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Graphical Abstract Angew. Chem. Int. Ed. 342005

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Contents
The following Communications have been judged by at least two referees to be “very
important papers” and will be published online at www.angewandte.org soon:
K. Haraguchi,* H.-J. Li
Control of the Coil-to-Globule Transition of
Poly(N-isopropylacrylamide) and Ultrahigh Mechanical
Properties in Nanocomposite Hydrogels
T. Buskas, S. Ingale, G.-J. Boons*
Towards a Fully Synthetic Carbohydrate-Based Anticancer
Vaccine: Synthesis and Immunological Evaluation of a Lipidated
Glycopeptide Containing the Tumor-Associated Tn Antigen
A. C. Filippou,* G. Schnakenburg, A. I. Philippopoulos,
N. Weidemann
Bonding Analysis of the MGeGeM Chain in the Germylidyne
Complexes trans,trans-[Cl(depe)2MGeGeM(depe)2Cl]
M. Veith*
Cubane-Type Li4H4 and Li3H3Li(OH): Stabilized in Molecular
Adducts with Alane
S. Protti, M. Fagnoni,* A. Albini*
Photochemical Cross-Coupling Reactions of Electron-Rich Aryl
Chlorides and Aryl Esters with Alkynes: A Metal-Free Alkynylation
V. Lavallo, Y. Canac, C. Pr-sang, B. Donnadieu, G. Bertrand*
Stable Cyclic (Alkyl)(amino)carbenes as Rigid or Flexible, Bulky,
Electron-Rich Ligands for Transition-Metal Catalysts
Meeting Reviews
Joint Meeting on Medicinal Chemistry in Vienna
R. E. Martin,* P. Mohr, W. Palmer,
H. Stalder
5364
Books
Biocatalysts and Enzyme Technology
Klaus Buchholz, Volker Kasche, Uwe T.
Bornscheuer
reviewed by O. May
5367
Handbook of RNA Biochemistry
Roland K. Hartmann, Albrecht Bindereif,
Astrid Sch)n, Eric Westhof
reviewed by W. Saenger
5367
Highlights
Molecular Electronics
D. F. Perepichka,*
M. R. Bryce*
5370 – 5373
Molecules with Exceptionally Small
HOMO–LUMO Gaps
5352
Mind the gap: HOMO–LUMO gaps less
than 0.5 eV have been recently engineered
in small organic molecules through
extended conjugation and donor–acceptor covalent coupling approaches (see
picture). Such compounds reveal a
number of unusual electronic properties
such as thermo-excited intramolecular
electron transfer (in solution) and metallic
conductivity (in the solid state).
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
Angewandte
Chemie
Minireviews
Fullerene Chemistry
L. S:nchez, N. Mart;n,*
D. M. Guldi*
Supramolecular chemistry of C60 is leading the way for the use of C60 as a unique
photo- and electroactive building block.
Arrays of hydrogen bonds ensure a high
degree of order on the nanometer scale, a
feature that will be critical in the applica-
tion of the resulting noncovalently bound
ensembles as molecular materials or
supramolecular catalysts (see scheme;
eT = electron transfer, ET = energy transfer).
5374 – 5382
Hydrogen-Bonding Motifs in Fullerene
Chemistry
Reviews
Biaryl Synthesis
Not only classic, atroposelective biaryl
couplings lead to stereochemically pure,
axially chiral biaryl compounds (see
scheme); recently, novel, highly original
strategies have also emerged. The authors
present a discussion of the structural
preconditions of axial chirality and the
most successful and innovative of these
strategies.
G. Bringmann,* A. J. Price Mortimer,
P. A. Keller, M. J. Gresser, J. Garner,
M. Breuning*
5384 – 5427
Atroposelective Synthesis of Axially Chiral
Biaryl Compounds
Communications
Two Bs in a pod: The first 1,2-diborylated
ferrocene (see structure) was obtained
upon reaction of PhBCl2 with 1,1’-bis(trimethylstannyl)ferrocene. Conformational
changes in this highly rigid species are
triggered either through redox chemistry
or the binding of nucleophiles, to render
the complex an interesting candidate for
the design of new types of molecular
machines.
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ANGEWANDTE CHEMIE International
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Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
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: US$ 4948.00/4498.00 (valid for print
and electronic / print or electronic delivery); for
individuals who are personal members of a
Ferrocenes
K. Venkatasubbaiah, L. N. Zakharov,
W. S. Kassel, A. L. Rheingold,
F. J=kle*
5428 – 5433
Reversible Expansion and Contraction of a
1,2-Diborylated Ferrocene Dimer
Promoted by Redox Chemistry and
Nucleophile Binding
national chemical society, or whose institution
already subscribes, or who are retired or selfemployed consultants, print only: US$ 394.00.
Postage and handling charges included. All
Wiley-VCH prices are exclusive VAT.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5353
Angewandte
Chemie
The challenging structure and potent
growth inhibition properties against a
variety of human cancer cell lines make
Spongistatin 1 (1) an exciting target for
total synthesis. Enantioselective total
synthesis has been achieved by exploiting
a latent element of pseudo-symmetry
(a = pseudo-C2 axis) within the ABCD
bis(spiroketal) fragment (red substructure).
The new star of Westerns: A highly
sensitive fluorescence probe for alkaline
phosphatase (ALP) based on a fluorescein
derivative has been prepared and found to
be suitable for use in Western blot
analysis. The probe 1 is nonfluorescent
but undergoes hydrolysis in the presence
of ALP to yield a green-fluorescent derivative 2 and may be used in multicolor
labeling in combination with other
probes.
Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
Natural Product Synthesis
M. Ball, M. J. Gaunt, D. F. Hook,
A. S. Jessiman, S. Kawahara, P. Orsini,
A. Scolaro, A. C. Talbot, H. R. Tanner,
S. Yamanoi, S. V. Ley*
5433 – 5438
Total Synthesis of Spongistatin 1:
A Synthetic Strategy Exploiting
Its Latent Pseudo-Symmetry
Fluorescent Probes
M. Kamiya, Y. Urano, N. Ebata,
M. Yamamoto, J. Kosuge,
T. Nagano*
5439 – 5441
Extension of the Applicable Range of
Fluorescein: A Fluorescein-Based Probe
for Western Blot Analysis
Stack ’em high: A polyimide with pyromellitic diimide units linked by hexaoxyethylene segments can be made to fold by
cooperative two-point interactions on
addition of a folding agent (see scheme).
The ammonium group of the folding
agent forms complexes with the oxyethylene spacer which greatly facilitates the
formation of charge-transfer complexes
between the aromatic units of the two
components.
Donor–Acceptor Systems
Monodisperse CdSe quantum dots (QDs)
with excellent optical properties can be
prepared with a gas–liquid segmented
flow microreactor with multiple temperature zones (see picture; red = heated;
blue = cooled quench zone). The
enhanced mixing and narrow residence
time distributions of segmented flow
produce QDs superior to those prepared
in single-phase operations.
Microreactor Fluidics
S. Ghosh,
S. Ramakrishnan*
5441 – 5447
Small-Molecule-Induced Folding of a
Synthetic Polymer
B. K. H. Yen, A. GLnther, M. A. Schmidt,
K. F. Jensen,*
M. G. Bawendi*
5447 – 5451
A Microfabricated Gas–Liquid Segmented
Flow Reactor for High-Temperature
Synthesis: The Case of CdSe Quantum
Dots
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5355
Contents
Fluorescent Probes
E. E. Nesterov, J. Skoch, B. T. Hyman,
W. E. Klunk, B. J. Bacskai,
T. M. Swager*
5452 – 5456
In Vivo Optical Imaging of Amyloid
Aggregates in Brain: Design of
Fluorescent Markers
Electrochemical Biosensors
Y. Xiao, A. A. Lubin, A. J. Heeger,
K. W. Plaxco*
5456 – 5459
Label-Free Electronic Detection of
Thrombin in Blood Serum by Using an
Aptamer-Based Sensor
Metal Chains
K. Uemura, K. Fukui, H. Nishikawa, S. Arai,
K. Matsumoto,* H. Oshio
5459 – 5464
Paramagnetic Platinum–Rhodium
Octamers Bridged by Halogen Ions To
Afford a Quasi-1D System
Routine diagnostics and studies of Alzheimer’s disease might benefit form the
noninvasive optical imaging of amyloid-b
plaques in the brain. A rational design
strategy for in vivo amyloid-imaging
agents that enter the brain and selectively
stain amyloid plaques is presented (see
picture), and properties of a promising
lead biomarker candidate are reported.
Blue, gold, and DNA: A methylene blue
(MB) tagged, thrombin-binding DNA
aptamer immobilized on a gold surface
undergoes a large conformational change
upon target binding (see schematic
representation; eT: electron transfer).
This folding produces a large, readily
measurable change in redox current and
allows the electrochemical detection of
thrombin in blood serum.
Down to the wire: A new class of 1D
chain, [-Pt-Rh-Pt4-Rh-Pt-Cl-]n, composed of
Pt–Pt and Pt–Rh dimeric complexes linked
through metal–metal bonds has been
prepared (see structure). This chain of
mixed-valent metals (PtII/PtIII and
RhII/RhIII) contains one unpaired electron
in each octameric segment, leading to
unique electrical and magnetic properties.
Molecular Motors
R. Nutiu, Y. Li*
5464 – 5467
A DNA–Protein Nanoengine for
“On-Demand” Release and Precise
Delivery of Molecules
5356
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
A DNA aptamer (green in the scheme), an
antisense DNA strand (purple), and an
enzyme (blue) form a nanoengine that
responds to a small-molecule input (red)
and dispatches a DNA output. The addition of the input promotes the first stroke
of the nanoengine, the action of the
enzyme the second stroke. Joint exploration of all components could lead to
bionanodevices that can detect a biological malfunction and initiate a repair.
Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
Angewandte
Chemie
Reactivity Studies
V. K. Aggarwal,* J. N. Harvey,*
R. Robiette
5468 – 5471
On the Importance of Leaving Group
Ability in Reactions of Ammonium,
Oxonium, Phosphonium, and Sulfonium
Ylides
What controls reactivity of ylides? Computational data show that reactivity in the
reactions shown in the scheme is mainly
determined by the leaving group ability of
the onium group, and this decreases for
both intrinsic and thermochemical
reasons in the order O > S > N > P. The
results are consistent with experimental
observations and account for the dearth of
examples of phosphorus ylides in these
reactions.
Coordination Polymers
S. Hu, J.-C. Chen, M.-L. Tong,* B. Wang,
Y.-X. Yan, S. R. Batten
5471 – 5475
The hydrothermal reaction of 1,3-di(4pyridyl)propane with Cu(OH)2 in the presence of 1,4-cyclohexanedicarboxylic acid
and dilute HCl generates an unprecedented tetratopic ligand (chtpy) and a family
of interesting coordination networks in
situ (see scheme). The topological diversification of the CuI–chtpy nets can be
controlled simply by changing the molar
ratio of the starting materials.
Cu2+-Mediated Dehydrogenative Coupling
and Hydroxylation of an N-Heterocyclic
Ligand: From Generation of a New
Tetratopic Ligand to the Designed
Assembly of Three-Dimensional
Copper(i) Coordination Polymers
Biomineralization
An eggshell finish: Designed peptides can
be used as a tool to unravel the structure–
activity relationships of eggshell matrix
proteins. The ordered arrangement of
doublets of charged residues on the
peptide and its self-assembling characteristics play a key role in the biomimetic
nucleation of polycrystalline calcite crystal
aggregates (see picture), which models
that initiated by the goose eggshell matrix
protein, ansocalcin.
P. K. Ajikumar, S. Vivekanandan,
R. Lakshminarayanan, S. D. S. Jois,
R. M. Kini, S. Valiyaveettil*
5476 – 5479
Mimicking the Function of Eggshell
Matrix Proteins: The Role of Multiplets of
Charged Amino Acid Residues and SelfAssembly of Peptides in Biomineralization
Protein Interactions
W.-S. Yeo, D.-H. Min, R. W. Hsieh,
G. L. Greene, M. Mrksich*
5480 – 5483
Eliminating the middle-man: The combination of MALDI-TOF mass spectrometry
and self-assembled monolayers on gold
(SAMDI) offers a new detection method
for protein–ligand (shown) and protein–
Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
protein interactions. Proteins and protein
complexes are selectively bound to biochips and then directly analyzed by
MALDI-TOF MS without the need for
labels.
Label-Free Detection of Protein–Protein
Interactions on Biochips
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5357
Contents
Structure Elucidation
A.-V. Mudring,* A. Babai, S. Arenz,
R. Giernoth
5485 – 5488
The “Noncoordinating” Anion Tf2N
Coordinates to Yb2+: A Structurally
Characterized Tf2N Complex from the
Ionic Liquid [mppyr][Tf2N]
Carbon Nanoparticles
D. S. Su,* X. Chen, G. Weinberg,
A. Klein-Hofmann, O. Timpe,
S. B. A. Hamid, R. Schl)gl
5488 – 5492
Hierarchically Structured Carbon:
Synthesis of Carbon Nanofibers Nested
inside or Immobilized onto Modified
Activated Carbon
Not as innocent as it looks: The first
anionic Tf2N complex, [Yb(Tf2N)4]2, has
been prepared in the ionic liquid
[mppyr][Tf2N] (see crystal structure; blue:
N, yellow: S, gray: C, green: F, orange: Yb,
red: O; mppyr = 1-methyl-1-propyl-pyrrolidinium, Tf = trifloromethanesulfonyl).
The coordination of the presumed noncoordinating (“innocent”) Tf2N2 ion
could have a decisive influence on reactions in ionic liquids.
Filling in the gaps of activated carbon by
chemical vapor decomposition of ethylene
results in hierarchically structured carbon
with carbon nanofibers (CNFs) nested
inside and immobilized on the surface
(see picture). The adsorption experiments
show that this nanostructuring of carbon
creates novel functions on the surface of
activated carbon.
Asymmetric Synthesis
A useful transformation in enantioselective synthesis: ()-Sparteine-assisted
lithiation of the propargylic 1-thiocarbamate 1 (Cb = CONiPr2) forms the enantiomerically and diastereomerically pure
lithium ()-sparteine complex 2. Its solidstate structure and application in the
asymmetric synthesis of highly enantioenriched 1-thioallenes 3 were investigated.
R. Otte, R. Fr)hlich, B. Wibbeling,
D. Hoppe*
5492 – 5496
Solid-State Structure and Enantioselective
Reactions of a Complex of a 1-ThioSubstituted Propargyllithium and
()-Sparteine
Odd-Electron Bonds
T. Kato, H. Gornitzka, W. W. Schoeller,
A. Baceiredo, G. Bertrand* 5497 – 5500
Dimerization of a Cyclo-1s4,3s2,4s2Triphosphapentadienyl Radical: Evidence
for Phosphorus–Phosphorus OddElectron Bonds
5358
www.angewandte.org
How odd! The title radical can be represented by resonance structures A and B.
From A, dimerization refers to a [p2þp2]
reaction and results in the formation of
two inter-ring PP single bonds, whereas
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
from B, only one unpaired electron is
supplied from each radical unit, which
leads to two inter-ring PP one-electron
bonds. As a consequence, the isolated
dimer features “short” PP half-bonds.
Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
Angewandte
Chemie
A gray area in gray matter: The CuII
complex of a truncated b-amyloid,
CuAb1–20, catalyzes the oxidation of catechol and the hydroxylation and oxidation
of phenol (see picture) with dramatic rate
accelerations ( 105–106-fold increases).
The Cu–oxygen chemistry of CuAb may
offer both a better understanding of the
chemical effect in the brains of patients
who suffer from Alzheimer’s disease as
well as possible treatment strategies of
this disease.
Bioinorganic Chemistry
G. F. Z. da Silva, L.-J. Ming* 5501 – 5504
Alzheimer’s Disease Related Copper(ii)b-Amyloid Peptide Exhibits Phenol
Monooxygenase and Catechol Oxidase
Activities
Surface Chemistry
S. Gabriel, P. Dubruel, E. Schacht,
A. M. Jonas, B. Gilbert, R. JTrUme,
C. JTrUme*
5505 – 5509
Hydrophilic adherent coatings: Electrografting of acrylate end-capped poly(ethylene glycol) (PEG) is an important technique for the one-step coating of electro-
Holding on to hydrido: The reactivity of
the asymmetric dinuclear ruthenium species 1, which is bridged by three different
ligands, is studied. It undergoes ligandexchange reactions, dehydration with
protic acids, and decarboxylation by oxidative addition. Only the bridging hydrido
ligand remains intact during all these
reactions.
Contrasting views: Entrapment of a paramagnetic shift reagent for water protons
inside liposomes dramatically improves
the sensitivity of chemical exchange
saturation transfer agents. The chemical
shift of the water entrapped within the
liposomes, relative to bulk water, depends
upon the nature and concentration of the
shift reagent as well as on the permeability
of the liposome membrane (see picture;
SR = shift reagent, Ln = lanthanide ion).
Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
conductive substrates by an adherent
hydrophilic coating (see figure). This
technique is very efficient for the production of new protein-repellent surfaces.
Electrografting of Poly(ethylene glycol)
Acrylate: A One-Step Strategy for the
Synthesis of Protein-Repellent Surfaces
Organometallic Chemistry
Y. Arikawa, S. Nagae, J.-i. Morishita,
K. Hiraki, M. Onishi*
5509 – 5513
Formation of An Unsymmetrical
Dinuclear Ruthenium Complex with m-H,
m-OH, and m-k2-CO2 Bridges and Multiple
Reactive Sites
Imaging Agents
S. Aime,* D. Delli Castelli,
E. Terreno
5513 – 5515
Highly Sensitive MRI Chemical Exchange
Saturation Transfer Agents Using
Liposomes
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5359
Contents
Synthetic Methods
V. K. Aggarwal,*
B. Olofsson
5516 – 5519
Enantioselective a-Arylation of
Cyclohexanones with Diaryl Iodonium
Salts: Application to the Synthesis of
()-Epibatidine
Short cut: Direct asymmetric a-arylation
of prochiral ketones has been effected
using chiral lithium amide bases and
diaryl iodonium salts. The methodology
Homogeneous Catalysis
has been employed in a short total
synthesis of the alkaloid ()-epibatidine
(see scheme).
Cleaning up: NaNO2, a simple, inexpensive and biodegradable inorganic compound, acts as a catalyst to activate
molecular oxygen for the destruction of
polychlorinated phenols. The NaNO2/O2
system efficiently oxidizes the recalcitrant
trichlorophenol into CO2 and/or CO and a
small fraction of biodegradable organic
products with a high rate of conversion
(see ion chromatogram).
X. Liang,* D. Fu, R. Liu,* Q. Zhang,
T. Y. Zhang, X. Hu*
5520 – 5523
Highly Efficient NaNO2-Catalyzed
Destruction of Trichlorophenol Using
Molecular Oxygen
Asymmetric Synthesis
M. Sakamoto,* A. Unosawa, S. Kobaru,
A. Saito, T. Mino, T. Fujita
5523 – 5526
Asymmetric Photocycloaddition in
Solution of a Chiral Crystallized
Naphthamide
Frozen chirality: Achiral naphthamide 1
can be crystallized to give chiral 1*, whose
chiral molecular conformation is retained
(“frozen”) after the crystals are dissolved
in cold THF. Asymmetric photocycloaddition of 1* with 9-cyanoanthracene (9CNAN) in solution gives cycloadduct 2
with high enantioselectivity.
A variety of 1,2-dihydroisoquinoline derivatives 3 have been prepared in good to
high yields by the AgOTf-catalyzed reaction of ortho-alkynylaryl aldimines 1 with
various pronucleophiles 2 (see scheme).
Treatment of 1 with a stoichiometric
amount of AgOTf followed by protonation
with TfOH produced 4, which suggests
the formation of an isoquinolinium intermediate in the present direct addition
reaction. Tf = trifluoromethanesulfonyl.
Nitrogen Heterocycles
N. Asao,* S. Yudha S., T. Nogami,
Y. Yamamoto
5526 – 5528
Direct Mannich and Nitro-Mannich
Reactions with Non-Activated Imines:
AgOTf-Catalyzed Addition of
Pronucleophiles to ortho-Alkynylaryl
Aldimines Leading to 1,2Dihydroisoquinolines
5360
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
Angewandte
Chemie
Service
Angew. Chem. Int. Ed. 2005, 44, 5352 – 5361
Keywords
5530
Authors
5531
Angewandte’s Sister Journals
5532
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5533
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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