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Graphical Abstract Angew. Chem. Int. Ed. 142004

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Contents
The following articles are available online (in Wiley InterScience). You can find them at
www.angewandte.org, under Early View.
S. Garratt, A. Guerrero, D. L. Hughes, M. Bochmann*:
Arylzinc Complexes as New Initiator Systems for the Production
of Isobutene Copolymers with High Isoprene Content
DOI: 10.1002/anie.200353787
Published online: March 15, 2004
H. Torii, M. Nakadai, K. Ishihara, S. Saito,* H. Yamamoto*:
Asymmetric Direct Aldol Reaction Assisted by Water and a
Proline-Derived Tetrazole Catalyst
DOI: 10.1002/anie.200352724
Published online: March 16, 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
Fulvio Cacace (1931–2003): Structure and Mechanism in Gas-Phase Chemistry
and Its Relevance to the Condensed State
G. A. Olah
1760
Books
Handbook of Chemoinformatics
1761
Johann Gasteiger
reviewed by G. Schneider
IR and Raman Spectroscopy
1761
Siegfried Wartewig
reviewed by H. P. Reisenauer
Contrasting styles: The two catalysts
shown are both effective for the cyanation
of ketimines. The metal-based catalyst 1,
developed by a standard approach, displays a very broad scope and substrate
generality. The metal-free catalyst 2 was
designed by a combination of random
screening and mechanism-based
optimization.
Highlights
Cyanation Reactions
C. Spino*
1764 – 1766
Recent Developments in the Catalytic
Asymmetric Cyanation of Ketimines
Carbenes
W. Kirmse*
1767 – 1769
Stable Singlet Carbenes—Plentiful and
Versatile
1750
Electron donation from substituents is the
principal mechanism of stabilizing singlet
carbenes. Two amino groups are optimal
(A). With additional steric protection, one
amino group is sufficient (B). The effect of
phosphanyl groups is enhanced by an
electron acceptor as the second
substituent (C).
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 1750 – 1757
Angewandte
Chemie
Essays
Must chemistry stink and go bang? The
laboratory as a forbidding setting, as a
workshop of extraordinary obscurantists
whose sole unholy purpose is to produce
all manner of poisons and acids, is a fond
Chemistry in Literature
stereotype in literary fiction. Realistic
descriptions are reserved exclusively for
chemist writers. A foray through the
literature shows that chemistry sometimes has a sinister public image.
O. Kr>tz*
1770 – 1780
The Chemical Laboratory: Source of
Progress or Chamber of Horrors?
Reviews
Bonding concepts: Agostic interactions in
early-transition-metal alkyl complexes are
reviewed, and shown to arise from delocalization of the MC bond rather than
through M···HC bonding: charge-density
analysis (see picture) reveals intimate
aspects of the phenomenon and shows
how the agostic interaction competes
with other ligand-induced effects at the
metal center.
Theoretical Chemistry
W. Scherer,*
G. S. McGrady*
1782 – 1806
Agostic Interactions in d0 Metal Alkyl
Complexes
Communications
Polymer Nanoparticles
The use of aqueous emulsions as the
media when conducting cross-coupling
reactions, instead of homogeneous solutions, produces covalently cross-linked
conjugated polymer particles (see picture). The size of the spherical particles
can easily be tuned over a wide range
(mm to nm) by modification of the
reaction conditions. The resulting materials are processable in the form of a
suspension and promise to have
interesting electronic properties.
E. Hittinger, A. Kokil,
C. Weder*
1808 – 1811
Synthesis and Characterization of CrossLinked Conjugated Polymer Milli-, Micro-,
and Nanoparticles
Drug Delivery
Breaking into cells: A new family of
peptides based on the amphipathic
proline-rich sequence (VXLPPP)n , where
n = 1–3 and X = His, Lys, or Arg, has been
designed (see picture). Their nonviral
origin, absence of toxicity at high concentrations, and high solubility in water
make this new series very promising for
use in drug delivery.
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Angew. Chem. Int. Ed. 2004, 43, 1750 – 1757
www.angewandte.org
J. FernDndez-Carneado, M. J. Kogan,
S. Castel, E. Giralt*
1811 – 1814
Potential Peptide Carriers: Amphipathic
Proline-Rich Peptides Derived from the
N-Terminal Domain of g-Zein
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1751
Contents
Cluster Compounds
You’re round and bound: A bowed
arrangement of bridging bidentate binding sites on a ligand framework precludes
a linear arrangement of metal ions. This
conformation allows a spin-coupled octanuclear copper(ii) circular array to be
formed from a single-stranded ligand (see
picture); this circular array displays weak
ferromagnetic exchange between metal
centers and is a rare example of such an
array containing more than six centers.
S. T. Onions, S. L. Heath, D. J. Price,
R. W. Harrington, W. Clegg,
C. J. Matthews*
1814 – 1817
Self-Assembly of a Spin-Coupled Octanuclear Copper(ii) Circular Array from a
Single-Stranded Ligand
Dawson Clusters
D.-L. Long, P. KNgerler,
L. Cronin*
1817 – 1820
Old Clusters with New Tricks: Engineering
S···S Interactions and Novel Physical
Properties in Sulfite-Based Dawson
Clusters
Unprecedented 18-molybdosulfite
Dawson clusters encapsulate two pyramidal sulfite ions as templates, and
exhibit a short S···S interaction between
the two ions, which was characterized by
DFT calculations. The [Mo18O54(SO3)2]4
ion is the first discrete thermochromic
polyoxometalate cluster: its color varies
from pale yellow at 77 K to deep red at
500 K (see picture).
Better by design: Exploitation of the
macrocyclic architecture of a cyclophanebased ligand provides new highly active
catalysts with improved thermal stability
for ethylene polymerization. The strategic
positioning of the metal center at the core
of the cyclophane-based ligand is the key
to the observed high activity and thermal
stability, and to the high molecular weight
of the polyethylene (see picture; red: Pd,
green: Cl, blue: N, gray: C).
Polymerization Catalysts
D. H. Camacho, E. V. Salo, J. W. Ziller,
Z. Guan*
1821 – 1825
Cyclophane-Based Highly Active LateTransition-Metal Catalysts for Ethylene
Polymerization
Nanomaterials
R. Harada, Y. Matsuda, H. Ōkawa,
T. Kojima*
1825 – 1828
A Porphyrin Nanotube: Size-Selective
Inclusion of Tetranuclear Molybdenum–
Oxo Clusters
1752
Mo takes the tube: A saddle-distorted
MoV–porphyrin complex forms a tubular
assembly through intermolecular p–p
interactions, which has an internal
diameter of 1 nm (see picture). Within
such tubes, tetranuclear MoVI–oxo
clusters could be size-selectively included
through intermolecular hydrogen-bonding
interactions.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 1750 – 1757
Angewandte
Chemie
Holey magnets: A pure organic nanoporous material (POROF-2) exhibiting
astonishing thermal stability, hydrophilic
one-dimensional channels (see structure), and a long-range ferromagnetic
ordering is prepared. This zeolite-like
material is the first example of a purely
organic robust open-framework magnet.
A cluster-forming ligand, p-tert-butylsulfonylcalix[4]arene (H4L), allows the formation of lanthanide wheels whose cluster cores contain eight lanthanide ions
(GdIII, SmIII, NdIII, or PrIII ; shown in green
in the picture) connected by L4 ions,
which act as both a tetradentate and a
bisbidentate m3-ligand, and eight bridging
acetate groups. The wheels form by a
“step-by-step” process via the mononuclear subunit {Ln(L)}.
Angew. Chem. Int. Ed. 2004, 43, 1750 – 1757
Magnetic Materials
D. Maspoch, N. Domingo,
D. Ruiz-Molina, K. Wurst, G. Vaughan,
J. Tejada, C. Rovira,
J. Veciana*
1828 – 1832
A Robust Purely Organic Nanoporous
Magnet
Wheel Complexes
T. Kajiwara,* H. Wu, T. Ito,* N. Iki,*
S. Miyano
1832 – 1835
Octalanthanide Wheels Supported by
p-tert-Butylsulfonylcalix[4]arene
Nest building: a method to create a rigid
hydrogen-bond receptor through the
simultaneous binding of three thiol
substituent groups to a gold surface is
reported (see picture: red = O, gray = C,
blue = N, yellow = S, purple = Au surface
atom). These receptors are able to distinguish and select for p surfaces with a
complementary size, shape, and hydrogen-bonding code.
Molecular Recognition
Better molecular wires could result from
an improved understanding of the effects
of nucleotide sequence on the efficiency of
excess electron transfer in DNA. Negative
charge migrates in duplex DNA from a
photoexcited aromatic amine residue (D;
see figure) to 5-bromo-2’-deoxyuridine
(BrU) in a sequence- and orientationdependent manner.
Electron Transfer in DNA
www.angewandte.org
G. S. Tulevski, M. L. Bushey, J. L. Kosky,
S. J. T. Ruter, C. Nuckolls*
1836 – 1839
Assembling Dimeric p Stacks on Gold
Surfaces by Using Three-Dimensional
Lock-and-Key Receptors
T. Ito, S. E. Rokita*
1839 – 1842
Criteria for Efficient Transport of Excess
Electrons in DNA
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1753
Contents
Electron Transfer in DNA
C. Haas, K. Kr>ling, M. Cichon, N. Rahe,
T. Carell*
1842 – 1844
Excess Electron Transfer Driven DNA
Does Not Depend on the Transfer
Direction
Electron Transfer in DNA
N. Amann, R. Huber,
H.-A. Wagenknecht*
1845 – 1847
Phenanthridinium as an Artificial Base
and Charge Donor in DNA
DNA is a two-way street: Excess electron
transfer in DNA over distances of 3.4–
23.8 V does not depend on the transfer
direction, as shown by probing DNA:PNA
hybrid double strands containing a
cyclobutane pyrimidine dimer (T¼T) and
flavin (Fl; see figure).
A tool for time-resolved studies: The
phenanthridinium unit of ethidium was
incorporated into oligonucleotides (see
scheme) as an artificial DNA base. The
resulting duplexes can be used to study
electron-transfer processes by spectroscopic techniques and to compare the
rates of reductive electron transfer and
oxidative hole transfer.
Electron Transfer in DNA
B. Giese,* B. Carl, T. Carl, T. Carell,*
C. Behrens, U. Hennecke, O. Schiemann,*
E. Feresin
1848 – 1851
Excess Electron Transport Through DNA:
A Single Electron Repairs More than One
UV-Induced Lesion
Coordination Networks
D.-L. Long, R. J. Hill, A. J. Blake,
N. R. Champness,* P. Hubberstey,*
D. M. Proserpio, C. Wilson,
M. SchrNder*
1851 – 1854
Site-selective injection of a single electron
into thymine (yellow) through the
modified nucleoside 1 (1!2) was used to
examine the dependence of excess
electron transfer in DNA on distance. The
DNA was cleaved upon arrival of the
electron at a thymine dimer (red). This
assay showed that one electron can repair
more than one UV-induced lesion in DNA
3.
Non-CsCl topologies for eight-connected
solid-state materials have been observed
for the first time in three networks based
on lanthanide cations and 4,4’-bipyridineN,N’-dioxide ligands. The structure of the
{[Yb(L)4](CF3SO3)3}¥ network is depicted.
Non-Natural Eight-Connected Solid-State
Materials: A New Coordination Chemistry
1754
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 1750 – 1757
Angewandte
Chemie
“Naked” Fluoride
Fs in rings: A cyclic multidentate Lewis
acidic receptor is coordinated by a weakly
bonded fluoride ion in 1 (see picture).
This host–guest system has properties
such as air- and moisture-stability, solubility in common organic solvents, and
utility as a source for “naked” fluoride
ions generated in situ.
M. J. Bayer, S. S. Jalisatgi, B. Smart,
A. Herzog, C. B. Knobler,
M. F. Hawthorne*
1854 – 1857
B-Octamethyl-[12]Mercuracarborand-4 as
Host for “Naked” Fluoride Ions
Step-Growth Polymerization
K. Miki, Y. Washitake, K. Ohe,*
S. Uemura*
1857 – 1860
Polyaddition and Polycondensation
Reactions of (2-Furyl)carbenoid as StepGrowth Polymerization Strategies:
Synthesis of Furylcyclopropane- and
Furfurylidene-Containing Polymers
Polymers from carbenoid intermediates: A
new approach to the synthesis of cyclopropane- and alkene-containing polymers
that contain both a carbenoid donor and
acceptor is described. The polymers can
be effectively obtained from enyne
ketones via carbenoid intermediates in
the presence of a [{Rh(OAc)2}2] catalyst
(see scheme).
Cycloadditions
D. Motoda, H. Kinoshita, H. Shinokubo,*
K. Oshima*
1860 – 1862
A highly active, cationic, phosphaneligand-free rhodium species is formed in
an aqueous anionic micellar system
(see scheme). The combination of
[{RhCl(nbd)}2]–sodium dodecyl sulfate
acts as an effective catalyst for the intramolecular [4þ2] annulation of 2,4-dienyl
propargyl ethers in water (nbd = norbornadiene).
Phosphane-Free Rhodium Catalyst in
an Anionic Micellar System for
[4þ2] Annulation of Dienynes
Microreactors
T.-C. Kuo, H.-K. Kim, D. M. Cannon, Jr.,
M. A. Shannon, J. V. Sweedler,*
P. W. Bohn*
1862 – 1865
Nanocapillary Arrays Effect Mixing and
Reaction in Multilayer Fluidic Structures
Reactant mixing is implemented in structures with characteristic length scales of
nanometers (see picture). Mixing occurs
within micron distances rather than the
Angew. Chem. Int. Ed. 2004, 43, 1750 – 1757
centimeters that are often needed for
laminar microflows. The application of the
nanocapillary mixer to detect Ca2+ ions
demonstrates its potential use in sensors.
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1755
Contents
Sigmatropic Rearrangement
E. E. Lee, R. A. Batey*
1865 – 1868
Palladium-Catalyzed [3,3] Sigmatropic
Rearrangement of (Allyloxy)iminodiazaphospholidines: Allylic Transposition of
CO and CN Functionality
A PV¼N to PV¼O interconversion is the
thermodynamic driving force for the title
reaction. Iminodiazaphospholidines 1
give phosphoramides 2, which are sub-
Fragmentation of the (R)-(þ)-1-phenyl-1propanol radical cation ([(BZC2H5)R]+) is
markedly affected by asymmetric microsolvation (see picture). The CaCb bond
cleavage in the heterochiral
[(BZC2H5)RCBDSS]+ cluster is more efficient
than in the homochiral [(BZC2H5)RCBDRR]+.
The difference is ascribed to structural
factors that make BDSS a better H-bond
acceptor than BDRR in their adducts with
[(BZC2H5)R]+. BZ = PhCHOH, BD = 2,3butanediol.
Bond Cleavage
D. Catone, A. G. Guidoni, A. Paladini,
S. Piccirillo, F. Rondino, M. Satta,
D. Scuderi, M. Speranza*
1868 – 1871
Homolytic CaCb Bond Cleavage in a
Chiral Alkylarene Radical Cation: Effects of
Asymmetric Microsolvation
Coupling Catalyst
S. D. Walker, T. E. Barder, J. R. Martinelli,
S. L. Buchwald*
1871 – 1876
A Rationally Designed Universal Catalyst
for Suzuki–Miyaura Coupling Processes
H2 Activation Mechanism
D. Sellmann, R. Prakash,*
F. W. Heinemann, M. Moll,
M. Klimowicz
1877 – 1880
Heterolytic Cleavage of H2 at a SulfurBridged Dinuclear Ruthenium Center
1756
sequently hydrolyzed under mild acidic
conditions to yield primary or tosylamines
3. R = alkyl, phenyl; Ts = p-toluenesulfonyl.
Unprecedented scope, reactivity, and stability are displayed by a new catalyst
system. This was demonstrated with
general and efficient syntheses of
sterically hindered (hetero)biaryls (see
examples shown), mild coupling reactions
of alkyl boron derivatives, and rapid
coupling reactions of aryl chlorides at
room temperature.
Incoming molecular hydrogen breaks the
RuS bridges in the diruthenium complex
[Ru(pybuS4)]2 (pybuS42 = 2,6-bis(2-sulfanyl-3,5-di-tert-butylphenylthio)dimethylpyridine(2)) shown, and the HH bond
is cleaved to give H+ and H in the
resulting thiol-protonated hydride
[Ru(H)(pybuS4-H)]. The proposed
mechanism of the heterolytic cleavage
of H2 at the RuS centers is intriguing
and possibly relevant to the activation
of H2 by hydrogenases.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 1750 – 1757
Angewandte
Chemie
Heck Reactions
S. S. PrNckl, W. Kleist, M. A. Gruber,
K. KNhler*
1881 – 1882
Needing a leach: Optimized palladium/
metal oxide systems are highly active
heterogeneous catalysts for the Heck
reaction. Non-activated and deactivated
aryl chlorides can be converted by
palladium/zeolite (NaY) catalysts (see
scheme). The dissolution of palladium
(leaching) from the surface of the support,
its redeposition, and the control of these
equilibria are found to be crucial for the
success of the reaction.
In Situ Generation of Highly Active
Dissolved Palladium Species from Solid
Catalysts—A Concept for the Activation
of Aryl Chlorides in the Heck Reaction
Chemical Constituents of Fungi
What do some fungi have in common with
chemists? Common earthballs (see picture) and peppery boletes are true artists
in natural product synthesis. In few biosynthetic steps they assemble structurally
fascinating alicyclic pigments from simple
aromatic precursors.
M. Winner, A. GimWnez, H. Schmidt,
B. Sontag, B. Steffan,
W. Steglich*
1883 – 1886
Unusual Pulvinic Acid Dimers from the
Common Fungi Scleroderma citrinum
(Common Earthball) and Chalciporus
piperatus (Peppery Bolete)
Prebiotic Chemistry
On the way to life, the formation of amino
acids on the primordial earth was one of
the essential prerequisites. To date, this
formation could only be explained
assuming a reducing atmosphere, which
according to contemporary geochemistry
could not have existed. Simulating a
neutral primitive CO2/N2/H2O atmosphere above liquid water with frequent
electric discharges (see picture) provides
a model for the formation of peptides, and
thus proteins and ultimately life.
K. Plankensteiner, H. Reiner, B. Schranz,
B. M. Rode*
1886 – 1888
Prebiotic Formation of Amino Acids in a
Neutral Atmosphere by Electric Discharge
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
Service
19/2004
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April 16
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Angew. Chem. Int. Ed. 2004, 43, 1750 – 1757
May 3
May 10
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Keywords
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Authors
1891
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