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Graphical Abstract Angew. Chem. Int. Ed. 402004

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Contents
The following Communications are available online (in Wiley InterScience). You can find them, as
well as forthcoming Reviews, Highlights, and Essays, at www.angewandte.org, under Early View.
A. Ismach, L. Segev, E. Wachtel, E. Joselevich*:
Atomic-Step-Templated Formation of Single-Wall Carbon Nanotube Patterns
DOI: 10.1002/anie.200460356
Published online: September 28, 2004
M. Lee,* M.-H. Park, N.-K. Oh, W.-C. Zin, H.-T. Jung, D. K. Yoon:
Supramolecular Crystalline Sheets with Ordered Nanopore
Arrays from Self-Assembly of Rigid-Rod Building Blocks
DOI: 10.1002/anie.200460378
Published online: September 23, 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.
Obituary
C. A. A. van Boeckel
Jacques van Boom (1937–2004): Biopolymers
5288 – 5289
Books
Handbook of Metalloproteins
Albrecht Messerschmidt, Wolfram Bode,
Mirek Cygler
reviewed by F. Tuczek
5290
NMR—From Spectra to Structures
Terence N. Mitchell, Burkhard Costisella
reviewed by N. Schlrer
5290
Color Chemistry
Heinrich Zollinger
reviewed by H. Langhals
5291
Highlights
Separation Methods
C. A. M. Afonso,*
J. G. Crespo*
5293 – 5295
Recent Advances in Chiral Resolution
through Membrane-Based Approaches
Ionic Liquids
J. Dupont,* J. Spencer
5296 – 5297
On the Noninnocent Nature of 1,3-Dialkylimidazolium Ionic Liquids
5278
Hollow-fiber membrane contactors, which
can be combined with enzymatic resolution, have already emerged as a potential
technology for enantiomeric resolution
under continuous operation (see scheme;
ORG denotes the organic phase). Furthermore, recently reported optically
active polyelectrolyte multilayer (PEMU)
membranes appear extremely promising
for future applications in preparative
chiral separations.
Presumed innocent, room-temperature
ionic liquids are clean, often reusable,
media for carrying out many synthetic,
catalytic, separation, and analytical processes. However, they are not simply inert
solvents, and a variety of decomposition
pathways have been detected. In the
structure of 1-n-butyl-3-methylimidazolium hexafluorophosphate shown, reactive bonds are marked with arrows (C grey,
N blue, F green, P red).
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5278 – 5286
Angewandte
Chemie
Minireviews
How important is the cooperative attack
of two or more metal centers for dinitrogen activation? The most recent literature,
which provides the focus for this Minireview, helps to improve our understanding
of the factors that determine such important processes as dinitrogen fixation,
cleavage, and elementary transformations.
Dinitrogen Activation
S. Gambarotta,* J. Scott
5298 – 5308
Multimetallic Cooperative Activation of N2
Reviews
Molecular Recognition
Noncovalent interactions are treated as a
form of hydrogen bonding to produce a
new universal scale that can be used to
estimate the free energies of interaction
between any pair of neutral functional
groups in any solvent. The important
parameters are provided by the molecular
electrostatic potential surface (the example depicted is that for carbon tetrachloride).
C. A. Hunter*
5310 – 5324
Quantifying Intermolecular Interactions:
Guidelines for the Molecular Recognition
Toolbox
Communications
Crystal Growth
Stunning tricolored crystals with distinct
regions of green, yellow, and orange
luminescence (see picture) are deposited
in solutions of potassium hydrogen
phthalate that contain proflavin. The dye
serves as a fluorescent probe of surface
charge while identifying the polar crystallographic axis. Optical probes, common
in biochemistry, can be used widely to
study the specificity of noncovalent
chemistry crystal growth from solution.
A. Barbon, M. Bellinazzi, J. B. Benedict,
M. Brustolon,* S. D. Fleming, S.-H. Jang,
B. Kahr,* A. L. Rohl*
5328 – 5331
Luminescent Probes of Crystal Growth:
Surface Charge and Polar Axis Sense in
Dye-Doped Potassium Hydrogen
Phthalate
The hole story: using a new synthetic
concept the title hexa-peri-hexabenzocoronenes (HBCs) were synthesized with
high atom economy. The coaxial arrangement of the HBCs and arylamines allowed
a “double-cable” hole transport (see picture), that is, transport through the central
core (white) and the outer shell (green).
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ANGEWANDTE CHEMIE International
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Angew. Chem. Int. Ed. 2004, 43, 5278 – 5286
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www.angewandte.org
Electron Transfer
J. Wu, M. Baumgarten, M. G. Debije,
J. M. Warman, K. MGllen*
5331 – 5335
Arylamine-Substituted Hexa-peri-hexabenzocoronenes: Facile Synthesis and Their
Potential Applications as “Coaxial” HoleTransport Materials
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 258.00/outside Europe US$ 394.00. Postage
and handling charges included. All Wiley-VCH
prices are exclusive VAT.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5279
Angewandte
Chemie
Nanotechnology
Making DNA work: A DNA nanomachine
with a mechanism based on a DNA
duplex–triplex transition (see figure) was
constructed. The key component is a DNA
triplex that contains C+GC triplets and is
only stable under acidic conditions. The
DNA machine uses H+ and OH ions as
fuel and its only waste products are H2O
and NaCl.
Y. Chen, S.-H. Lee, C. Mao* 5335 – 5338
A DNA Nanomachine Based on a Duplex–
Triplex Transition
Enzyme Labels
D. J. Vocadlo,*
C. R. Bertozzi*
A multipurpose flag: The inactivator 1
covalently labels the catalytic nucleophiles
of retaining b-glycosidases to form species 2. The small azide group allows
labeling of enzymes with sterically con-
gested active sites. Staudinger ligation of
2 with phosphine–FLAG yields adduct 3,
which can be used to detect and profile
retaining b-glycosidase activities in complex mixtures.
New drug design possibilities are suggested by the results of a biological
evaluation of the indole derivative 1 of
pancratistatin, a known anticancer agent,
in a panel of cancer cell lines. Enzymatic
dihydroxylation was one of the key steps in
the short, enantioselective synthesis of 1.
Virtual screening: Based on parameters
which do not have to be measured, sets of
attributes for solids are derived and used
to predict whether a catalyst falls into one
of five performance classes in propene
oxidation, with a predictive power substantially exceeding the statistically
expected values (see table (a confusion
matrix): prediction rate indicates the
5338 – 5342
A Strategy for Functional Proteomic Analysis of Glycosidase Activity from Cell
Lysates
Synthetic Methods
U. Rinner, T. Hudlicky,* H. Gordon,
G. R. Pettit
5342 – 5346
A b-Carboline-1-one Mimic of the Anticancer Amaryllidaceae Constituent Pancratistatin: Synthesis and Biological Evaluation
Combinatorial Catalysis
C. Klanner, D. Farrusseng, L. Baumes,
M. Lengliz, C. Mirodatos,
F. SchGth*
5347 – 5349
correct assignment by the new method,
ratio indicates the statistical expectation
value).
The Development of Descriptors for
Solids: Teaching “Catalytic Intuition” to a
Computer
Synthetic Methods
S. T. Staben, J. J. Kennedy-Smith,
F. D. Toste*
5350 – 5352
Cyclopentenoid structures including
compounds containing vinyl iodide,
1,3-diene, and heterocyclic moieties are
obtained through the gold(i)-catalyzed
5-endo-dig addition of b-dicarbonyl compounds to unactivated alkynes under
Angew. Chem. Int. Ed. 2004, 43, 5278 – 5286
neutral conditions and at room temperature (RT). Both monocyclic and bicyclic
cyclopentenes can be formed in excellent
yields and with good diastereoselectivity
(see scheme).
www.angewandte.org
Gold(i)-Catalyzed 5-endo-dig Carbocyclization of Acetylenic Dicarbonyl
Compounds
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5281
Contents
Brønsted Acids
M. Juhasz, S. Hoffmann, E. Stoyanov,
K.-C. Kim, C. A. Reed*
5352 – 5355
The Strongest Isolable Acid
Measure for measure: Several measures
indicate that carborane acids of the type
H(CHB11R5X6) (see scheme, green R,
red X, gray H, pink B) for R = H, Cl and
X = Cl, Br, I are the strongest pure Brønsted acids. Based on NMR and IR
spectroscopy, H(CHB11Cl11) can lay claim
to be the strongest isolable acid presently
known.
Cluster Compounds
M. W. DeGroot,
J. F. Corrigan*
That zinc in feeling: The complexes [(3,5Me2C5H3N)2Zn(ESiMe3)2] (E = Se, 1;
E = Te, 2) are prepared and found to be
good reagents for the generation of
ternary MM’E materials. From 2 (see
structure; Te red, Zn blue, Si yellow,
N green), the ternary ZnCdTe nanocluster
[Zn2.6Cd7.4Te4(TePh)12(PnPr3)4] (3) is prepared. The optical properties of 3 are
shown to be modulated relative to those
of related binary CdTe cluster molecules.
5355 – 5357
Imine-Stabilized Zinc Trimethylsilylchalcogenolates: Powerful Reagents for
the Synthesis of II-II’-VI Nanocluster
Materials
Alkaloid synthesis
F. Y. Miyake, K. Yakushijin,
D. A. Horne*
5357 – 5360
Preparation and Synthetic Applications of
2-Halotryptophan Methyl Esters:
Synthesis of Spirotryprostatin B
New N-acyliminium ion methodology: 2Halotryptophan esters serve as important
synthetic building blocks for the stereocontrolled construction of spiro[pyrroli-
Helical Structures
Chirality on the side suffices: The screw
sense of 310- and a-helices formed by the
oligopeptides 1, which have no a-carbon
chiral centers, is controlled by the chiral
centers in their side chains. These results
imply that just the side chain chiral
centers of isoleucine and threonine would
affect the secondary structure of their
oligopeptides.
M. Tanaka,* Y. Demizu, M. Doi,
M. Kurihara, H. Suemune* 5360 – 5363
Chiral Centers in the Side Chains of aAmino Acids Control the Helical Screw
Sense of Peptides
5282
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
dine-3,3’-oxindoles] (see scheme). The
cell-cycle inhibitor spirotryprostatin B is
assembled in rapid fashion by using this
methodology.
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5278 – 5286
Angewandte
Chemie
Ionic Liquids
Highly exothermic polymerization reactions of monomers have been carried out
in ionic liquids (ILs) by employing an
accelerating-rate calorimeter (ARC) to
assess the role of the IL. The results
indicate that the IL acts as an ideal heat
sink in controlling the potential for the
reactions to reach thermal runaway as well
as contributing to a significant pressure
reduction (see the acrylonitrile (AN)
example depicted).
R. Vijayaraghavan, M. Surianarayanan,
D. R. MacFarlane*
5363 – 5366
Ionic Liquids as Moderators in
Exothermic Polymerization Reactions
Methane, a building block for basic chemicals through its incorporation into
alkanes: when a methane/propane mixture is passed over a tantalum hydride
catalyst at 250 8C, propane is transformed
into two ethane molecules through the
incorporation of one methane unit. This
reaction corresponds to a cross-metathesis of propane and methane (see
scheme; Alk = alkyl).
C C Bond Formation
D. Soulivong, C. CopRret,*
J. Thivolle-Cazat, J.-M. Basset,*
B. M. Maunders, R. B. A. Pardy,
G. J. Sunley
5366 – 5369
Cross-Metathesis of Propane and Methane: A Catalytic Reaction of C C Bond
Cleavage of a Higher Alkane by Methane
Homogeneous Catalysis
T. Kondo,* Y. Taguchi, Y. Kaneko, M. Niimi,
T Mitsudo*
5369 – 5372
h4-Vinylketene and/or metallacyclopentenone complexes can be considered key
intermediates in the ruthenium- and rhodium-catalyzed ring-opening dimerization
of cyclobutenones to give 2-pyranones as
well as in the rhodium-catalyzed coupling
reactions of cyclobutenones with 2-norbornene (see scheme).
Ru- and Rh-Catalyzed C C Bond Cleavage
of Cyclobutenones: Reconstructive and
Selective Synthesis of 2-Pyranones,
Cyclopentenes, and Cyclohexenones
Imidozirconium Complexes
R. T. Ruck, R. L. Zuckerman, S. W. Krska,
R. G. Bergman*
5372 – 5374
Carboamination: Additions of Imine
C=N Bonds Across Alkynes Catalyzed by
Imidozirconium Complexes
A big plus for addition reactions: A
catalytic amount of an azazirconacyclobutene is used in a novel carboamination
reaction that involves net addition of an
Angew. Chem. Int. Ed. 2004, 43, 5278 – 5286
aldimine across a symmetrical alkyne to
generate highly substituted a,b-unsaturated ketimine products (see scheme;
Cp = C5H5).
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5283
Contents
Reaction Mechanisms
R. T. Ruck, R. G. Bergman*
5375 – 5377
Zirconium-Mediated Conversion of
Amides to Nitriles: A Surprising Additive
Effect
Chloride coordination is the key: Dimethylzirconocene reacts with amides to
form methylzirconium amide complexes.
On heating, in the presence of a chloride
source, these compounds are converted
into N-acylimidozirconocene complexes
that react intramolecularly to form the
corresponding nitrile compounds (see
scheme; Cp = C5H5). Mechanistic studies
reveal that chloride coordination to zirconium is required for this transformation to
occur.
Highly successful tin-free, radical-mediated alkylations of a,b-unsaturated carboxylic amides have been carried out.
Alkyl iodides and bromides bearing aelectron-withdrawing groups undergo
selective g-additions to diene O,N-acetals
(see scheme). This approach to g-functionalization was further extended to the
use of hetero groups, such as phenylsulfanyl and phenylsulfonyl species.
Radical Reactions
S. Kim,* C. J. Lim
5378 – 5380
Radical-Mediated g-Functionalizations of
a,b-Unsaturated Carboxylic Amides
CuCl Nanoplatelets
A. Taubert*
Green approach to inorganic nanostructures: CuCl nanoplatelets (see picture)
were synthesized from mixtures of a Cucontaining ionic liquid crystal and 6-Opalmitoyl ascorbic acid. The particle size,
thickness, and connectivity can be adjusted through varying the reaction temperature. The copper-containing precursor acts as both the template and the
copper source. The ligand is not consumed in the precipitation and can be
reused.
5380 – 5382
CuCl Nanoplatelets from an Ionic LiquidCrystal Precursor
Nanotechnology
H. Skaff, T. Emrick*
5383 – 5386
Reversible Addition Fragmentation Chain
Transfer (RAFT) Polymerization from
Unprotected Cadmium Selenide
Nanoparticles
5284
Nanoparticles functionalized with a trithiocarbonate ligand allow RAFT poly-
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
merization to be performed from their
surface. Homopolymers, random copolymers, and block copolymers can be grown
radially from trithiocarbonate-covered
CdSe nanoparticles (see scheme). This
technique gives excellent nanoparticle
dispersion in a wide range of polymers,
while maintaining the unique photophysical properties of the nanoparticles.
Angew. Chem. Int. Ed. 2004, 43, 5278 – 5286
Angewandte
Chemie
Considerable oxacarbenium ion character
may be in the transition state of a highly bselective mannosylation reaction that
proceeds via an a-mannosyl triflate. An adeuterium kinetic isotope effect of 1.2 was
measured at 78 8C (= 1.1 at 25 8C). This
information may be interpreted in terms
of a stereoselective trapping of a transient
contact ion pair or, alternatively, as representative of an “exploded” transition state
(see scheme).
Glycosylation Mechanism
D. Crich,*
N. S. Chandrasekera
5386 – 5389
Mechanism of 4,6-O-BenzylideneDirected b-Mannosylation as Determined
by a-Deuterium Kinetic Isotope Effects
Erythrina Alkaloids
S. A. A. El Bialy, H. Braun,
L. F. Tietze*
Domino effect: The skeleton of erythrina
and B-homoerythrina alkaloids can be
constructed in an efficient manner from
readily available substrates (see Scheme)
by a three-step domino reaction. These
natural products constitute an interesting
class of compounds because of their
extensive biological activity.
A Highly Efficient Synthesis of the
Erythrina and B-Homoerythrina Skeleton
by an AlMe3-Mediated Domino Reaction
Bright particles: The optical properties of
luminescent nanocrystals (quantum dots,
QDs) can be exploited only if they are have
an appropriate surface derivatization. A
straightforward method is presented to
encapsulate single QDs with a homogeneous silica shell, while retaining their
high luminescence (see picture).
Nanostructures
T. Nann,* P. Mulvaney
5393 – 5396
Single Quantum Dots in Spherical Silica
Particles
Metal–Nucleobase Complexes
A mechanism goes platinum: Hydrolytic
deamination of cytosine is a major mutagenic event in DNA. Studies with a model
system and DFT calculcations demonstrate that deamination is facilitated by
coordination of the PtII center to the N3
atom (see scheme; C = cytosine,
U = uracil).
Angew. Chem. Int. Ed. 2004, 43, 5278 – 5286
5391 – 5393
J. E. Šponer,* P. J. Sanz Miguel,
L. RodrTguez-Santiago, A. Erxleben,
M. Krumm, M. Sodupe,* J. Šponer,
B. Lippert*
5396 – 5399
Metal-Mediated Deamination of Cytosine:
Experiment and DFT Calculations
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5285
Contents
Fluorescent Probes
Glowing marks: A new class of protein
stains, the pyrylium dyes, undergo a
strong color change (typically from blue to
red, see picture) on covalently binding to
proteins. While the free stains are almost
nonfluorescent, the protein-conjugated
forms are highly fluorescent. The dyes do
not alter the charge of a protein, and thus
do not change its electrophoretic properties. The stains also can be used in
quantitative protein assays.
B. K. Wetzl, S. M. Yarmoluk, D. B. Craig,
O. S. Wolfbeis*
5400 – 5402
Chameleon Labels for Staining and
Quantifying Proteins
Acid-free Friedel–Crafts chemistry: A
paradox? Nucleophilicity scales, based on
reactions with benzhydrylium ions, show
that many p systems are more nucleophilic than aqueous or alcoholic solutions
that are generally employed as solvents
for SN1 reactions. Solvolytically generated
carbocations can, therefore, be trapped by
donor-substituted arenes and alkenes to
form products of Friedel–Crafts-type
reactions in neutral aqueous solutions
(see scheme).
Friedel–Crafts Reactions
M. Hofmann, N. Hampel, T. Kanzian,
H. Mayr*
5402 – 5405
Electrophilic Alkylations in Neutral
Aqueous or Alcoholic Solutions
Synthetic Methods
As part of a succinct synthesis, a new
functionalization method leads to hitherto
unknown polysilanols with an oligosilane
backbone, a class of compounds with
remarkable electronic properties. The trifluoroacetolysis of phenyl-substituted
hydroxyoligosilanes yield trifluoroacetoxyoligosilanes almost quantitatively,
and these can be converted into tri- and
tetrasilanol, such as that shown, simply by
hydrolysis.
C. Krempner,* J. Kopf, C. Mamat,
H. Reinke, A. Spannenberg 5406 – 5408
Novel Polysilanols by Selective
Functionalizations of Oligosilanes
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
Service
Keywords
5410
Authors
5411
Angewandte’s
Sister Journals
Preview
5286
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5412 – 5413
5415
Angew. Chem. Int. Ed. 2004, 43, 5278 – 5286
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