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Graphical Abstract Angew. Chem. Int. Ed. 292003

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The following articles are available online (in Wiley Interscience). You can find them at, under Full Text, Forthcoming Articles.
M. Toganoh, Y. Matsuo, E. Nakamura*:
Rhenium-Templated Regioselective Polyhydrogenation Reaction
of [60]Fullerene
DOI: 10.1002/anie.200351722
Published online: July 11, 2003
R. R. Davda, J. A. Dumesic*:
Catalytic Reforming of Oxygenated Hydrocarbons for Hydrogen
with Low Levels of Carbon Monoxide
DOI: 10.1002/anie.200351664
Published online: June 18, 2003
N. T. Tran, L. F. Dahl*:
Nanosized [Pd69(CO)36(PEt3)18]: Metal-Core Geometry Containing
a Linear Assembly of Three Face-Sharing Centered Pd33 Icosahedra Inside of a Hexagonal-Shaped Pd30 Tube
DOI: 10.1002/anie.200351738
Published online: July 11, 2003
I. D. Hills, G. C. Fu*:
Catalytic Enantioselective Synthesis of Oxindoles and Benzofuranones that Bear a Quaternary Stereocenter
DOI: 10.1002/anie.200351666
Published online: July 3, 2003
Articles judged by the referees or the editior as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editiorial office in 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.
Ilya Prigogine (1917 – 2003) 3324 – 3325
Structure Formation far from Equilibrium
Grgoire Nicolis
Encyclopedia of Electrochemistry,
Vol. 9
Encyclopedia of Electrochemistry,
Vol. 1
George S. Wilson
reviewed by Wolfgang Schumann
Eliezer Gileadi, Michael Urbakh
reviewed by Rudolf Holze
A model debate: The recent review of the
book “Chemical Bonding and Molecular
Geometry” has led to a discussion
Bonding and Geometry
between the authors and the reviewer
regarding the validity of the models
chosen and the conclusions drawn.
R. J. Gillespie,* P. L. A. Popelier 3331 – 3334
G. Frenking*
“Chemical Bonding and Molecular
Geometry”: Comments on a Book Review
and Reply to the Comments of Gillespie
and Popelier
More immobile and more stable: The
advantages of the immobilization of biocatalysts, for example, through the formation of aggregates or linking to iron
oxide nanoparticles and organic supports
(see scheme), include an enhanced stability, simple separation from the reaction
mixture, and often an increased activity of
the immobilizate.
Angew. Chem. Int. Ed. 2003, 42, 3315 – 3322
Immobilized Biocatalysts
U. T. Bornscheuer*
3336 – 3337
Immobilizing Enzymes: How to Create
More Suitable Biocatalysts
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
NMR of Biomacromolecules
K. WEthrich*
3340 – 3363
NMR Studies of Structure and Function
of Biological Macromolecules (Nobel
The structure of proteins (such as that of
bovine prion protein, see picture) and
further information on the dynamics and
structural, thermodynamic, and kinetic
aspects of their interactions with other
components in solution can be obtained
by NMR methods developed by
K. WEthrich and his group. In his Nobel
Lecture, WEthrich delves into the past,
present, and future of these techniques,
and offers us a glimpse into his life.
Clean Hydrogen Oxidation
G. Rothenberg,* E. A. de Graaf,
A. Bliek
3366 – 3368
Solvent-Free Synthesis of Rechargeable
Solid Oxygen Reservoirs for Clean
Hydrogen Oxidation
Self-Assembling Circuits
M. Boncheva, R. Ferrigno, D. A. Bruzewicz,
G. M. Whitesides*
3368 – 3371
Plasticity in Self-Assembly: Templating
Generates Functionally Different Circuits
from a Single Precursor
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Cutting out the coke: The concept of
catalytic oxidative dehydrogenation by
using solid oxygen exchangers and a
solvent-free parallel synthesis of a set of
ten bimetallic catalysts is described. The
compounds were tested in the selective
oxidation of hydrogen in the presence of
ethane and ethylene (HCs) at 600 8C.
Cerium tungsten oxide was found to be a
superb rechargeable “oxygen reservoir”
(see picture), with 97 % chemoselectivity
and negligible coking levels.
The structures and patterns of electrical
connections within 3D self-assembled
aggregates can be templated by the
geometry of the space in which the selfassembly proceeds. This finding demonstrates that, in principle, multiple functions can be derived from the same set of
components by controlling a macroscopic
variable (see picture).
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Angew. Chem. Int. Ed. 2003, 42, 3315 – 3322
[70]Fullerene-Based Photovoltaics
Owing to their increased absorption of
light in the visible region, [70]fullerene
derivatives provide a high photocurrent
when incorporated as the electron
acceptor in thin-film polymer photovoltaic
cells. An incident-photon-to-current efficiency of 66 % is obtained when [70]PCBM
(see picture) is used in combination with
a poly(p-phenylene vinylene). These high
currents originate from an ultrafast charge
transfer that occurs upon photoexcitation
of either the fullerene or the polymer.
M. M. Wienk, J. M. Kroon,*
W. J. H. Verhees, J. Knol, J. C. Hummelen,*
P. A. van Hal,
R. A. J. Janssen*
3371 – 3375
Efficient Methano[70]fullerene/MDMOPPV Bulk Heterojunction Photovoltaic
Corannulene Complexes
Corannulene, the smallest subunit of C60
that retains a curved surface, forms
crystalline h2-coordinated p complexes
with dirhodium(ii) tetrakis(trifluoroacetate) by using solvent-free gas-phase
deposition. As many as three metal atoms
coordinate to the double bonds found at
the rim of each corannulene, with one
such atom always located on the concave
surface (see picture).
M. A. Petrukhina,* K. W. Andreini,
J. Mack, L. T. Scott
3375 – 3379
Transition-Metal Complexes of an Open
Geodesic Polyarene
A simple versatile route to polyrotaxanes
with a variety of topologies is described
through the synthesis and subsequent
polymerization of readily accessible and
stable rotaxane monomers containing
bulky blocked isocyanate stopper groups.
T. J. Kidd, T. J. A. Loontjens,* D. A. Leigh,*
J. K. Y. Wong
3379 – 3383
Rotaxane Building Blocks bearing Blocked
Isocyanate Stoppers: Polyrotaxanes
through Post-Assembly Chain Extension
Desymmetrizing meso-Diols
An effective catalyst for the asymmetric
monobenzoylation of meso-1,2-diols was
designed—the phosphinite derivative of
cinchonine (see formula). In the presence
of 30 mol % of this catalyst the monobenzoylated products were obtained with
high yields and enantioselectivities.
Angew. Chem. Int. Ed. 2003, 42, 3315 – 3322
S. Mizuta, M. Sadamori, T. Fujimoto,*
I. Yamamoto
3383 – 3385
Asymmetric Desymmetrization of meso1,2-Diols by Phosphinite Derivatives of
Cinchona Alkaloids
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Metal-Ion Induced Isomerization
V. W.-W. Yam,* X.-X. Lu,
C.-C. Ko
3385 – 3388
First Observation of Alkali Metal Ion
Induced Trans–Cis Isomerization of
Palladium(ii) Phosphane Complexes
Containing Crown Ether Moieties
Solvent-Driven Helix Equilibria
P. Pengo, L. Pasquato,* S. Moro, A. Brigo,
F. Fogolari, Q. B. Broxterman, B. Kaptein,
P. Scrimin*
3388 – 3392
Quantitative Correlation of Solvent Polarity with the a-/310-Helix Equilibrium:
A Heptapeptide Behaves as a SolventDriven Molecular Spring
Ion switches: The addition of small metal
ions (such as Li+ and Na+) to transpalladium(ii) complexes of PPh2-substituted benzo[15]crown-5 and benzo[18]crown-6 results in the formation of
1:1 trans adducts. However, the addition
of large alkali ions (such as K+, Rb+, and
Cs+) enforces the complexes to undergo a
trans–cis isomerization to enable formation of intramolecular sandwich adducts
(see schematic representation).
The long and the short of it: Just by
changing the polarity of the solvent the
highly folded heptapeptide Ac-[Aib-l(aMe)Val-Aib]2-l-His-NH2 converts from
an a into a 310 helix (see picture). The
equilibrium constant between the two
conformations correlates with the empirical solvent polarity parameter ENT. Molecular dynamics calculations show that the
peptide elongates (310 helix) or shortens
(a helix) on switching from one conformation to the other.
Allylation of Aliphatic Aldehydes
M. Kimura, M. Shimizu, K. Shibata,
M. Tazoe, Y. Tamaru*
3392 – 3395
Pd-Catalyzed Nucleophilic Alkylation of
Aliphatic Aldehydes with Allyl Alcohols:
Allyl, 2-Tetrahydrofuryl, and 2-Tetrahydropyranyl Ethers as Useful C3, C4, and C5
A combination of Pd0 and Et2Zn generates
an allyl anion species from allyl alcohols
which can be used for the allylation of
aliphatic aldehydes to provide homoallyl
Olefin Metathesis in Ionic Liquids
Q. Yao,* Y. Zhang
Designer labels: Ruthenium carbene
complex 1 bearing an ionic tag was shown
to be a highly reactive catalyst for the ringclosing metathesis of various diene and
enyne substrates in minimally ionic solvent systems (see scheme; Bmim = 1butyl-3-methylimidazolium, Ts = toluene4-sulfonyl). The catalyst can be repeatedly
recycled and reused (up to at least
10 cycles) without significant loss of its
activity, whereas other catalysts tested
exhibited a dramatic diminishment in
their activity upon recovery from the ionic
3395 – 3398
Olefin Metathesis in the Ionic Liquid
1-Butyl-3-methylimidazolium Hexafluorophosphate Using a Recyclable Ru
Catalyst: Remarkable Effect of a Designer
Ionic Tag
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
alcohols in good yields (see scheme). The
reaction proceeds at room temperature in
poor coordination solvents, such as a
mixture of toluene and n-hexane.
Angew. Chem. Int. Ed. 2003, 42, 3315 – 3322
Hydroboration Reagents
A. V. Kalinin, S. Scherer,
V. Snieckus*
The best of the old: The new hydroboration reagent 1 combines the selectivity of
disiamylborane (2) with the reactivity
towards carbonyls of allyl boranes 3.
Conventional oxidative workup conditions
are avoided, as facile hydrolysis in protic
media provides the corresponding boronic acids with up to 99 % anti-Markovnikov selectivities. A one-pot hydroboration/Suzuki–Miyaura protocol adds to the
synthetic value of 1.
Making derivatives of organic side chains
on polyoxometalates is an important prerequisite for their application in biology.
Compounds a1- and a2[P2W17O61{Sn(CH2)2CO2H}]7 (depicted)
were prepared for the first time and
coupled with alcohols and amines,
including C-protected amino acids.
3399 – 3404
Di(isopropylprenyl)borane: A New
Hydroboration Reagent for the Synthesis
of Alkyl and Alkenyl Boronic Acids
Functionalizing Polyoxotungstates
S. Bareyt, S. Piligkos, B. Hasenknopf,*
P. Gouzerh, E. LacQte, S. Thorimbert,
M. Malacria*
3404 – 3406
Highly Efficient Peptide Bond Formation
to Functionalized Wells-Dawson-Type
Natural Product Synthesis
D. L. J. Clive,* J. Wang
Stereoselective hydrogenation of the
tetrasubstituted double bond in enone 1
is possible, provided the keto group at C7
is first removed and the a face is blocked
by tert-butyldimethylsiloxy groups at
positions 10 and 11. The resulting product
2 is easily converted into hamigeran B (3),
a marine natural product with powerful
activity against herpes and polio viruses.
Si* = tBuMe2Si.
A good starting point for the design of
potent bactericidal compounds is the
aminoglycoside paromomycin (1). The
A-ring (shown in red) was replaced with a
range of heterocycles. An ESIMS-based
RNA-binding assay was used to screen the
binding affinities of the products.
3406 – 3409
Stereospecific Total Synthesis of the Antiviral Agent Hamigeran B—Use of Large
Silyl Groups to Enforce Facial Selectivity
and to Suppress Hydrogenolysis
Aminoglycoside Mimetics
Y. Ding,* S. A. Hofstadler, E. E. Swayze,
L. Risen, R. H. Griffey
3409 – 3412
Design and Synthesis of ParomomycinRelated Heterocycle-Substituted Aminoglycoside Mimetics Based on a Mass
Spectrometry RNA-Binding Assay
In a multicomponent coupling reaction,
1,3-butadienes underwent Ni-catalyzed
dimerization and carbosilylation in the
presence of a chlorosilane and a Grignard
reagent at 20 8C (see scheme). The
Angew. Chem. Int. Ed. 2003, 42, 3315 – 3322
coupling product was obtained regio- and
stereoselectively when unsubstituted 1,3butadiene was used. (R = H, Me, or C9H19 ;
R’, R’’ = hydrocarbon substituent.)
J. Terao, A. Oda, A. Ikumi, A. Nakamura,
H. Kuniyasu, N. Kambe*
3412 – 3414
Nickel-Catalyzed Dimerization and
Carbosilylation of 1,3-Butadienes with
Chlorosilanes and Grignard Reagents
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Regioselective Hydrosilylation
B. M. Trost,* Z. T. Ball,
T. JTge
3415 – 3418
Regioselective Hydrosilylation of Propargylic Alcohols: An Aldol Surrogate
Aldol products from a non-aldol reaction:
A one-pot protocol effects hydrosilylation
of propargyl alcohols and subsequent
oxidative cleavage to yield b-hydroxy
ketones in a chemo-, regio-, and enantio-
Natural Product Analogues
K. C. Nicolaou,* M. Nevalainen, M. Zak,
S. Bulat, M. Bella,
B. S. Safina
3418 – 3424
selective fashion. Further structural elaboration of the intermediate g-hydroxyvinylsilane is possible before the carbonyl
group is unmasked (see scheme).
Leading the way: The novel thiostrepton
analogue 1 and its 5S,6S diastereomer
were synthesized through macrolactamization reactions. Forays towards the total
synthesis of the natural product itself
should follow a similar strategy.
Synthetic Studies on Thiostrepton:
Construction of Thiostrepton Analogues
with the Thiazoline-Containing
Element Mass Spectrometry
M. Wind, A. Wegener, A. Eisenmenger,
R. Kellner, W. D. Lehmann* 3425 – 3427
Sulfur as the Key Element for Quantitative
Protein Analysis by Capillary Liquid Chromatography Coupled to Element Mass
The impact of 32S quantification by capillary chromatography coupled to element
mass spectrometry was demonstrated for
three areas in proteomic analysis: for
absolute quantification of a peptide, for
the characterization of a protein digest
(see chromatogram), and for the estimation of the efficiency of electrospray
Electrodeposition of Nanocrystals
F. Endres,* M. Bukowski,
R. Hempelmann,*
H. Natter
Better than water: A method for the
electrodeposition of nanocrystalline
metals and alloys from ionic liquids has
been developed (see schematic representation). This method enables the synthesis of aluminum nanocrystals with average grain sizes of about 10 nm, Al-Mn
alloys, as well as Fe and Pd nanocrystals.
3428 – 3430
Electrodeposition of Nanocrystalline
Metals and Alloys from Ionic Liquids
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2003, 42, 3315 – 3322
A heteroleptic benzylcalcium complex
decomposes by means of C–H activation
(see picture), a reaction typical for d0metal complexes. This finding closes the
gap between the chemistry of the heavier
alkaline-earth and the early d- and f-block
metals. The product, a dimeric calcium
complex, was characterized by X-ray
C–H Activation in Ca Complexes
Surprisingly polar: The single-sided scissoring-induced sudden-polarization effect
in D2d ethene is first order (see picture).
The important role of this coordinate was
until now overlooked, although it was
known for a long time that each geometrical distortion that leads to a breakage of the D2d symmetry results in a
charge separation.
Sudden-Polarization Effects
S. Harder*
3430 – 3434
Intramolecular C–H Activation in
Alkaline-Earth Metal Complexes
A. Viel, R. P. Krawczyk, U. Manthe,
W. Domcke*
3434 – 3436
The Sudden-Polarization Effect and its
Role in the Ultrafast Photochemistry of
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
The publication of Communications labeled with this symbol has been accelerated because of their topical or highly competitive
The issues for July 2003 appeared online on the following dates
Issue 25: June 24. · Issue 26: July 2. · Issue 27: July 10. · Issue 28: July 16
Angew. Chem. Int. Ed. 2003, 42, 3315 – 3322
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
In the minireview “Recent Methods for the
Synthesis of (E)-Alkene Units in Macrocyclic Natural Products” by J. Prunet
(Angew. Chem. Int. Ed. 2003, 42, 2826–
2830) an incorrect formula was given in
Scheme 9 on p. 2828 for 21a–c. A methylene group is shown instead of the
correct isopropylidene group. The corrected formula is shown on the right.
The text on p. 2829 should read:
On the other hand, De Brabander et al.
obtained a 10:1 ratio of (E)-22 c/(Z)-22 c
when they exposed a monosubstituted
olefin analogue of 21c to catalyst 7 in
dichloromethane,[31] and Labrecque et al.
observed a 9:1 E selectivity for the
formation of a product nearly identical to
7.[32] These results can be explained by the
nature of the RCM catalyst, as shown by
De Brabander:[31] With the first-generation
catalyst 7 kinetic ratios are obtained, while
thermodynamic equilibrium is reached
with the more active second-generation
catalysts, as it is the case for herbarumin I
(Scheme 6).
References [31] and [32] should be completed:
[31] a) Y. Wu, L. Esser, J. K. De Brabander,
Angew. Chem. 2000, 112, 4478 – 4480;
Angew. Chem. Int. Ed. 2000, 39, 4308 –
4310; b) Y. Wu, X. Liao, R. Wang, X.-S.
Xie, J. De Brabander, J. Am. Chem. Soc.
2002, 124, 3245 – 3253.
[32] The side chain at C15 has an extra
methylene unit, and the primary hydroxy
function is protected as a benzyl ether:
D. Labrecque, S. Charron, R. Rej, C.
Blais, S. Lamothe, Tetrahedron Lett.
2001, 42, 2645 – 2648. Smith and Zheng
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
reported a 10:1 E selectivity for the
formation of an analogue of 24
(CH2OPMB instead of COOMe, Meprotected phenol) with catalyst 7, see:
A. B. Smith III, J. Zheng, Synlett, 2001,
1019 – 1023
Angew. Chem. Int. Ed. 2003, 42, 3315 – 3322
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