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Graphical Abstract Angew. Chem. Int. Ed. 422004

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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. Rencurosi, E. P. Mitchell, G. Cioci, S. Prez, R. Pereda-Miranda,*
A. Imberty*:
Crystal Structure of Tricolorin A: Molecular Rationale for the
Biological Properties of Resin Glycosides Found in Some
Mexican Herbal Remedies
DOI: 10.1002/anie.200460327
Published online: September 21, 2004
J. P. Rolland, E. C. Hagberg, G. M. Denison, K. R. Carter,*
J. M. De Simone*:
High-Resolution Soft Lithography: Enabling Materials for
Nanotechnologies
DOI: 10.1002/anie.200461122
Published online: October 11, 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.
News
Siegfried Medal Awarded to Joel
M. Hawkins
5568
Arndt Simon Receives
Liebig Medal
5568
Lutz F. Tietze Is Awarded the
Emil Fischer Medal
5568
Books
Handbook of Elemental Speciation
Rita Cornelis, Joe Caruso, Helen Crews,
Klaus Heumann
reviewed by U. Karst
5569
Pseudo-Peptides in Drug Discovery
Peter E. Nielsen
reviewed by K. Kawai
5569
Highlights
Total Syntheses
U. Koert*
Syntheses of Tetrodotoxin
5558
5572 – 5576
A meal of carefully prepared puffer fish,
which hopefully does not contain the toxic
livers and ovaries, tests the courage of
gourmets and cooks. Tetrodotoxin (formula shown), the poisonous principle of
the puffer fish, presents a challenge for
synthesis, which has been mastered by
three teams using different strategies and
key steps.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
Angewandte
Chemie
High-Throughput Screening
Survival of the fittest describes a new
method for screening dynamic combinatorial libraries. A mixture of dipeptides is
tested for binding to a target protein, and
the weaker binding compounds are
destroyed by pronase. The released components are then recoupled to regenerate
the library. By repeating this cycle of
selection, destruction, and regeneration, a
small binding preference eventually
results in a large enrichment of the
tightest binding compound. Photo credit
Douglas Jager (http://www.mindspring.com/~bjager/akpix2.html).
J.-L. Reymond*
5577 – 5579
Outrunning the Bear
Minireviews
OC without CO: Innovative strategies for
solving the drawbacks associated with the
handling of toxic, gaseous carbon monoxide in carbonylation reactions are
described. These strategies, some of
which are shown schematically, highlight
a variety of experimentally simple and safe
tools for carbonylation that will be useful
to synthetic organic chemists.
Carbonylation Catalysts
T. Morimoto,* K. Kakiuchi
5580 – 5588
Evolution of Carbonylation Catalysis: No
Need for Carbon Monoxide
Reviews
Synthesis Planning
Collected and combined: A strategy for
guiding the search for new chemical
reactions is described by giving concrete
examples from the many years of research
from the authors group. Three major
research topics—oxidative–reductive
condensation, the Lewis acid catalyzed
aldol reaction, and glycosylation of glycosyl fluoride—are described to show how
the initial concept was formulated and
then expanded into broadly applicable
methods.
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Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
T. Mukaiyama*
5590 – 5614
Explorations into New Reaction Chemistry
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5559
Angewandte
Chemie
Communications
Chirality and Magnetism
Magnetism gets a new twist: The crystal
structure and magnetic properties of a
chiral 3D ferrimagnet with Tc of 35 K,
[{CrIII(CN)6}{MnII(d- or l-NH2ala)}3]
·3 H2O (NH2ala = aminoalanine ion) are
described. The complex has an extended,
chiral, triple-strand helical arrangement of
MnII ions, formed by the coordination of
the organic ligands (see picture; purple Mn, gray C, blue N, red O). The triple
helixes are linked to each other by the
{CrIII(CN)6} units.
H. Imai, K. Inoue,* K. Kikuchi, Y. Yoshida,
M. Ito, T. Sunahara,
S. Onaka
5618 – 5621
Three-Dimensional Chiral Molecule-Based
Ferrimagnet with Triple-Helical-Strand
Structure
Simple banana-shaped organic molecules
self-organize into finite, spherical coordination networks with a diameter of up to
7 nm (see structure; green Pd, red O,
blue N, gray C). These molecular spheres
consist of 12 equivalent metal centers and
24 equivalent ligands and have cuboctahedral symmetry. Functional groups (C60
or porphyrin) attached to each ligand are
aligned equivalently at the periphery of the
sphere.
Surface replication: Three-dimensional
ordered colloidal crystals are used as
templates in creating surface gratings
from a large variety of functional materials, such as metals, semiconductors, and
dielectrics, provided that the material
deposition only occurs on the periodic
surfaces of the templates. By this nonlithographic technique wafer-scale samples with submicron periodicity can be
rapidly created (see picture).
M. Tominaga, K. Suzuki, M. Kawano,
T. Kusukawa, T. Ozeki, S. Sakamoto,
K. Yamaguchi, M. Fujita*
5621 – 5625
Finite, Spherical Coordination Networks
that Self-Organize from 36 Small
Components
Nanostructured Films
P. Jiang*
5625 – 5628
Surface-Templated Nanostructured Films
with Two-Dimensional Ordered Arrays of
Voids
Bioinorganic Chemistry
A compound with potential: The title
compound (see structure) not only
resembles the relevant protein active sites
geometrically and spectroscopically, but
also possesses the least negative
[Fe4S4(L)4]2 /3 and [Fe4S4(L)4]3 /4 (L is a
monoanionic ligand) redox potentials of
all protein Fe4S4 analogues. The value of
the Fe4S4+/0 redox potential implies a new
route to the isolation of the elusive Fe4S40
cluster.
Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
Self-Assembly
T. A. Scott, H.-C. Zhou*
5628 – 5631
The First All-Cyanide Fe4S4 Cluster:
[Fe4S4(CN)4]3
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5561
Contents
Inclusion Compounds
S. T. Mough, J. C. Goeltz,
K. T. Holman*
5631 – 5635
Isolation and Structure of an “Imploded”
Cryptophane
Container crushing: Thermal liberation of
the encapsulated guest in a cryptophane
has been shown to cause conformational
“implosion” in the solid state. The resulting collapsed form is kinetically stable,
can be isolated, and its unexpected
structure has been elucidated by X-ray
diffraction. It eventually re-inflates, however, to the occupied container-like species on standing in solution (see scheme).
Sensitive and selective, a modular-based
fluorescent polymer combines a rigid
electron-conducting block (see picture; B)
with a flexible binding block (A). The
monopyridyl group of the coordinating
module has a great affinity for PdII ions
and selectively binds them through selfassembly. Thus, the fluorescent conjugated polymer may be used for sensing PdII
ions.
Sensors
H. Huang, K. Wang,* W. Tan, D. An,
X. Yang, S. Huang, Q. Zhai, L. Zhou,
Y. Jin
5635 – 5638
Design of a Modular-Based Fluorescent
Conjugated Polymer for Selective Sensing
Nanoparticles
Finding the right angle: The contact angle
of nanoparticles at the water/oil interface
can be engineered close to 908 by capping
with ligands containing carboxylic ester
terminal groups. This drives the nanoparticles to self-assemble into closepacked films (see picture), and thus
provides the opportunity to create two- or
three-dimensional homo- or heterogeneous nanostructures for electronic,
optoelectrical, and magnetic applications.
H. Duan, D. Wang,* D. G. Kurth,
H. MShwald
5639 – 5642
Directing Self-Assembly of Nanoparticles
at Water/Oil Interfaces
Bioorganic Chemistry
M. Endo,* K. Nakayama, Y. Kaida,
T. Majima*
5643 – 5645
Design and Synthesis of Photochemically
Controllable Caspase-3
5562
The selective cleavage achieved by activated caspase-8 has been mimicked by
using a photofunctionalized caspase-3
having 2-nitrophenylglycine (Npg) at a
specific position of the peptide chain (see
picture). The study shows that the activity
of caspase-3 has been clearly expressed by
photoirradiation and that autocleavage of
caspase-3 has been suppressed by the
site-selective incorporation of the Npg
residue.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
Angewandte
Chemie
The best of both worlds: The synthesis of
carbon-encapsulated iron-based magnetic
nanoparticles is described (see picture:
left TEM image, right model). With such
small catalysts that have macroscopic
magnetic properties, the advantages of
homogeneous or colloidal and heterogeneous catalysts can be combined.
Nanostructures
S. C. Tsang,* V. Caps, I. Paraskevas,
D. Chadwick, D. Thompsett 5645 – 5649
Magnetically Separable, CarbonSupported Nanocatalysts for the
Manufacture of Fine Chemicals
Peptide Structures
G. E. Job, B. Heitmann, R. J. Kennedy,
S. M. Walker, D. S. Kemp*
5649 – 5651
Calibrated Calculation of Polyalanine
Fractional Helicities from Circular
Dichroism Ellipticities
Maximally helical polyalanines, 9 to
24 residues in length, are used to calibrate
the assignment of fractional helicity (FH)
from circular dichroism ellipticities.
Water-solubilizing, helix-stabilizing N- and
C-caps induce FHs > 0.9 in core polyala-
nine regions. Linear length regressions of
peptide molar ellipticities (blue-green
curves) yield slopes (red arrows) that
define molar per-residue ellipticities of a
fully helical alanine residue (red curve).
Spontaneous formation of microspheres
is observed when charged poly(amino
acid)s are combined with certain oppositely charged, multivalent organic ions.
The surfaces of the spheres are chemically
active and act as templates for silica
condensation, and the assemblies can be
made hollow or polymer-filled, depending
on the silica precursor (see image; the
fluorescent polymer forms a layer inside a
colloidal-silica-coated sphere).
B. J. McKenna, H. Birkedal,* M. H. Bartl,
T. J. Deming, G. D. Stucky* 5652 – 5655
Micrometer-Sized Spherical Assemblies
of Polypeptides and Small Molecules by
Acid–Base Chemistry
Porphyrins
There’s nothing confusing about the
dimer (see picture) that forms from Nconfused porphyrin! The dimer was
obtained as a directly b–b-linked structure
through a simple acid-catalyzed condensation reaction of the monomeric macrocycles, and the electronic interaction
between the porphyrin subunits was studied for both the free-base form and for
the bis(nickel(ii)) complex.
Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
Hybrid Materials
P. J. Chmielewski*
5655 – 5658
Synthesis and Characterization of a
Directly Linked N-Confused Porphyrin
Dimer
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5563
Contents
Carbon Nitrides
A high-nitrogen compound, 3,6-di(azido)1,2,4,5-tetrazine, was used as precursor
for the preparation of carbon nanospheres
(see SEM picture) and nitrogen-rich
carbon nitrides. The conversions into both
carbon-based materials are simple, occur
under mild conditions (low temperature,
no applied pressure), and require no
vacuum systems, extraction, carbonization, and purification.
M. H. V. Huynh,* M. A. Hiskey,*
J. G. Archuleta, E. L. Roemer,
R. Gilardi
5658 – 5661
3,6-Di(azido)-1,2,4,5-Tetrazine: A Precursor for the Preparation of Carbon
Nanospheres and Nitrogen-Rich Carbon
Nitrides
Polyoxometalates
S. P. de Visser, D. Kumar, R. Neumann,*
S. Shaik*
5661 – 5665
Computer-Generated High-Valent Iron–
Oxo and Manganese–Oxo Species with
Polyoxometalate Ligands: How do they
Compare with the Iron–Oxo Active
Species of Heme Enzymes?
Coordination Frameworks
Y.-F. Zhou, F.-L. Jiang, D.-Q. Yuan,
B.-L. Wu, R.-H. Wang, Z.-Z. Lin,
M.-C. Hong*
5665 – 5668
Copper Complex Cation Templated
Gadolinium(iii)–Isophthalate
Frameworks
Binuclear Complexes
K. van der Schilden, F. GarcVa,
H. Kooijman, A. L. Spek, J. G. Haasnoot,
J. Reedijk*
5668 – 5670
A Highly Flexible Dinuclear
Ruthenium(ii)–Platinum(ii) Complex:
Crystal Structure and Binding to
9-Ethylguanine
5564
The structure and reactivity of high-valent
FeVO and MnVIO oxidation catalysts containing a polyoxometalate [PW11O39]7
lacunary ligand (2) have been investigated
by a computational study. Calculations
have demonstrated there is an intriguing
analogy between these species and the
active species (1) of the enzyme cytochrome P450 (see scheme).
Ions in cages: Hydrothermal reactions
give two novel 3D heterometallic frameworks, [{[Gd4(ip)7(H2O)2][Cu(bpy)2]2}n] (1,
bpy = 2,2’-bipyridine, H2ip = isophthalic
acid; see structure, space filling models:
[Cu(bpy)2], polyhedra: Gd) and
[{Gd3Cu(ip)5(Hip)(bpy)}n]·n H2O (2). The
structure of 1 consists of charged cages
containing two encapsulated CuI complex
cations, whereas that of 2 contains
charged cavities in which CuII complex
cations are bound.
The length and high flexibility of the linker
in a heterodinuclear ruthenium–platinum
complex (see X-ray crystal structure)
enables the platinum unit to independently interact with DNA by p–p stacking
or coordination, possibly after pre-association of the 2 + charged ruthenium unit.
A prototype of this challenging class of
potentially cytostatic compounds is
presented.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
Angewandte
Chemie
Nanowires
A low turn-on voltage is revealed by
repeating field emission tests of NbS2,
which is a highly reliable field emitter.
Well-defined NbS2 nanowires (see picture)
can be generated in the bulk by direct
heating of Nb and S powders in sealed
quartz tubes in the presence of I2.
Y. Z. Jin, W. K. Hsu, Y. L. Chueh, L. J. Chou,
Y. Q. Zhu,* K. Brigatti, H. W. Kroto,
D. R. M. Walton
5670 – 5674
Large-Scale Production of NbS2
Nanowires and Their Performance in
Electronic Field Emission
Transfer interference: Synthesis of the
bisubstrate-type N-acetylglucosaminyltransferase (GnT) inhibitor 1 was
achieved by a polymer-resin hybrid capture–release strategy for the construction
of the acceptor component. One-pot
ligation in aqueous media produced the
coupling product, and subsequent construction of a diphosphate linkage led to
1. Inhibitory activities toward GnT-V and
GnT-IX were evaluated and revealed the
potency of 1 toward the latter enzyme.
Glycosyltransferase Inhibitor
S. Hanashima, S. Manabe, K.-i. Inamori,
N. Taniguchi, Y. Ito*
5674 – 5677
Synthesis of a Bisubstrate-Type Inhibitor
of N-Acetylglucosaminyltransferases
Fluorinated Carbohydrates
A. J. Boydell, V. Vinader,
B. Linclau*
A Sharpless asymmetric dihydroxylation
of the commercially available building
block 1 affords the common chiral inter-
mediate 2 for the synthesis of the fluorinated monosaccharides 3–5 (Bn=benzyl).
A practical and scalable operation: The
reaction shown in the scheme, which uses
catalytic amounts of hexacarbonyldicobalt, gives access to versatile bicyclic
systems, which until now could only be
obtained in low quantities by a photochemical process starting from tropolones. An isolation of the primary Pauson–
Khand products is not necessary.
Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
www.angewandte.org
5677 – 5679
Enantioselective Synthesis of
Tetrafluoroethylene-Containing
Monosaccharides
Cyclopentenone Synthesis
S. E. Gibson,* N. Mainolfi,
S. B. Kalindjian, P. T. Wright 5680 – 5682
A Cyclobutadiene Equivalent in the
Catalytic Pauson–Khand Reaction
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5565
Contents
Organophosphine Polymers
C.-W. Tsang, B. Baharloo, D. Riendl,
M. Yam, D. P. Gates*
5682 – 5685
Radical Copolymerization of a
Phosphaalkene with Styrene: New
Phosphine-Containing Macromolecules
and Their Use in Polymer-Supported
Catalysis
P=C bonds mimic C=C bonds in the
radical-initiated copolymerization of a
phosphaalkene 1 and styrene (see
scheme). The resulting copolymers 2 have
unprecedented phosphine-containing
backbones with phosphorus composi-
Nanostructures
tions that vary depending on the monomer ratios. These novel functional hybrid
inorganic–organic macromolecules are
used as polymeric supports for the Pdcatalyzed Suzuki coupling. VAZO = 1,1’azobis(cyclohexanecarbonitrile).
In control! Ag2S nanocrystals of predictable size and shape were synthesized
from the precursor Ag(SCOPh) in the
presence of an amine. Careful tuning of
several parameters, such as the reaction
temperature and the ratio of amine to
precursor, led to Ag2S nanocrystals of
varying morphology (red: nanocubes;
blue: faceted nanocrystals; yellow: nanorods) and size. x = particle size. HDA =
hexadecylamine.
W. P. Lim, Z. Zhang, H. Y. Low,
W. S. Chin*
5685 – 5689
Preparation of Ag2S Nanocrystals of
Predictable Shape and Size
Epoxide Ring Opening
C. Schneider,* A. R. Sreekanth,
E. Mai
5691 – 5694
Scandium–Bipyridine-Catalyzed Enantioselective Addition of Alcohols and Amines
to meso-Epoxides
A winning combination of metal and
ligand: The catalyst formed in situ from
Sc(OTf)3 and bipyridine 1 (10 mol %)
mediates the alcoholysis and aminolysis
of meso-epoxides in high enantioselectivities and furnishes valuable chiral 1,2-diol
monoethers 2 and 1,2-amino alcohols 3 as
products (PMB = para-methoxybenzyl).
Two ring closures, a ring opening, and two
intermolecular proton shifts are the crucial steps in a cascade reaction that is
triggered by the simple deprotonation of
alkynylimines and leads ultimately to
aminobenzannulation products (see
scheme). The reactions proceed in good
to very good yield and with excellent
chemoselectivity.
Annulations
P. Sagar, R. FrShlich,
E.-U. WWrthwein*
5694 – 5697
A Versatile Aminobenzannulation
Method Based on the Deprotonation of
2-(1-Alkynyl)benzaldimines and Similar
2-Aza-2,4-heptadienyl-6-ynes: A Multistep
Rearrangement Cascade
5566
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
Angewandte
Chemie
Like a chlorinated golf ball aptly describes
a new kind of chlorosiloxane particle
(SixOyClz, CSN; see picture). Under suitable conditions they are formed by the
reaction between SiCl4 and O2 in the gas
phase. The surface of these spherical,
amorphous particles is densely covered by
chlorine atoms. These can be substituted
by nearly any group. Thus, the surface of
the particles can be customized for the
particular purpose.
Silica Particles
T. Giesenberg, S. Hein, M. Binnewies,*
G. Kickelbick
5697 – 5700
Synthesis and Functionalization of a New
Kind of Silica Particle
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
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Keywords
5702
Authors
5703
Angewandte’s
Sister Journals
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Angew. Chem. Int. Ed. 2004, 43, 5558 – 5567
www.angewandte.org
5704 – 5705
5707
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5567
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