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Graphical Abstract Angew. Chem. Int. Ed. 132006

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The following Communications have been judged by at least two referees to be “very
important papers” and will be published online at soon:
G. Dolphin, P. Dumy,* J. Garcia*
Control of Amyloid b-Peptide Protofibril Formation by a Designed
Template Assembly
A. Kaminaga, V. Vanag, I. Epstein*
A Reaction-Diffusion Memory Device
V. Stamenkovic, B. S. Moon, K. J. Mayrhofer, P. Ross, N. Markovic,
J. Rossmeisl, J. Greeley, J. Nørskov*
Changing the Activity of Electrocatalysts for Oxygen Reduction
by Tuning the Surface Electronic Structure
J. Blumberger,* B. Ensing, M. Klein
Formamide Hydrolysis in Alkaline Aqueous Solution: Insights
from Ab Initio Metadynamics Calculations
J. M. B. v. Colbe, W. Schmidt,* M. Felderhoff, B. Bogdanovic,
Hydrogen Isotope Scrambling on Doped Sodium Alanate
W. Zhao, Y. Gao, S. Kandadai, M. Brook,* Y. Li*
DNA Polymerization on Gold Nanoparticles through Rolling
Circle Amplification: Towards Scaffolds for Three-Dimensional
Periodical Nanoassemblies
Organic Chemistry:
Buchwald Awarded
Bioinorganic Chemistry:
Wieghardt Receives Prize
Materials Science:
Meijer Honored
Multiphase Homogeneous Catalysis
B. Cornils, W. A. Herrmann,
I. T. Horv%th, W. Leitner, S. Mecking,
H. Olivier-Bourbigou, D. Vogt
reviewed by O. Walter
Boronic Acids
Dennis G. Hall
reviewed by S. Marsden
Genetic Engineering Renders Plants
Attractive to “Bodyguards”
A continuous cry for help is let out by
transgenic Arabidopsis thaliana plants that
are modified to produce volatile terpe-
noid derivatives, such as dimethylnonatriene, which are well-known attractants
for predatory mites or “bodyguards” (see
picture). Such transgenic plants are
important in ecological experiments to
obtain insights into indirect chemical
defense strategies.
Hydrogen Storage
Captured and caged: The capture of H2 in
H2O cages to give clathrate hydrogen
hydrate is a recent breakthrough in the
development of hydrogen storage materials. Pure H2 hydrate is stabilized only
under high pressures (typically 220 MPa
at 249 K). However, inclusion of THF as a
second guest allows stabilization of the
resultant clathrate at pressures of only
5 MPa at 279.6 K (see picture; THF blue,
H2 red).
Chemical Defense
G. Pohnert*
Y. H. Hu,* E. Ruckenstein
2008 – 2010
2011 – 2013
Clathrate Hydrogen Hydrate—A
Promising Material for Hydrogen Storage
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
Improvements in play-back quality of
stored information and the rapidly
increasing demand for media with greater
storage capacity have led to a very fast
development in optical storage media
(CD, DVD) in the last 20 years. The most
successful systems are those based on
organic dyes. This Review describes the
general developments in this area and
discusses the optical and thermal properties of the dyes and dye layers in more
Data Storage Media
H. Mustroph,* M. Stollenwerk,
V. Bressau
2016 – 2035
Current Developments in Optical Data
Storage with Organic Dyes
Heavy metal triangles: A class of actinide
metallomacrocycles has been prepared in
which three (C5Me5)2An (An = Th, U)
fragments are coordinated by three 5,6dicyano-1-methyl-3-(N-methylamino)isoindolyl bridging ligands (N blue). The
tetravalent actinide centers form a triangular array in the products obtained
through an unprecedented actinide-mediated cyclization of 1,2,4,5-tetracyanobenzene and subsequent self-assembly.
Steric effects govern the catalytic reductive epoxide ring opening. This is the
result of combined experimental and
theoretical studies, which revealed interesting features of the catalyst structure,
substrate binding, transition state (see
picture), and reaction energies. In light of
these, highly selective conditions for the
ring opening can be proposed.
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Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
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individuals who are personal members of a
Actinide Supramolecular Chemistry
J. L. Kiplinger,* J. A. Pool, E. J. Schelter,
J. D. Thompson, B. L. Scott,
D. E. Morris*
2036 – 2041
Actinide-Mediated Cyclization of 1,2,4,5Tetracyanobenzene: Synthesis and
Characterization of Self-Assembled
Trinuclear Thorium and Uranium
Catalyzed Ring Opening
K. Daasbjerg,* H. Svith, S. Grimme,*
M. Gerenkamp, C. MDck-Lichtenfeld,
A. GansEuer,* A. Barchuk,
F. Keller
2041 – 2044
Elucidation of the Mechanism of
Titanocene-Mediated Epoxide Opening by
a Combined Experimental and Theoretical
national chemical society prices are available
on request. Postage and handling charges
included. All prices are subject to local VAT/
sales tax.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
BN Nanotubes
Peeling off the layers: Boron nitride
nanotubes (BNNTs) can be successfully
peeled upon heating in dimethyl sulfoxide
solution. The peeled BN shells can be
reassembled into nanotubes branching
from BNNT trunks to form Y-junction
BNNTs (see TEM images).
Double take: Paired carceroisomers of a
resorcin[4]arene-based C4v carceplex with
an included DMF molecule are formed
when a non-interacting second guest
(CH3CN) exists in excess. The two most
stable carceroisomers of the carceplex
with an included molecule each of DMF
and CH3CH (see picture) were observed in
a 2:1 ratio at 25 8C in CDCl3 by 1H NMR
spectroscopy, and their spatial arrangements were studied by 1H-1H ROESY
Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
Q. Huang,* Y. Bando, C. Zhi, D. Golberg,
K. Kurashima, F. Xu, L. Gao 2044 – 2047
Chemical Peeling and Branching of Boron
Nitride Nanotubes in Dimethyl Sulfoxide
Light fingered: Highly photoluminescent
(PL) polycrystalline dendrites have been
grown by a controlled thermodynamic
process from CdSe/ZnS core/shell quantum dots (see PL image, left) and quantum rods (see confocal PL image, right).
In these dendrites, energy transfer takes
place from the fingers to the core region.
Implications for the nervous system: The
formation of polymeric myelin structures
was studied at the copolymer/water
interface and then elaborated in a dispersed phase. Sun-like structures formed
with a complex multilamellar core and a
corona made of short myelins. Myelin
growth is solvent-promoted, in a strong
analogy to natural myelins, which have
membranes with a higher proportion of
fluidizing molecules such as cholesterol.
Polymer Membranes
A. Sukhanova, A. V. Baranov, T. S. Perova,
J. H. M. Cohen, I. Nabiev*
2048 – 2052
Controlled Self-Assembly of Nanocrystals
into Polycrystalline Fluorescent Dendrites
with Energy-Transfer Properties
G. Battaglia,* A. J. Ryan*
2052 – 2056
Neuron-Like Tubular Membranes Made of
Diblock Copolymer Amphiphiles
Host–Guest Chemistry
C. Ihm, E. Jo, J. Kim,
K. Paek*
2056 – 2059
Paired Carceroisomers
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Platinum Carbonyl Clusters
C. Femoni, F. Kaswalder, M. C. Iapalucci,
G. Longoni,* M. MehlstEubl, S. Zacchini,
A. Ceriotti
2060 – 2062
Synthesis and Crystal Structure of
[NBu4]2[Pt24(CO)48]: An Infinite 1D Stack of
{Pt3(CO)6} Units Morphologically
Resembling a CO-Insulated Platinum
Solvent Effects
C. P. Price, G. D. Glick,
A. J. Matzger*
2062 – 2066
Dissecting the Behavior of a Promiscuous
Solvate Former
Computational Chemistry
D. A. R. S. Latino,
J. Aires-de-Sousa*
2066 – 2069
Genome-Scale Classification of Metabolic
Reactions: A Chemoinformatics Approach
Pieces of eight: Upon crystallization,
[NBu4]2[Pt24(CO)48] self-assembles into
infinite one-dimensional stacks of
{Pt3(CO)6} units arranged in layers
separated by [NBu4]+ ions. Close examination of the {Pt3(CO)6} stacks, which
resemble CO-insulated platinum cables
(see picture; CO ligands omitted), shows
them to be composed of alternating
blocks of seven {Pt3(CO)6} units and
single {Pt3(CO)6} units.
Take any partner: Benzodiazepine derivative Bz-423 (see picture) can be described
as an indiscriminate solvate former as it
cocrystallizes with a diverse array of small
molecules. This behavior was investigated
by analysis of the packing efficiency of
these crystal forms relative to that of
unsolvated Bz-423 and an appropriate
model compound.
On the map: A Kohonen self-organizing
map distributes 3468 metabolic reactions
over a 2D surface according to their
similarity (neurons activated by reactions
of the same enzyme class are identically
colored). No specification of the reaction
center was used. General agreement with
EC numbers was observed. Red = oxidoreductases, dark blue = transferases,
green = hydrolases, yellow = lyases, light
blue = isomerases, pink = ligases.
Computational Chemistry
S. X. Tian,* J. Yang
2069 – 2072
Effects of Intramolecular Hydrogen
Bonding on the Ionization Energies of
Ab initio studies show the influence of
intramolecular hydrogen bonding on the
ionization energies of proline conformers
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
(see picture). These results were used to
assign the UV photoelectron spectrum.
Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
Artemisinin—the next generation: Efficacies of artemisone against the malaria
parasite are substantially greater than
those of the current artemisinin “gold
standard”, artesunate. Also, in contrast to
most current artemisinins it displays low
lipophilicity and negligible neuro- and
cytotoxicity in in vitro and in vivo assays.
Thus, the drug offers promise for use in
artemisinin-based combination therapy.
Two become one: An AB-type monomer
containing both 2-ureido-4[1H]-pyrimidinone and 2,7-diamido-1,8-naphthyridine
quadruple hydrogen-bonding moieties is
obtained by selective olefin cross metathesis. This monomer addresses the issue
of stoichiometric imbalance in the selfassembly of AA + BB-type supramolecular
polymers. Moreover, as the linker between
both motifs is quite flexible, this monomer
exists as a monocycle at low concentrations.
Models incorporated: Two model systems
representing the core structures of antitumor compounds lomaiviticins A and B
have been prepared through a temporary
bridge strategy (the structures of lomaiviticin A and its model core structure 1 are
shown; BOM = benzyloxymethyl). A feature of the approach is a stereocontrolled
Michael addition of dimethyl malonate to
a dimeric enone.
Natural Products
O. A. Scherman, G. B. W. L. Ligthart,
R. P. Sijbesma,*
E. W. Meijer*
2072 – 2076
A Selectivity-Driven Supramolecular
Polymerization of an AB Monomer
K. C. Nicolaou,* R. M. Denton, A. Lenzen,
D. J. Edmonds, A. Li, R. R. Milburn,
S. T. Harrison
2076 – 2081
Stereocontrolled Synthesis of Model Core
Systems of Lomaiviticins A and B
Antimalarial Drugs
R. K. Haynes,* B. Fugmann, J. Stetter,
K. Rieckmann, H.-D. Heilmann,
H.-W. Chan, M.-K. Cheung, W.-L. Lam,
H.-N. Wong, S. L. Croft, L. Vivas, L. Rattray,
L. Stewart, W. Peters, B. L. Robinson,
M. D. Edstein, B. Kotecka, D. E. Kyle,
B. Beckermann, M. Gerisch, M. Radtke,
G. Schmuck, W. Steinke, U. Wollborn,
K. Schmeer, A. RSmer
2082 – 2088
Artemisone—A Highly Active Antimalarial
Drug of the Artemisinin Class
Straightening out chirality: Chiral mesostructured silica nanofibers of MCM-41
with one (see TEM image, the arrows
indicate periodic fringes) and two twist
axes were fabricated from a simple dilute
synthesis system without any chiral additives. A continuous transformation from a
chiral mesostructure to an achiral straight
mesostructure was observed, thus
demonstrating an interesting relationship
between these two seemingly different
Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
Mesoporous Materials
B. Wang, C. Chi, W. Shan, Y. H. Zhang,
N. Ren, W. L. Yang, Y. Tang* 2088 – 2090
Chiral Mesostructured Silica Nanofibers
of MCM-41
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Cyclization Sequence
J. Barluenga,* A. DiTguez, A. Fern%ndez,
F. RodrUguez, F. J. FaVan%s 2091 – 2093
Gold- or Platinum-Catalyzed Tandem
Cycloisomerization/Prins-Type Cyclization
Straightforward and efficient: Functionalized eight-membered carbocycles are
easily obtained from simple allyl-substituted 5-hexyn-1-ol derivatives by a cataly-
Gas-Phase studies
Changing the state: The electrophilicity of
benzhydryl cations (see formula) towards
neutral amine nucleophiles in the gas
phase was determined. It was found that
the kinetics of electrophile–nucleophile
gas-phase reactions correlate well with
values known in solution although the
actual electrophilicity parameters are
considerably smaller in the gas phase.
C. Denekamp,* Y. Sandlers
2093 – 2096
Electrophilicity–Nucleophilicity Scale Also
in the Gas Phase
tic tandem sequence involving a 6-exo
cycloisomerization followed by a Prinstype cyclization (see scheme).
Asymmetric Synthesis
A. Blanc, F. D. Toste*
2096 – 2099
Enantioselective Synthesis of Cyclic Ethers
through a Vanadium-Catalyzed
Resolution/Oxidative Cyclization
Two steps, one catalyst: A vanadium(v)–
oxo complex with a tridentate Schiff base
as an additional ligand catalyzes the title
reaction which transforms racemic bishomoallylic a-hydroxyesters into transtetrahydropyrans (THPs) and cis-tetrahy-
drofurans (THFs). This synthetic method
provides an efficient asymmetric synthesis of cyclic ethers as demonstrated by
the first enantioselective synthesis of
( )-pantofuranoid E. TBHP = tert-butylhydroperoxide.
Switch over: All the disulfide moieties in
the cations of an iodoplumbate display
the same chiral conformation in a single
crystal; however, during a phase transition
(75 8C) half of these molecules undergo a
conformational change, from the left- to
the right-handed helical form, and a true
racemate is formed. This transition is
reversible, and thus this compound can
act as a second harmonic generation
N. Mercier,* A.-L. Barres, M. Giffard,
I. Rau, F. Kajzar, B. Sahraoui 2100 – 2103
Reversible Solid-State Transition in
Crystals of an Organic Disulfide-Based
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
The missing link: Chiral catenanes have
been obtained by including prochiral
phosphorus centers in both rings of a
[2]catenane moiety. These compounds,
which also contain stereogenic carbon
atoms, have been prepared by the well
known copper(i) template synthesis and
have been isolated as enantiomerically
pure, single diastereoisomers.
Template Synthesis
A. Theil, C. Mauve, M.-T. Adeline,
A. Marinetti,* J.-P. Sauvage 2104 – 2107
Phosphorus-Containing [2]Catenanes as
an Example of Interlocking Chiral
Breaking the rule: The metal-carbide
endofullerene Sc2C2@C68 was isolated and
characterized (see picture). It has a
valence state (Sc3+)2(C2)2 @C684 , and its
carbon cage does not comply with the
isolated-pentagon rule (IPR). This result,
in combination with previous work on
Sc3N@C68, shows that different non-IPR
C68 cages can be synthesized by using
different endohedral clusters as templates.
Z.-Q. Shi, X. Wu, C.-R. Wang,* X. Lu,*
H. Shinohara*
2107 – 2111
Isolation and Characterization of
Sc2C2@C68 : A Metal-Carbide
Endofullerene with a Non-IPR Carbon
Lipid Bilayers
M. J. Spencelayh, Y. Cheng, R. J. Bushby,
T. D. H. Bugg, J.-j. Li, P. J. F. Henderson,
J. O’Reilly, S. D. Evans*
2111 – 2116
At the end of its tether: Solid-supported
tethered lipid bilayers that present native
versions of the peptidoglycan precursors
lipid I and lipid II are used to compare the
binding of vancomycin and ramoplanin.
Through the use of E. coli inner mem-
branes, the resulting “proteolipid layer”
contains the full range of intrinsic and
extrinsic proteins found in vivo, thus
allowing the in vitro biosynthesis of a
peptidoglycan cell wall. E = enzyme.
Antibiotic Action and Peptidoglycan
Formation on Tethered Lipid Bilayer
A. McNally, B. Evans,
M. J. Gaunt*
Simple secondary amine organocatalysts
induce a general [2,3] Wittig rearrangement via an enamine under extremely
mild conditions. The organocatalytic
rearrangement gives good diastereose-
Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
lectivities over a range of substrates and
generates the syn isomer, which is contrary to what would be expected from the
conventional [2,3]-reaction.
2116 – 2119
Organocatalytic Sigmatropic Reactions:
Development of a [2,3] Wittig
Rearrangement through Secondary Amine
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
F. de Montigny, R. Macias, B. C. Noll,
T. P. Fehlner*
2119 – 2122
Molybdenum-Mediated Alkyne
Incorporation into an Iridaborane
Framework—Release of the
Iridacarborane from the Molybdenum
Coordination Sphere through a
Dissociative Equilibrium
Microporous Materials
F. Stallmach,* S. GrSger, V. KDnzel,
J. KErger, O. M. Yaghi, M. Hesse,
U. MDller*
2123 – 2126
NMR Studies on the Diffusion of
Hydrocarbons on the Metal-Organic
Framework Material MOF-5
Chaperone service: An iridacarborane–
Mo(CO)3 coordination equilibrium follows the insertion of two 2-butyne units
into iridaborane [(Cp*IrH)B4H9] to give
[Cp*Ir(B3H3C4Me4){Mo(CO)3}] (1; yellow
On the move: High intracrystalline mobilities and fast exchange between the
crystal and the surrounding gas phase
were found in NMR studies on the diffusion of methane, ethane, n-hexane, and
benzene in large crystals of the metalorganic framework MOF-5 (see SEM
image). The results support future use of
metal-organic framework materials as
tailorable sorbents for fast gas processing
and gas-storage materials in industry.
Switchable Biostructures
D. Strohbach, N. Novak,
S. MDller*
Ir, green B, magenta Mo, black C, red O,
cyan H); a reduced binding affinity frees
the iridacarborane [Cp*Ir(B3H3C4Me4)]
On and off: A flavine mononucleotide
(FMN) dependent hairpin ribozyme can
sense the oxidative state of its environment. Although oxidized FMN is planar
and thus binds to the allosteric domain of
the ribozyme, binding is interrupted by
reduction of FMN due to the change from
planar to rooflike geometry reflected in
dramatically decreased ribozyme activity.
2127 – 2129
Redox-Active Riboswitching: Allosteric
Regulation of Ribozyme Activity by
Ligand-Shape Control
Asymmetric Polymerization
I. Hilker, G. Rabani, G. K. M. Verzijl,
A. R. A. Palmans, A. Heise* 2130 – 2132
Chiral Polyesters by Dynamic Kinetic
Resolution Polymerization
Problem resolved: Enzymatic polymerization was combined with an in situ Rucatalyzed racemization process. The
reaction mixture comprises a racemic
mixture of a chiral diol and dimethyl
adipate. Because of the high stereoselec-
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
tivity of the enzyme Candida antarctica
lipase B (CALB), the S-configured stereocenters of the chiral diol are practically
nonreactive. Polycondensation was
achieved by concurrent racemization of
the S- into the R-configured centers.
Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
Coordination Chemistry
All good things come in fours: Thermal
metal–metal borylene transfer from the
terminal borylene complexes
[(OC)5M=BN(SiMe3)2] (M = Cr, W) leads
to the new tetranuclear rhodium complex
(see structure), which is the first doubly
borylene-bridged transition-metal
complex. In the solid state, the tetranuclear units aggregate (dashed lines),
giving a rare example of a neutral chain of
rhodium atoms.
H. Braunschweig,* M. Forster,
K. Radacki
2132 – 2134
Borylene Transfer under Thermal
Conditions: Synthesis and Structure of a
Tetrarhodium Bisborylene Complex
Extremely little is known about the factors
governing the efficiency of photoionizations. The comparison of propiophenone
and g-methylvalerophenone highlights
that a spontaneous intramolecular transformation accompanied by small structural and electronic changes—the conversion of a triplet moiety into a radical
(anion) moiety by a Norrish II reaction—
can have a pronounced effect on the
electron yield.
Clamping down: A new class of aspartic
protease inhibitors that target the malarial
protease family Plasmepsin are reported.
These ligands utilize a novel “diamine
clamp” to engage the catalytic dyad. They
are potent inhibitors of plasmepsins I, II,
and IV, while retaining good selectivity
against the closely related human cathepsins D and E.
M. Goez,* V. Zubarev
2135 – 2138
Efficient Photoionization of a Norrish II
Enzyme Inhibitors
F. Hof, A. SchDtz, C. FEh, S. Meyer, D. Bur,
J. Liu, D. E. Goldberg,
F. Diederich*
2138 – 2141
Starving the Malaria Parasite: Inhibitors
Active against the Aspartic Proteases
Plasmepsins I, II, and IV
The issues for March 2006 appeared online on the following dates
Issue 9: February 13 · Issue 10: February 21 · Issue 11: March 1 · Issue 12: March 6
Angew. Chem. Int. Ed. 2006, 45, 1992 – 2001
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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