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Graphical Abstract Angew. Chem. Int. Ed. 352003

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Contents
The following articles are available online (in Wiley InterScience). You can find them at
www.angewandte.org, under Full Text, Early View.
G. Hfner, K. T. Wanner*:
Competitive Binding Assays Made Easy with a Native Marker
and Mass Spectrometric Quantification
DOI: 10.1002/anie.200351806
Published online: September 1, 2003
G. Dyker,* D. Hildebrandt, J. Liu, K. Merz:
Gold(iii) Chloride Catalyzed Domino Processes with Isobenzopyrylium Cation Intermediates
DOI: 10.1002/anie.200352160
Published online: September 1, 2003
D. G. Shchukin, G. B. Sukhorukov,* H. Mhwald:
Smart Inorganic/Organic Nanocomposite Hollow Microcapsules
DOI: 10.1002/anie.200352068
Published online: September 1, 2003
V. S. Iyer, K. P. C. Vollhardt,* R. Wilhelm:
Near-Quantitative Solid-State Synthesis of Carbon Nanotubes
from Homogeneous Diphenylethynecobalt and –Nickel Complexes
DOI: 10.1002/anie.200352201
Published online: September 1, 2003
S. Ahlert, W. Klein, O. Jepsen, O. Gunnarsson, O. K. Andersen,
M. Jansen*:
Ag13OsO6 : A Silver Oxide with Interconnected Icosahedral Ag134+
Clusters and Dispersed [OsO6]4 Octahedra
DOI: 10.1002/anie.200351740
Published online: September 1, 2003
F. M. H. de Groot,* C. Albrecht, R. Koekkoek, P. H. Beusker,
H. W. Scheeren:
“Cascade-Release Dendrimers” Liberate All End Groups upon a
Single Triggering Event in the Dendritic Core
DOI: 10.1002/anie.200351942
Published online: September 1, 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.
Web Sites
4122
Wiley InterScience Relaunched
M. Mller
The Art of Chemistry
4125
Arthur Greenberg
reviewed by H. Hopf
The Road to Stockholm
4126
István Hargittai
reviewed by G. B. Kauffman,
L. M. Kauffman
http://interscience.wiley.com
Books
Highlights
Microfluidic Systems
R. F. Ismagilov*
Microchips: Multistep reactions may be
catalyzed by enzymes immobilized on
microbeads trapped inside microfluidic
channels. Large integrated microfluidic
circuits can be created by using multilayer
soft lithography in poly(dimethylsiloxane).
These circuits (see schematic representation) can be used to perform hundreds of
different reactions simultaneously, and
can be applied to a range of problems,
from enzymatic assays to crystallization of
proteins.
4130 – 4132
Integrated Microfluidic Systems
4112
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
Angewandte
Chemie
Conjugated Belts
Undeterred by the propensity of trigonal
carbon atoms to strive for planarity,
synthetic chemists have recently succeeded in constructing novel macrocycles
with inward-pointing p orbitals (see picture). Individual metal ions are too small
to fill the cavity, but fullerenes are just the
right size for some of these electron-rich,
p-lined hosts.
L. T. Scott*
4133 – 4135
Conjugated Belts and Nanorings with
Radially Oriented p Orbitals
Reviews
Combinatorial Chemistry
D. L. Boger,* J. Desharnais,
K. Capps
4138 – 4176
Solution-Phase Combinatorial Libraries:
Modulating Cellular Signaling by Targeting Protein–Protein or Protein–DNA
Interactions
To bead or not to bead? This is the
question posed at the start of the construction of every combinatorial library.
The pros and cons of solid-phase and
solution-phase library synthesis are discussed along with the authors personal
experiences in constructing and using
solution-phase libraries (see scheme) to
study the modulation of protein–protein
and protein–DNA interactions in cellular
signal transduction.
Communications
Small Polyoxomolybdates
D.-L. Long, P. KAgerler, L. J. Farrugia,
L. Cronin*
4180 – 4183
A mixed-valence polyoxomolybdate cluster [H2MoVI12MoV4O52]10 was isolated by a
new “shrink-wrapping” approach to trap
clusters that display low symmetry and
nonspherical topology (see scheme;
HMTAH = protonated hexamethylene-
tetraamine). The unprecedented cluster
topology results from the restriction of the
reorganization of the cluster framework to
more symmetrical clusters, yet it reacts
with electrophiles, such as FeII.
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Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
www.angewandte.org
Restraining Symmetry in the Formation of
Small Polyoxomolybdates: Building
Blocks of Unprecedented Topology
Resulting From “Shrink-Wrapping”
[H2Mo16O52]10 -Type Clusters
delivery); for individuals who are personal
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4113
Contents
Rotational Barrier in Ethane (1)
F. M. Bickelhaupt,
E. J. Baerends*
4183 – 4188
The Case for Steric Repulsion Causing the
Staggered Conformation of Ethane
Rotational Barrier in Ethane (2)
F. Weinhold*
4188 – 4194
Rebuttal to the Bickelhaupt–Baerends
Case for Steric Repulsion Causing the
Staggered Conformation of Ethane
The barrier to rotation in ethane (see
picture) is considered a prototypical case
of steric hindrance. This view has been
recently contradicted, and hyperconjugation has been put forward as the right
explanation. The authors argue that there
is no reason to abandon the steric
repulsion explanation, and discuss why
different electronic structure analyses
yield different views.
Two tenets of qualitative MO theory
suggest contradictory explanations of
ethane torsional barriers, but only one
stands up to rigorous examination (see
energy level diagrams). Bickelhaupt and
Baerends’ defense of the neo-steric “fourelectron destabilization” concept (right) is
shown to be as illusory as its predecessors.
Organic/Inorganic Nanocapsules
K. Koh, K. Ohno, Y. Tsujii,
T. Fukuda*
4194 – 4197
Precision Synthesis of Organic/Inorganic
Hybrid Nanocapsules with a SilanolFunctionalized Micelle Template
In a nutshell: An amphiphilic block
copolymer that bears protected silanol
groups was synthesized by atom-transfer
radical polymerization, and the amphiphile was assembled to form a micelle in
an aqueous medium. The micelle was
Colorimetric Glucose Sensor
D. Nakayama, Y. Takeoka,* M. Watanabe,*
K. Kataoka
4197 – 4200
Simple and Precise Preparation of a
Porous Gel for a Colorimetric Glucose
Sensor by a Templating Technique
Red for danger! A glucose-sensitive gel is
systematically prepared by careful control
of the gel recipe to produce the desired
4114
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
mixed with a solution of active silicate,
which resulted in the formation of a silica
layer on the micelle surface to produce a
novel type of organic/inorganic hybrid
nanocapsule (see scheme).
swelling ratio at a given glucose concentration. Subsequently, a periodically
ordered porous gel is obtained from the
bulk gel by using a closest-packing colloidal crystal as a template; this template
is subsequently removed. The gel exhibits
expected structural color at certain glucose concentrations and thus can be used
as a colorimetric glucose sensor, which
may applied as a test for diabetes (see
picture).
Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
Angewandte
Chemie
Taking control: One-dimensional mesostructured silica materials and their arrays
are prepared in anodic alumina mem-
branes. By adjusting the wettability of the
alumina pore wall, nanofibers and nanotubes are prepared in a controlled way.
The mesostructured silica morphology
(see picture) can be adjusted by changing
the surfactant concentration. Both the
mesopores and the tubular cavities can be
incorporated with functional materials,
thus forming hierarchical nanocomposites.
1D Mesostructured Silica Materials
Z. Yang, Z. Niu, X. Cao, Z. Yang,* Y. Lu,*
Z. Hu, C. C. Han
4201 – 4203
Template Synthesis of Uniform 1D Mesostructured Silica Materials and Their
Arrays in Anodic Alumina Membranes
Material for Lithium-Battery Anodes
M. Yoshio,* H. Wang,
K. Fukuda
Lithium-ion batteries are the most convenient form of electrical storage. But
their natural-graphite anodes are not
compatible with propylene carbonatebased electrolytes. The edge planes of the
graphite are attacked by the electrolyte,
whereas the basal planes remain inert. A
technique can be applied to form spherical graphite particles, which maximize
the basal-plane exposure while the edge
planes remain hidden (see picture). Thus
only a small amount of carbon coating is
now needed to protect the graphite core
from the electrolyte.
4203 – 4206
Spherical Carbon-Coated Natural
Graphite as a Lithium-Ion Battery-Anode
Material
Carbon Nanotube–Ferrocene Hybrids
D. M. Guldi,* M. Marcaccio, D. Paolucci,
F. Paolucci,* N. Tagmatarchis, D. Tasis,
E. VPzquez, M. Prato*
4206 – 4209
A long-lived charge-separated state,
SWNTC –FcC+, is formed by photoinduced
electron transfer in a novel single-wall
carbon nanotube–ferrocene (SWNT–Fc)
Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
nanohybrid. The presence of SWNTC ,
detected by laser flash photolysis, was
confirmed by time-resolved pulse radiolysis and steady-state bulk electrolysis.
www.angewandte.org
Single-Wall Carbon Nanotube–Ferrocene
Nanohybrids: Observing Intramolecular
Electron Transfer in Functionalized
SWNTs
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4115
Contents
Fluctuating electron-transfer rates, both
forward and back (see picture), were
measured at the single-molecule level for
a triphenylamine–perylenediimide donor–
acceptor dendrimer. These fluctuations,
reminiscent of those seen for forward
electron transfer in some large biomolecules and so far not documented for
synthetic systems, are induced by the
local environment and conformational
changes in the dendrimer.
Single-Molecule Electron Transfer
R. Gronheid, A. Stefan, M. Cotlet,
J. Hofkens, J. Qu, K. MRllen,
M. Van der Auweraer, J. W. Verhoeven,
F. C. De Schryver*
4209 – 4214
Reversible Intramolecular Electron Transfer at the Single-Molecule Level
Controlling Regioselectivity
S. Ma,* G. Wang
Tuning the regioselectivity of the Pdcatalyzed coupling reaction of propargylic
mesylates and (Z)-2-ethoxycarbonylethenyl zinc iodide or PhZnBr is acheived
by subtle choice of the ligand. When PPh3
is the ligand, alkynes are formed, whereas
when 2-diphenylphosphanyl-2’-hydroxy1,1’-binaphthalene is the ligand, allenes
are formed.
4215 – 4217
Regioselectivity Control by a Ligand
Switch in the Coupling Reaction Involving
Allenic/Propargylic Palladium Species
Nanostructured graphitelike carbon films
are prepared through a simple pyrolysis
method. The as-prepared films are superhydrophobic for not only pure water but
also corrosive liquids, such as acidic and
basic solutions. The picture shows water
droplets with pH values of 1.07 (left) and
13.76 (right) in contact with a nanostructured carbon film. This is the first example
of superhydrophobicity over the whole
range of pH values, without the presence
of fluorine-containing compounds.
The dynamic duo: A more than tenfold
increase in the yield of the chiral macropolycyclic polyether containing two 2,6disubstituted 1,3,5,7-cis-tetraoxadecalin
systems was obtained under thermodynamic conditions from a dynamic combi-
natorial virtual library with templating
cesium ions (> 95 % yield, see schematic
representation) relative to kinetic syntheses (< 8 % yields in their macropolycyclization steps), even when the same template was used.
Superhydrophobic Carbon Films
L. Feng, Z. Yang, J. Zhai, Y. Song, B. Liu,
Y. Ma, Z. Yang,* L. Jiang,*
D. Zhu
4217 – 4220
Superhydrophobicity of Nanostructured
Carbon Films in a Wide Range of pH
Values
Dynamic Covalent Chemistry
B. Fuchs, A. Nelson, A. Star,
J. F. Stoddart,* S. Vidal
4220 – 4224
Amplification of Dynamic Chiral Crown
Ether Complexes During Cyclic Acetal
Formation
4116
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
Angewandte
Chemie
Natural Product Synthesis
The unique spiroxalactone framework of
lateriflorone (1) consists of a prenylated
dihydrobenzoquinone moiety and a trioxatetracyclotetradecane system. A tandem
Claisen rearrangement/Diels–Alder cascade was the key step in the synthesis of
the complex tetradecane system, which
was then used to prepare 1-O-methyllateriflorone (2).
K. C. Nicolaou,* P. K. Sasmal, H. Xu,
K. Namoto, A. RitzTn
4225 – 4229
Total Synthesis of 1-O-Methyllateriflorone
Stereoselective Radical Reactions
A tin-free radical tandem reaction leads to
optically active a-methylenelactones (e.g.
1). The initial radical-mediated hydrogenatom abstraction from a chiral acetal is
highly stereoselective (see scheme).
The stereochemical outcome of such
reactions is governed by rules similar to
those developed for related cyclization
processes.
P. Renaud,* F. Beaufils, L. Feray,
K. Schenk
4230 – 4233
Diastereoselective Radical-Mediated
Hydrogen-Atom Abstraction
Organocatalytic Domino Reactions
D. B. Ramachary, N. S. Chowdari,
C. F. Barbas III*
4233 – 4237
A practical and environmentally friendly
organocatalytic process for the synthesis
of optically active highly substituted
spiro[5,5]undecane-1,5,9-triones was
achieved through the reaction of an
aldehyde, an enone, and Meldrum’s acid
Organocatalytic Asymmetric Domino
Knoevenagel/Diels–Alder Reactions: A
Bioorganic Approach to the Diastereospecific and Enantioselective Construction of Highly Substituted Spiro[5,5]undecane-1,5,9-triones
in the presence of a catalytic amount of
chiral amino acid (see scheme). The
Diels–Alder products were obtained as
single diastereomers in excellent yields
and enantiomeric excesses.
The absolute configuration
(aR, S, S, S, S, S) was assigned to the natural product RP-66453 (1) after the total
synthesis of its atropdiastereomer and
spectroscopic studies on the two compounds. A sequence of SNAr-based cycloetherification and an intramolecular
atropdiastereoselective Suzuki–Miyaura
coupling were used for the construction of
the elusive A-B-O-C bicyclic skeleton of
RP-66453.
Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
www.angewandte.org
Natural Product Synthesis
M. Bois-Choussy, P. Cristau,
J. Zhu*
4238 – 4241
Total Synthesis of an Atropdiastereomer of
RP-66453 and Determination of Its Absolute Configuration
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4117
Contents
Asymmetric Oxy-Michael Addition
N. J. Adderley, D. J. Buchanan,
D. J. Dixon,* D. I. LainT
4241 – 4244
Highly Diastereoselective Oxy-Michael
Additions of Enantiopure d-Lactol Anions
to Nitroalkenes: Asymmetric Synthesis of
1,2-Amino Alcohols
The “naked” alkoxide 1 of (S)-6-methyl-dlactol acts as an excellent chiral hydroxide
equivalent in highly diastereoselective oxyMichael additions to nitroalkenes (see
scheme). The excellent stereoinduction
arises from what becomes a superb
protecting group in the resulting 1,2amino alcohol products. R1 = alkyl,
aryl, furanyl, thiophenyl;
R2,R3 = (CH2)3CHCH3O .
Readily available amino acid based chiral
ligands are used in a three-component Zrcatalyzed enantioselective synthesis of
propargylamines (see schemes). The
reaction affords important enantiomerically enriched building blocks that are not
conveniently accessible by alternative
catalytic methods.
R- or S-configured 1,2-diol precursors are
formed in good yields (54–86 %) and with
excellent enantioselectivities (94 to
99 % ee) by using a simple one-pot
sequence—catalytic a-aminoxylation of
aldehydes followed by in situ reduction
with NaBH4—with l- or d-proline as the
catalyst and nitrosobenzene as the oxygen
source (see scheme).
Synthesis of Propargylamines
L. C. Akullian, M. L. Snapper,*
A. H. Hoveyda*
4244 – 4247
Three-Component Enantioselective
Synthesis of Propargylamines through
Zr-Catalyzed Additions of Alkyl Zinc
Reagents to Alkynylimines
Asymmetric Catalysis
G. Zhong*
4247 – 4250
A Facile and Rapid Route to Highly
Enantiopure 1,2-Diols by Novel Catalytic
Asymmetric a-Aminoxylation of
Aldehydes
High-Surface-Area Aluminum Fluoride
Super acidic solids: A new two-step route
to high-surface-area metal fluorides is
reported, by which amorphous AlF3 can be
prepared having a BET(N2) surface area of
more than 200 m2 g 1 (see SEM image).
This HS-AlF3 shows a very high Lewis
acidity and consequently a high catalytic
activity.
E. Kemnitz,* U. Groß, S. RRdiger,
C. S. Shekar
4251 – 4254
Amorphous Metal Fluorides with
Extraordinary High Surface Areas
4118
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
Angewandte
Chemie
Combinatorial Synthesis
Stereochemical diversity as a novel concept in combinatorial chemistry for the
synthesis of nonpeptidic biologically
active compounds is introduced. As an
example, the combination of the hydrogenation of imines in the presence of
either enantiomer of a chiral Ru catalyst
with a domino reaction led to the targeted
construction of 12 of the 16 possible
stereoisomers of emetine (1).
L. F. Tietze,* N. Rackelmann,
G. Sekar
4254 – 4257
Catalyst-Controlled Stereoselective
Combinatorial Synthesis
Pd-Catalyzed Heteroanulation
B. Witulski,* C. Alayrac,
L. Tevzadze-Saeftel
Chelates are the key: A conceptually novel
indole ring forming reaction through
heteroanulation is available through the
palladium-catalyzed reaction of N-alkenylanilides with primary or secondary
amines. The key feature is the formation
4257 – 4260
Palladium-Catalyzed Synthesis of
2-Aminoindoles by a Heteroanulation
Reaction
of an unprecedented s,p-chelated palladium species (see scheme); nitrogen
nucleophiles can add to the activated
alkyne unit of this species to form the
indole skeleton. (X = I, Br; HNR2R3 =
prim. or sec. amine; Ts = tosyl.)
Antennary Oligosaccharides
H. Weiss, C. Unverzagt*
4261 – 4263
Highly Branched Oligosaccharides:
A General Strategy for the Synthesis of
Multiantennary N-Glycans with a
Bisected Motif
Squeezing in a sugar: A modular buildingblock approach was the strategy used in a
clever general synthesis of the sterically
crowded triantennary N-glycans bearing
an additional bisecting GlcNAc motif (see
formula). Key steps include the use of the
small trifluoroacetyl protective group and
the late introduction of the a1,6-arm.
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
nature.
Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4119
Contents
Service
Keywords
4264
Authors
4265
Vacancies
4121
Preview
4267
Corrigendum
*
A reader has noticed that in the Review by
E. A. Meyer, R. K. Castellano, and F. Diederich, in Angew. Chem. Int. Ed. 2003, 42,
1210, the structural formula for compound
4120
31 b in Figure 26 is incorrect. The correct
formula is given here. Furthermore, this
receptor was not developed by Dvornikovs
and Smithrud, as stated in the accompa-
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
nying text, but, as correctly cited, was
developed by Thompson and Smithrud.
Angew. Chem. Int. Ed. 2003, 42, 4112 – 4120
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