent reorganization for the formation of an intermolecular hydrogen bond in a biomolecular
complex was determined by comparing
the solution and gas-phase stabilities of
structurally related complexes.
Biological Complexes
Robo copper: A mechanically robust corrugated sheet, 1 DOP-Cu, is composed of
mats of individual chain-bundles joined by
p–p interactive forces (see structure).
Upon electrochemical charge injection
into 1 DOP-Cu, the variations of the cell
parameters of the Li-inserted phase were
observed by X-ray diffraction. The
mechanical deformation of the whole
sheet is produced by a CuII/CuI redox
Supramolecular Machines
E. N. Kitova, D. R. Bundle,
J. S. Klassen*
Partitioning of Solvent Effects and
Intrinsic Interactions in Biological
K.-J. Lin,* S.-J. Fu, C.-Y. Cheng, W.-H. Chen,
4186 – 4189
H.-M. Kao
Towards Electrochemical Artificial
Muscles: A Supramolecular
Machine Based on a One-Dimensional
Copper-Containing Organophosphonate
Contact Printing
Pressing a rubber stamp inked with
carboxylic acids onto an amine-terminated surface leads to the formation of
amide bonds at room temperature (see
scheme). Oligopeptides were created on
the surface in this way from a monolayer.
This rapid and uncatalyzed formation of
amide bonds is attributed to the nanoscale confinement of the molecules
between the stamp and the preorganized
monolayer substrate.
PDMS = poly(dimethylsiloxane).
Angew. Chem. Int. Ed. 2004, 43, 4114 – 4121
4183 – 4186
T. P. Sullivan, M. L. van Poll,
P. Y. W. Dankers,
W. T. S. Huck*
4190 – 4193
Forced Peptide Synthesis in Nanoscale
Confinement under Elastomeric Stamps
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Cysteine Protease Inhibitors
P. M. O’Neill,* P. A. Stocks, M. D. Pugh,
N. C. Araujo, E. E. Korshin, J. F. Bickley,
S. A. Ward, P. G. Bray, E. Pasini, J. Davies,
E. Verissimo, M. D. Bachi* 4193 – 4197
Design and Synthesis of Endoperoxide
Antimalarial Prodrug Models
A masked combination chemotherapy
which relies on the embedding of a
number of active components, in a latent
form, within a single endoperoxidic
chemical entity is the aim of the research
presented. The approach is illustrated by
means of purposely designed bicyclic
endoperoxide prodrug prototypes 1 and
subsequently validated through the study
of model compounds 2 (Ar = Ph, p-FC6H4,
Z. Yuan, C.-W. Lee,
S.-H. Lee*
4197 – 4200
Reversible Thermochromism in
Hydrogen-Bonded Polymers Containing
Out of the blue: A reversible temperaturedependent change in the absorption
characteristics of spin-coated terephthalic
acid/diacetylene polymers is observed.
The polymer is prepared by topochemical
photopolymerization of the diacetylene
First among unequals: Equal CC bond
lengths, as found in benzene, are not
necessary for aromaticity. [18]Annulene is
the next HMckel monocycle where D6h
symmetry is possible topologically (see
picture). However, this widely accepted
structure of [18]annulene is not correct.
The 1H NMR chemical shifts and energy
computations show that [18]annulene
prefers CC bond-length alternation and
C2 symmetry.
C. S. Wannere, K. W. Sattelmeyer,
H. F. Schaefer III,
P. v. R. Schleyer*
4200 – 4206
Aromaticity: The Alternating CC Bond
Length Structures of [14]-, [18]-, and
Natural Products Synthesis
The five crucial steps in the first total
synthesis of (þ)-scyphostatin from darabinose involve (see picture): a) stereoselective aldol coupling to form a
quaternary stereocenter, b) ring-closing
metathesis (RCM) to construct the cyclohexene ring, c) Negishi coupling for the
preparation of the fatty acid side chain,
d) amide formation to connect the cyclohexene and fatty acid segments, e) stereospecific epoxide-ring formation.
M. Inoue, W. Yokota, M. G. Murugesh,
4207 – 4209
T. Izuhara, T. Katoh*
Total Synthesis of (þ)-Scyphostatin, a
Potent and Specific Inhibitor of Neutral
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
side chains of the stacked terephthalic
acid units (see picture). The absorption
bands of the polymeric product move
reversibly from 640 nm (blue form of the
polymer) to 580 nm (red form) during
heating–cooling cycles.
Angew. Chem. Int. Ed. 2004, 43, 4114 – 4121
CH Activation
Y. Cui, C. He*
Opportunities with silver: A dinuclear
silver(i) compound was found to
efficiently catalyze the intramolecular
amidation of saturated CH bonds of
carbamates and sulfamates (see scheme).
This highly regioselective, stereospecific
reaction offers a practical method for the
construction of cyclic nitrogen-containing
organic molecules.
4210 – 4212
A Silver-Catalyzed Intramolecular
Amidation of Saturated CH Bonds
Nickel Hydroxide Tubes
Higher capacity rechargeable batteries
can be constructed by using mesoscale
nickel hydroxide tubes as the positiveelectrode material. The tubes were prepared by deposition of nickel ions and
aqueous ammonia in an anodic alumina
membrane as the template. The picture
shows a high-resolution TEM image of the
F.-S. Cai, G.-Y. Zhang, J. Chen,* X.-L. Gou,
4212 – 4216
H.-K. Liu, S.-X. Dou
Ni(OH)2 Tubes with Mesoscale Dimensions as Positive-Electrode Materials of
Alkaline Rechargeable Batteries
The folding/unfolding of a protein structure has been studied through measuring
the donor–donor energy migration
between two fluorescent probes (F)
coupled selectively to the N termini of the
homodimeric DsbC protein (see picture).
The fluorometric strategy provides a convenient and reliable method to investigate
conformational changes in dimeric
Fluorescence Spectroscopy
X. Duan, Z. Zhao, J. Ye, H. Ma,* A. Xia,*
G. Yang, C.-C. Wang*
4216 – 4219
Donor–Donor Energy-Migration
Measurements of Dimeric DsbC Labeled
at Its N-Terminal Amines with Fluorescent
Probes: A Study of Protein Unfolding
Domino Radical Cyclization
D. Leca, L. Fensterbank,* E. LacTte,*
M. Malacria*
4220 – 4222
A phosphinoyl radical leaving group in
the b position is a key feature of a new
TiIII-mediated domino radical cyclization/
Angew. Chem. Int. Ed. 2004, 43, 4114 – 4121
b elimination reaction of vinylic phosphine oxides, which affords alkylidenepyrrolidines in good yields (see scheme).
Titanium-Mediated Domino Radical
Cyclization/b Elimination of Phosphine
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Natural Products Synthesis
X. Pu, D. Ma*
A common bicyclic intermediate was used
in an efficient strategy towards lepadins B,
D, E, and H shown. These alkaloids are
members of a family of natural products
with diverse biological activity. The
described total syntheses of lepadins D, E,
and H enabled the full elucidation of their
4222 – 4225
Total Synthesis of Lepadins B, D, E, and
H; Determination of the Configuration of
the Latter Three Alkaloids
Asymmetric Oxidations
J. Legros, C. Bolm*
4225 – 4228
Highly Enantioselective Iron-Catalyzed
Sulfide Oxidation with Aqueous Hydrogen
Peroxide under Simple Reaction
An attractive alternative to the currently
existing methods for the metal-catalyzed
oxidation of sulfides to sulfoxides is
asymmetric iron-catalyzed oxidation with
hydrogen peroxide as the terminal oxidant
(see scheme). In the presence of a
benzoic acid derivative, this simple
process provides sulfoxides with up to
96 % ee in moderate to good yields
(up to 78 %).
Extracting the P: Two novel amorphous
allotropes of elemental phosphorus that
consist of polymeric chains (see example
depicted) were obtained in a pure form by
extraction from their copper iodide
adducts with an aqueous solution of
potassium cyanide. 31P NMR spectra and
high-resolution TEM images suggest that
the structure of these phosphorus nanorods is unchanged after extraction.
Exclusive coupling: High turnover numbers were attained in the dehydrogenative
coupling reaction between C(sp2) and
C(sp3) atoms. A zirconium catalyst mediates the coupling reactions of heterocyclic
arenes and lactams exclusively at the
carbon atom adjacent to the nitrogen
atom of the latter under an oxygen
atmosphere (see scheme).
Phosphorus Nanorods
A. Pfitzner,* M. F. BrUu, J. Zweck,
G. Brunklaus, H. Eckert*
4228 – 4231
Phosphorus Nanorods—Two Allotropic
Modifications of a Long-Known Element
Coupling Reactions
T. Tsuchimoto,* Y. Ozawa, R. Negoro,
E. Shirakawa,* Y. Kawakami 4231 – 4233
Zirconium Triflate Catalyzed Direct
Coupling Reaction of Lactams with
Heterocyclic Arenes under Atmospheric
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 4114 – 4121
Angew. Chem. Int. Ed. 2004, 43, 4114 – 4121
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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