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Graphical Abstract Angew. Chem. Int. Ed. 442003

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The following articles are available online (in Wiley InterScience). You can find them at, under Full Text, Early View.
D. Stamou,* C. Duschl, E. Delamarche,
H. Vogel*:
Self-Assembled Microarrays of Attoliter
Molecular Vessels
DOI: 10.1002/anie.200351866
Published online: November 5, 2003
X. Gao, T. Friščić, L. R. MacGillivray*:
Supramolecular Construction of Molecular Ladders in the Solid State
DOI: 10.1002/anie.200352713
Published online: November 5, 2003
S. L. Tripp, R. E. Dunin-Borkowski, A. Wei*:
Flux Closure in Self-Assembled Cobalt
Nanoparticle Rings
DOI: 10.1002/anie.200352825
Published online: November 5, 2003
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 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.
Meeting Reviews
J. Kurreck
Nucleic Acids Chemistry and
5384 – 5385
What Einstein Told his Cook
Robert L. Wolke, Marlene Parrish
reviewed by P. Weyerstahl
De Artes Chemiae
Lothar Beyer, Rainer Behrends
reviewed by R. Zott, G. Boeck
What’s Cooking in Chemistry?
Hubertus P. Bell, T. Feuerstein, C. E.
G&ntner, S. H(lsken, J. K. Lohmann
reviewed by G. Mrkl
W. R. Thiel*
5390 – 5392
On the Way to a New Class of Catalysts—
High-Valent Transition-Metal Complexes
That Catalyze Reductions
Surprise! Owing to its rhenium(v) center,
which bears two terminal oxo ligands,
[ReI(O)2(PPh3)2] appears at first glance to
be an oxygen-transfer reagent. The complex is, however, a novel catalyst for a
reduction: the hydrosilylation of aldehydes and ketones (see scheme).
Cross-Coupling Reactions
A. Zapf*
5394 – 5399
Novel Substrates for Palladium-Catalyzed
Coupling Reactions of Arenes
Alternative coupling partners: Not only
haloarenes, but also aryl carbonic acids
and heteroaryl thioethers (see formulas)
can take part in palladium-catalyzed coupling reactions. The substrate scope has
thus become broader and the catalyst
systems simpler. Furthermore, the reaction of carbonic acid derivatives allows the
simple synthesis of ketones.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2003, 42, 5374 – 5380
The right conditions: The development of
new stoichiometric and catalytic variants
of the copper-mediated arylation of heteroatoms (see figure) is of particular
interest for the synthetic chemist. The
authors give a thorough account of the
state-of-the-art of the reaction and discuss
the broad range of substrates and suitable
choices of catalyst systems and reaction
Ullmann Condensation
S. V. Ley, A. W. Thomas*
5400 – 5449
Modern Synthetic Methods for CopperMediated C(aryl) O, C(aryl) N, and
C(aryl) S Bond Formation
Proton wires: One-dimensional water
chains play an important role in proton
permeation through transmembrane proteins. The X-ray crystal structures as well
as solid-state 2H and 17O NMR and
calorimetry studies of two imidazole
hydrates that stabilize infinite onedimensional water chains are reported
(see picture; N blue, O red, H white).
The 2H NMR spectroscopic studies
One-Dimensional Water Chains
L. E. Cheruzel, M. S. Pometun, M. R. Cecil,
M. S. Mashuta, R. J. Wittebort,
R. M. Buchanan*
5452 – 5455
Structures and Solid-State Dynamics of
One-Dimensional Water Chains Stabilized
by Imidazole Channels
suggest that water molecules in both
compounds undergo different reorientational dynamics.
K. Aikawa, K. Mikami*
Axial chirality is generated upon complexation of the novel triphos ligand with a
metal. In the presence of the diamine dmdabn, isomerization to the enantiopure
triphos–Ru complex was observed. The
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Angew. Chem. Int. Ed. 2003, 42, 5374 – 5380
dm-dabn ligand of the Ru complex
exchanges with dpen at room temperature
without racemization. dm-dabn = 3,3’dimethyl-2,2’-diamino-1,1’-binaphthyl,
dpen = 1,2-diphenylethylenediamine.
5455 – 5458
Atropos but Achiral Tris(phosphanyl)biphenyl Ligands for Ru-Catalyzed
Asymmetric Hydrogenation
Both axial and helical chirality are generated by complexation of the novel tetrakis(phosphanyl)terphenyl (tetraphos) ligand
to a metal center (see picture). The tropos
nature of the ligand was confirmed, and
enantiopure Pd complexes controlled by
diamines were applied as asymmetric
Lewis acid catalysts in carbonyl–ene
Atropisomerism and Helicity
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K. Aikawa, K. Mikami*
5458 – 5461
Helical Chirality Control of Palladium
Complexes That Bear a Tetrakis(phosphanyl)terphenyl Ligand: Application as
Asymmetric Lewis Acid Catalysts
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Super-Acid Catalysts
Z.-Y. Yang,* L. Wang,* N. Drysdale,
M. Doyle, Q. Sun, S. K. Choi 5462 – 5464
Benign by Molecular Design: Active Polymeric Super-Acid Catalysts and Highly
Conductive Polymeric Lithium Electrolytes
Architectures of copolymers of ethylene
with a-olefinic fluorosulfonates are well
controlled by tailoring palladium- or
nickel-a-diimine catalysts and polymerization conditions (see scheme). These
polymeric acids are shown to be “green”
homogenous and heterogeneous super-
acid catalysts for industrially important
reactions. Their lithium salts exhibit
excellent ionic conductivities as well as
mechanical properties, and are attractive
candidates for use in lithium batteries.
(MAO = methylalumoxane)
Natural weapons against HIV, litseaverticillols A (2) and C, have been synthesized
from sesquirosefuran (1) by a rapid and
efficient biomimetic total synthesis
involving a chemo- and stereoselective
singlet-oxygen-initiated tandem sequence
(see scheme). Litseaverticillols D, F, and
G were readily synthesized from litseaverticillol A through a regioselective 1O2
ene reaction.
Natural Product Synthesis
G. Vassilikogiannakis,*
M. Stratakis*
5465 – 5468
Biomimetic Total Synthesis of Litseaverticillols A, C, D, F, and G: Singlet-OxygenInitiated Cascades
Solid-State Reactions
S. Nomura, T. Itoh,* M. Ohtake, T. Uno,
M. Kubo, A. Kajiwara, K. Sada,
M. Miyata
5468 – 5472
Polymerization by Insertion of Molecular
Oxygen into Crystals of 7,7,8,8-Tetrakis(ethoxycarbonyl)quinodimethane
Slipping through the lattice: Molecular
oxygen reacts with crystals of quinodimethane 1 to give highly crystalline alternating copolymers by means of a radical
mechanism. An X-ray crystallographic
study indicates that the unique arrangement of 1 in the crystal is crucial to the
Asymmetric Reductive Amination
R. Kadyrov,* T. H. Riermeier 5472 – 5474
Highly Enantioselective HydrogenTransfer Reductive Amination: Catalytic
Asymmetric Synthesis of Primary Amines
Ammonium formate is the hydrogen
source in the catalytic asymmetric reductive amination of ketones presented here
(Leuckart–Wallach-type reaction). The
reaction proceeds smoothly in methanol
in the presence of Ir, Rh, and Ru catalysts.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Primary amines were obtained as products in good yields with high enantioselectivities after hydrolytic workup when
[((R)-tol-binap)RuCl2] was used as the
catalyst (see scheme). R1, R2 = alkyl, aryl.
Angew. Chem. Int. Ed. 2003, 42, 5374 – 5380
Enyne Cyclization
F. Monnier, D. Castillo, S. DSrien,
L. Toupet, P. H. Dixneuf*
5474 – 5477
(C*p = C5Me5, cod = cyclop
octadiene) promotes the reaction of 1,6enynes with an excess of diazoalkane in
dioxane in one step to afford selectively
1-alkenyl bicyclo[3.1.0]hexane derivatives
(see scheme, X = O, NTs; Y = CO2Et;
R1 = H, Me; R2 = H; Ts = p-toluenesulfonyl). This novel reaction involves the
stereoselective formation of three C C
bonds and a cyclopropanation step.
Addition of Diazoalkanes to Enynes Promoted by a Ruthenium Catalyst: Simple
Synthesis of Alkenyl Bicyclo[3.1.0]hexane
Catalytic Carbonyl-Ene Reaction
Y. Yuan, X. Zhang, K. Ding*
5478 – 5480
Quasi Solvent-Free Enantioselective
Carbonyl-Ene Reaction with Extremely
Low Catalyst Loading
Simply mixing the neat substrates and a
small amount of the chiral catalyst (0.1–
0.01 mol %) under nearly solvent-free
conditions makes the enantioselective
carbonyl-ene reaction of glyoxylate ester
with a variety of olefins proceed smoothly
to afford the corresponding a-hydroxy
esters in high yields with excellent enantioselectivities [Eq. (1)].
Chemical Biology
G. C. Adam, C. D. Vanderwal,
E. J. Sorensen,*
B. F. Cravatt*
5480 – 5484
Activity-based profiling and reportergroup-tagged compounds were used to
identify carboxylesterase-1 (CE-1) as a
specific target of the natural product
CO2 is an ideal feedstock for chemical
synthesis; unfortunately its thermodynamic stability is a barrier to widespread
use. Active cobalt catalysts for the
copolymerization of propylene oxide and
CO2 are reported (see scheme; L = N,N’bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine), which have excellent
( )-FR182877 (see scheme). Now that a
target is known, specific modification of
the lactone natural product may lead to
even more effective inhibitors of CE-1.
Polycarbonate Synthesis
Z. Qin, C. M. Thomas, S. Lee,
G. W. Coates*
5484 – 5487
regioselectivity for polycarbonate synthesis without concomitant production of
cyclic carbonate by-products.
An iron in the fire: Iron-based catalysts
promote the asymmetric oxidation of alkyl
aryl sulfides to the corresponding sulfoxides with up to 90 % ee (see scheme).
Simple hydrogen peroxide (30 % in water)
serves as the terminal oxidant.
Angew. Chem. Int. Ed. 2003, 42, 5374 – 5380
( )-FR182877 Is a Potent and Selective
Inhibitor of Carboxylesterase-1
Cobalt-Based Complexes for the Copolymerization of Propylene Oxide and CO2 :
Active and Selective Catalysts for Polycarbonate Synthesis
Iron-Catalyzed Oxidations
J. Legros, C. Bolm*
5487 – 5489
Iron-Catalyzed Asymmetric Sulfide Oxidation with Aqueous Hydrogen Peroxide
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Asymmetric Alkylation of Ketones
K. Funabashi, M. Jachmann, M. Kanai,
M. Shibasaki*
5489 – 5492
Multicenter Strategy for the Development
of Catalytic Enantioselective Nucleophilic
Alkylation of Ketones: Me2Zn Addition to
An array of heteroatoms is essential for
the activity and enantioselectivity of the
catalyst 2 in the addition of Me2Zn to
a-ketoesters 1 (e.g. see equation).
a-Hydroxyesters 3 were obtained with up
to 96 % ee in the presence of a catalytic
amount of additive iPrOH, which serves to
generate the catalytically active monomeric species (based on the observation
of nonlinear effects).
Visible-light irradiation of the hexafluorophosphate salt of [Cp*IrIII(bpy)H]+ (1,
Cp* = h5-C5Me5, bpy = 2,2’-bipyridine)
results in excited-state deprotonation to
form the conjugate base [Cp*IrI(bpy)].
The H/D exchange reaction of 1 also
occurs during photoirradiation of 1 in
[D4]methanol in the steady state (see
H/D Exchange in an Excited Hydride
T. Suenobu, D. M. Guldi,* S. Ogo,
S. Fukuzumi*
5492 – 5495
Excited-State Deprotonation and H/D
Exchange of an Iridium Hydride Complex
Elastic Films
N. Yamada,* T. Komatsu, H. Yoshinaga,
K. Yoshizawa, S. Edo,
M. Kunitake
5496 – 5499
Self-Supporting Elastic Film without
Covalent Linkages as a Hierarchically
Integrated b-Sheet Assembly
Inclusion Complexes
A. Scarso, L. Trembleau,
J. Rebek, Jr.*
5499 – 5502
Encapsulation Induces Helical Folding
of Alkanes
Hierarchic self-assembly: The formation
of a self-supporting elastic film without
the use of macromolecular materials is
described. The film is prepared by using a
peptide-containing amphiphile that has
three or four consecutive leucinate residues. The amphiphile initially forms bsheet structures, which stack in a fastenerlike fashion between the side chains of
leucine within the different b-sheets (see
Doing the twist: Incorporation of long
hydrocarbons during the self-assembly of
a cylindrical capsule containing an elongated cavity lined with eight benzene rings
and additional p surfaces induces helical
conformations of the chains so that they
are fully encapsulated within the cavity
(see picture).
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2003, 42, 5374 – 5380
Terminal OH-Containing Alumoxane
Towards new polymerization-catalyst
activators: A new synthetic approach is
described for the hitherto unknown
[{LAl(OH)}2(m-O)]·0.5 (C7H8)·C6H14 species (1; L = HC[(CMe)(2,6-iPr2C6H3N)]2).
Further reaction of the Br(nsted acidic
OH groups of 1 with Me2AlH results in the
formation of trimeric alumoxane containing a three coordinate Al center [(LAl)2(MeAl)(m-O)3]·2 C7H8, the core of which is
depicted. These compounds may have
use as activators for olefin-polymerization
G. Bai, H. W. Roesky,* J. Li, M. Noltemeyer,
H.-G. Schmidt
5502 – 5506
Synthesis, Structural Characterization,
and Reaction of the First Terminal Hydroxide-Containing Alumoxane with an
[{Al(OH)}2(m-O)] Core
The first carbaalanate consists of a carbaalane dianion [(AlH)8(CCH2tBu)6]2
that is coordinated through hydride
bridges to two lithium ions on opposite
sides of the cluster (see picture).
Additionally, the lithium ions are each
further coordinated to a neutral [tBuCH2C(AlH2·NMe3)3] unit. In this arrangement,
the lithium ion prevents condensation of
the [tBuCH2C(AlH2·NMe3)3] units.
Cluster Compounds
A. Stasch, H. W. Roesky,*
P. von R. Schleyer, J. Magull 5507 – 5509
A Threefold AlH2-Coordinated Carbon
Atom as Part of the First Carbaalanate
Artificial Adrenergic Receptors
O. Molt, T. Schrader*
Almost like the real thing: Amphiphilic
properties ensure that an artificial adrenaline receptor can be embedded in lipid
monolayers just like the natural example.
Here it forms large domains by selfassembly, which were investigated by
Langmuir–Blodgett techniques. Embed-
ded, the macrocyclic receptor is much
more sensitive and selective than in
solution. Monolayers containing receptor
molecules can distinguish between adrenergic receptor substrates with similar
Highly Sensitive Recognition of
Substrates of Adrenergic Receptors
at the Air/Water Interface
Core–Shell Particles
Quantum leap: Very high quantum yields,
thought to be impossible for nanocrystalline phosphor materials, were achieved
with CePO4 :Tb/LaPO4 core–shell nanoparticles (see picture). Because the LaPO4
shell reduces energy losses at the particle
surface, transparent colloidal solutions of
these 8-nm particles are highly photoluminescent.
Angew. Chem. Int. Ed. 2003, 42, 5374 – 5380
5509 – 5513
K. K(mpe, H. Borchert, J. Storz, A. Lobo,
S. Adam, T. M(ller,
M. Haase*
5513 – 5516
Green-Emitting CePO4 :Tb/LaPO4 Core–
Shell Nanoparticles with 70 % Photoluminescence Quantum Yield
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Reaction Mechanisms
O. P. Balaj, I. Balteanu, B. S. Fox-Beyer,
M. K. Beyer,*
V. E. Bondybey*
5516 – 5518
Addition of a Hydrogen Atom to Acetonitrile by Hydrated Electrons in Nanodroplets
Nanodroplets that contain hydrated electrons provide information complementary
to standard radiolysis techniques.
Although the reaction of hydrated electrons with acetonitrile was observed in
solution 25 years ago, its product has only
now been identified in a gas-phase
experiment as the hydrogen adduct. The
picture shows a solvent-stabilized radical
anion, which is suggested as a reactive
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
Sister Journals
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5520 – 5521
Angew. Chem. Int. Ed. 2003, 42, 5374 – 5380
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