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Graphical Abstract Angew. Chem. Int. Ed. 212003

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Contents
Obituary
2330
Biophysics and Self-Organization
M. Engelhard and S. C. Mller
Modern Organocopper Chemistry
2331
Norbert Krause
reviewed by S. R. Waldvogel
Molecular Devices and Machines
2331
Vincenzo Balzani, Margherita Venturi,
Alberto Credi
reviewed by F. Vgtle, C. A. Schalley
Chemically Speaking
2332
Carl C. Gaither, Alma E. Cavozos-Gaither
reviewed by H.-J. Quadbeck-Seeger
Practical Sonochemistry
2333
Timothy J. Mason, Dietmar Peters
reviewed by N. E. Leadbeater
Microwaves in Organic Synthesis
2334
André Loupy
reviewed by N. E. Leadbeater
Benno Hess (1922 – 2002)
Books
Highlights
Control of Chemical Reactivity
M. Goez*
Selection of a conformer by a laser pulse
and conformation-specific cleavage by a
second laser pulse can be used to control
the outcome of a chemical reaction. One
of the most recent examples is the
selective wavelength-dependent generation of either the 2-propyl cation or cornerprotonated cyclopropane from 1-iodopropane (see scheme).
2336 – 2337
Conformation-Selective Laser Chemistry
Minireviews
Ketene Synthesis and Reactions
A. Rafai Far*
Ketenes, which are versatile intermediates
in organic synthesis, have found a niche of
their own in polymer-assisted organic
transformations for the preparation of
small-molecule libraries. Many of the
methods of generating ketenes for such
transformations are examined, and the
scope of their reactions is discussed.
2340 – 2348
Ketenes in Polymer-Assisted Synthesis
Reviews
Organization of Nanostructures
H. C7lfen, S. Mann*
2350 – 2365
Higher-Order Organization by Mesoscale
Self-Assembly and Transformation of
Hybrid Nanostructures
The architecture of organization: By coupling synthesis, self-assembly, and trans-
2322
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
formation at the mesoscopic scale it
should be possible to develop a chemistry
of emergent structures based on the timeand scale-dependent coupling of interactive components. This review highlights
how the interplay between the aggregation
and crystallization of hybrid inorganic–
organic building blocks can lead to complex single crystals, organized nanoparticle arrays, and embedded nanostructures
with higher-order architecture (see picture).
Angew. Chem. Int. Ed. 2003, 42, 2322 – 2328
Angewandte
Chemie
Communications
An optimized cyclic peptidomimetic (see
picture) of the NPNA-repeat region in the
circumsporozoite (CS) protein of P. falciparum was designed. When delivered to
the immune system on human-compatible viruslike particles (virosomes), the
mimetic effectively elicits sporozoitebinding antibodies. This virosome-mimotope (virotope) approach may be of general value for the design and testing of
new synthetic-vaccine candidates.
Peptidomimetic Vaccine Design
B. Pfeiffer, E. Peduzzi, K. Moehle,
R. Zurbriggen, R. Gl;ck, G. Pluschke,*
J. A. Robinson*
2368 – 2371
A Virosome-Mimotope Approach to Synthetic Vaccine Design and Optimization:
Synthesis, Conformation, and Immune
Recognition of a Potential Malaria-Vaccine
Candidate
Taking DNA analysis for a spin: Amplified
detection of viral DNA and single-base
mutations in nucleic acids is accomplished by the thermally cycled incorporation of biotin labels into DNA replica
associated with magnetic particles, by the
electrocatalyzed biochemiluminescence
transduction of the DNA recognition
events, and by the rotation of the magnetic particles on electrode surfaces (see
schematic representation).
Detecting Single-Base Mutations
The importance of the pKa value: Phenols,
carboxylic acids, and compounds containing comparably acidic functional
groups are covalently captured on a
diazobenzylidene-functionalized glass
surface. This new covalent slide-capture
method has been used to print 6336
diversity-oriented synthesis-derived
phenol-containing fused bicycles and tetracycles, from which new calmodulin
ligands were identified (see schematic
representation).
Diversity-Oriented Synthesis
For the USA and Canada:
ANGEWANDTE CHEMIE International
Edition (ISSN 1433-7851) is published weekly
by Wiley-VCH PO Box 191161, D 69451 Weinheim, Germany. Air freight and mailing in the
USA by Publications Expediting Inc. 200 Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2003, 42, 2322 – 2328
F. Patolsky, Y. Weizmann, E. Katz,
I. Willner*
2372 – 2376
Magnetically Amplified DNA Assays
(MADA): Sensing of Viral DNA and
Single-Base Mismatches by Using Nucleic
Acid Modified Magnetic Particles
D. Barnes-Seeman, S. B. Park,
A. N. Koehler,
S. L. Schreiber*
2376 – 2379
Expanding the Functional Group Compatibility of Small-Molecule Microarrays:
Discovery of Novel Calmodulin Ligands
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
NJ 07030. Annual institutional subscription
price for institutions: Europe E 2998.00/
3148.00. Outside Europe US$ 3718.00/3904.00
(valid for print or electronic/print and electronic
www.angewandte.org
delivery); for individuals who are personal
members of a national chemical society, or
whose institution already subscribes, or who
are retired or self-employed consultants, print
only (including postage and handling charges):
Europe E 248.00/Outside Europe US$ 348.00.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2323
Contents
Probes for Cell Division
S. Hotha, J. C. Yarrow, J. G. Yang,
S. Garrett, K. V. Renduchintala,
T. U. Mayer, T. M. Kapoor* 2379 – 2382
HR22C16: A Potent Small-Molecule Probe
for the Dynamics of Cell Division
Crystallized Mesoporous Ta-Nb Oxide
T. Katou, B. Lee, D. Lu, J. N. Kondo,
M. Hara, K. Domen*
2382 – 2385
Crystallization of an Ordered Mesoporous
Nb–Ta Oxide
A high-throughput, microscopy-based
chemical-genetic screen identified
HR22C16, which causes a monoastral
mitotic block, as a small-molecule probe
for cell division (see picture). By using a
diastereoselective, traceless solid-phase
synthesis and biological assays, a more
potent HR22C16 analogue was then
identified. A photocaging strategy for
HR22C16 was also developed to allow fast
temporal control over the function of the
target protein Eg5.
The ordered pore structure of 2D hexagonally ordered mesoporous niobium and
tantalum mixed oxide has been successfully preserved during crystallization by
filling the pores of the precursor with
carbon prior to crystallization. Subsequent thermal treatment in an inert
atmosphere produces the crystallized
product without loss of the ordered
mesoporous structure, and the carbon
template is removed by calcination in air.
Transmission electron microscopy and
electron diffraction analyses clarify the
preservation of the 2D hexagonally
ordered mesoporous structure in singlecrystal domains of about 100 nm.
Zwitterionic Catalysts
T. A. Betley, J. C. Peters*
–
B
2385 – 2389
Zwitterionic Relatives to the Classic
[(P–P)Rh(solv)2]+ Ions: Neutral Catalysts
Active for H E Bond Additions to Olefins
(E = C, Si, B)
–
B
Ph2
P
P
Ph2
Me2
N
N
Me2
+
Rh
+
Rh
L
L
L
L
Making Carbon – Phosphorus Bonds
P.-Y. Renard,* P. Vayron, E. Leclerc,
A. Valleix, C. Mioskowski*
2389 – 2392
Lewis Acid Catalyzed Room-Temperature
Michaelis–Arbuzov Rearrangement
2324
The taming of the shrew! For the first time,
a broadly applicable efficient room-temperature Arbuzov rearrangement is
described. This reaction is accomplished
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Formally zwitterionic bis(phosphanyl)and bis(amino)borate rhodium(i) complexes (see picture) can catalytically
mediate the hydrogenation, hydroacylation, hydroboration, and hydrosilation of
double bonds. These neutral systems are
shown to be highly active, even under
conditions incompatible with their isostructural, but formally cationic, relatives.
through an atom-economical Lewis acid
catalyzed process (see scheme,
TMSOTf = trimethylsilyl trifluoromethanesulfonate). The method has been generalized to primary and activated secondary
phosphites, phosphinites, and phosphonites.
Angew. Chem. Int. Ed. 2003, 42, 2322 – 2328
Angewandte
Chemie
A remarkable lack of cleavage of the S S
bond characterizes the insertion of thiocyanogen into a P C bond of 1 (see
scheme) to afford 2. Compound 2 is a
valuable reagent for the synthesis of new
dimetallic polysulfide derivatives (3 a–c,
n = 2–4). [Mn] = [Mn(CNtBu)(CO)3].
C70Br10 is the most stable and, apparently,
the only product of the C70 bromination in
pure bromine and in solution in odichlorobenzene. In accordance with the
quantum chemical calculations, the ten
bromine atoms (orange) form a belt in the
equatorial region of the C70 molecule, with
nine adjacent pairs of Br atoms located at
the 1,4-positions and one pair at the 1,2position.
H
N
N
O
O
O
NH
H
N
O
H
N
Thiocyanogen Insertion
J. Ruiz,* R. Quesada, V. Riera, M. Vivanco,
S. GarcMa-Granda,
M. R. DMaz
2392 – 2395
Insertion of Thiocyanogen into a P C
Bond and Subsequent Formation of
Polysulfide Derivatives
Bromination of C70: C70Br10
S. I. Troyanov,* A. A. Popov,
N. I. Denisenko, O. V. Boltalina,*
L. N. Sidorov, E. Kemnitz
2395 – 2398
The First X-ray Crystal Structures of
Halogenated [70]Fullerene: C70Br10 and
C70Br10·3 Br2
The end is in sight for the use of
difluorocarbene (generated from toxic or
inconvenient heavy-metal or gaseous
reagents) in the preparation of geminal
difluorocyclopropenyl compounds. A
series of fluorinated alkynes now serve as
precursors to these important small-ring
systems (e.g. see picture) through a
remarkably facile and convenient transformation initiated by tert-butyllithium.
Difluorocyclopropenes
Diamine-linked syn-a,b-dialkyl b-amino
acid residues (see picture) have been
shown to exhibit parallel sheet secondary
structure. Adoption of the parallel hairpin
folding pattern is less strongly influenced
by linker stereochemistry than for similar
parallel hairpins in analogous a-peptide
systems.
Foldamer Structure
A. K. Brisdon,* I. R. Crossley, K. R. Flower,
R. G. Pritchard, J. E. Warren 2399 – 2401
Ringing the Changes: A Remarkable
Carbene-Free Synthesis of Difluorocyclopropenes
J. M. Langenhan, I. A. Guzei,
S. H. Gellman*
2402 – 2405
Parallel Sheet Secondary Structure in
b-Peptides
O
Angew. Chem. Int. Ed. 2003, 42, 2322 – 2328
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2325
Contents
Iodoindole Synthesis
J. Barluenga,* M. Trincado, E. Rubio,
J. M. GonzQlez
2406 – 2409
IPy2BF4-Promoted Intramolecular
Addition of Masked and Unmasked
Anilines to Alkynes: Direct Assembly of
3-Iodoindole Cores
All at once! Indoles can be assembled and
iodinated in a one-pot process (see
scheme) from anilines and their derivatives. This metal-free addition of nitrogen
compounds to alkynes is a clean reaction
that is promoted by iodonium cations.
Such a process provides a general pathway towards utilization of the biologically
relevant indole core.
Ph
Dual Catalysis
E
Ph
Rh l (cat.), phosphane ligands E
O
+
Aqueous Catalytic Pauson–Khand-Type
Reactions of Enynes with Formaldehyde:
Transfer Carbonylation Involving an
Aqueous Decarbonylation and a Micellar
Carbonylation
H
E
K. Fuji, T. Morimoto,* K. Tsutsumi,
K. Kakiuchi*
2409 – 2411
1
H
5 equiv
H2O, surfactant, 100 °C
E = CO2Et
O
E
2 (96%)
One rhodium(i) complex catalyzes two
processes in an overall Pauson–Khandtype reaction of enynes such as 1 with
formaldehyde in an aqueous medium to
give bicyclic cyclopentenones such as 2 in
excellent yields. The use of a water-soluble
phosphane ligand in conjunction with a
hydrophobic phosphane ligand in the
presence of a surfactant promotes the
decarbonylation of formaldehyde in the
aqueous phase and the carbonylation of
enynes in the micellar phase.
Entropically Driven Ring-Opening-Metathesis Polymerization of Macrocyclic
Olefins with 21–84 Ring Atoms
Giant rings make neat monomers: Macrocyclic olefins with up to 84, and possibly
even more, ring atoms undergo ringopening-metathesis polymerization
(ROMP) to give high-molecular-weight
polymers when the monomer is used neat
or at very high concentration (see
scheme). This type of ROMP is driven by
entropy changes, unlike standard ROMP,
which is carried out using strained cyclic
monomers and is driven by the enthalpy
change of the reaction.
Modified Aluminum Oxide
Stoichiometric hydrolysis of the monomeric adduct 1 formed from an amine
and aluminum tert-butoxide provides aluminum oxide 2 with a high density of
Lewis acidic Al surface ions and few
hydroxy groups. The amine acts as a
protection agent for the coordination site
of Al. After the formation of the solid, the
amine can be exchanged readily with other
Lewis bases, and the surface Al ions that
the amine is coordinated to are catalytically active Lewis acid sites.
Macrocycle Polymerization
P. Hodge,* S. D. Kamau
2412 – 2414
A. I. Kozlov, M. C. Kung,* W. M. Xue,
H. H. Kung*
2415 – 2418
A “Soft-Chemical” Method To Synthesize
Lewis Acid Surfaces of Aluminum Oxide
2326
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 2322 – 2328
Angewandte
Chemie
1
3
8
5
10
OH
H
17
20'
9
7
18
11
13
15
H
Archaea Membrane Lipids
H
16'
19
19'
16
15'
OH
H
10'
E. Montenegro, B. Gabler, G. Paradies,
M. Seemann,
G. Helmchen*
2419 – 2421
1'
7'
9'
20
17'
18'
8'
1
The fat controller: Thermoacidophilic
Archaea possess membranes containing
lipids consisting of mixtures of macrocyclic, 72-membered tetraethers composed of saturated isoprenoid chains
linked to glycerol or higher sugars. Lipids
Family resemblance: While the cluster
chemistry of gallium generally proved to
be quite different from that of the polyboranes or polyborates, the transfer of one
electron to the nonagallium cluster
Ga9(CMe3)9 and the formation of its
persistent radical anion emphasizes (see
formula R = tBu) the close relationship
between gallium and boron. The reduction results in a considerable alteration of
structural parameters, with the compression of the cluster parallel to its threefold
rotation axis.
of this type form highly stable liposomes
and, therefore, are of commercial interest.
The configurations of lipids containing
cyclopentane units have now been determined by total synthesis of the diol 1.
Reduction of a Gallium Cluster
R
Ga
RGa
R
Ga
R
Ga
Ga
R
RGa
Determination of the Configuration of an
Archaea Membrane Lipid Containing
Cyclopentane Rings by Total Synthesis
GaR
Ga
R
GaR
W. Uhl,* L. Cuypers, W. Kaim,
B. Schwederski, R. Koch
2422 – 2423
[Ga9(CMe3)9]C —A Persistent Cluster
Radical Anion: Boron-Analogous
Chemistry with the Heavier Homologue
Gallium
RNA Repair
Repair of deletion mutations at the RNA
level: A small synthetic twin ribozyme
supports the insertion of four additional
nucleotides into a predefined site of an
arbitrarily chosen substrate RNA (see
scheme). This method of RNA repair
constitutes a novel approach to the therapy of medically relevant mutations.
R. Welz, K. Bossmann, C. Klug, C. Schmidt,
H.-J. Fritz, S. M;ller*
2424 – 2427
Site-Directed Alteration of RNA Sequence
Mediated by an Engineered Twin
Ribozyme
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.
The issues for May 2003 appeared online on the following dates
Issue 17: April 30. · Issue 18: May 8. · Issue 19: May 14. · Issue 20: May 21
Angew. Chem. Int. Ed. 2003, 42, 2322 – 2328
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2327
Contents
Service
Keywords
2428
Authors
2429
Vacancies
Preview
2328
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
2328, 2329
2431
Angew. Chem. Int. Ed. 2003, 42, 2322 – 2328
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