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Graphical Abstract Angew. Chem. Int. Ed. 232003

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Contents
Meeting Reviews
Molecule-Based Magnetic
Materials
2570 – 2572
Eugenio Coronado, Fernando Palacio and
Jaume Veciana
Books
Chirality in Natural and Applied
Science
2573
Biomimetic Materials and Design
2574
W. J. Lough, I. W. Wainer
reviewed by D. Heller
Angela K. Dillow, Anthony M. Lowman
reviewed by J. Frahn
Highlights
Supertetrahedral Sulfides
G. F'rey*
2576 – 2579
Supertetrahedra in Sulfides: Matter
against Mathematical Series?
The game continues… Self-assembled
sulfide supertetrahedra can be used to
generate porous solids with unusual
electoluminescence and semiconducting
properties. Recent advances, including
the discovery of corner-linked superclusters (see picture) and super-supertetrahedral clusters, may lead to materials, the
properties of which could be superior to
the best quantum dots known to date.
Pd in Natural Product Synthesis
T. Graening,
H.-G. Schmalz*
2580 – 2584
Pd-Catalyzed Enantioselective Allylic
Substitution: New Strategic Options for
the Total Synthesis of Natural Products
As versatile as Nature: Pd-catalyzed
enantioselective allylic substitution is a
powerful reaction in modern synthetic
chemistry. The reactions of cyclic allylic
substrates (see figure) have recently been
proven to be of particular value as they
lead to novel and highly efficient strategies in the total synthesis of various
natural products.
Reviews
Transition-Metal Alkyne Complexes
N. J. Long,* C. K. Williams
2586 – 2617
Metal Alkynyl s Complexes: Synthesis and
Materials
2562
The M CC structural unit, which can be
used to establish a wide variety of molecular topologies (see, for example, the
tris(ferrocenylalkynyl) complex and the
molecular rigid-rod polymer shown),
together with the increasing importance
of material properties such as electron
transfer, nonlinear optical behavior, and
luminescence, combine to make transition-metal alkynyl complexes, especially
as oligomers and polymers, of particular
current interest.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 2562 – 2568
Angewandte
Chemie
Communications
Telling top and bottom apart: Supramolecular receptors can discriminate
between the “top” and “bottom” sides of
a single guest molecule, such as caffeine
(see picture). This reversible enantiofacial
differentiation results in the preferential
formation of the a or b complexes.
Stereoselective Complex Formation
M. C. Schopohl, C. Siering, O. Kataeva,
S. R. Waldvogel*
2620 – 2623
Reversible Enantiofacial Differentiation of
a Single Heterocyclic Substrate by Supramolecular Receptors
A Soluble Germanium Cluster
“Naked” but refined! The reaction of
germanium(i) bromide with Li{Si(SiMe3)3} gives the polyhedral Ge9 cluster
ion [Ge9{Si(SiMe3)3}3] (see structure), in
which only three of the nine germanium
atoms are bound to a ligand, the remaining germanium atoms are naked. The
unusually high solubility of this cluster
opens the possibility of using it as a
starting material for further reactions.
A. Schnepf*
2624 – 2625
[Ge9{Si(SiMe3)3}3] : A Soluble Polyhedral
Ge9 Cluster Stabilized by Only Three Silyl
Ligands
Welcome to the family: The previously
unknown discrete pentafluoroaluminate
[(CH3)4N]+2[AlF5]2 salt, a missing link of
the homoleptic fluoroaluminate family, is
synthesized from [(CH3)4N]+[AlF4] and
[(CH3)4N]+F . IR and Raman spectroscopic data along with 27Al MAS NMR
spectroscopy investigations reveal a perfect and unperturbed trigonal-bipyramidal
structure (see picture).
Discrete Fluoroaluminates
A breath of fresh air: Air oxidation of
[nBu4N]2[NiII(1-nor)3Br], prepared from
[nBu4N]2[NiIIBr4] and 1-norbornyllithium
generates the title pseudotetrahedral
organometallic complex in which a nickel
center with the formal oxidation state of
+ 4 is present (see structure; Ni purple,
Br brown, C black, H green).
High-Oxidation-State Ni Complex
For the USA and Canada:
ANGEWANDTE CHEMIE International
Edition (ISSN 1433-7851) is published weekly
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USA by Publications Expediting Inc. 200 Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2003, 42, 2562 – 2568
U. Groß,* D. M@ller,
E. Kemnitz*
2626 – 2629
Coordination Geometry of the Discrete
Pentafluoroaluminate Dianion [AlF5]2
V. Dimitrov,* A. Linden
2631 – 2633
A Pseudotetrahedral, High-OxidationState Organonickel Compound:
Synthesis and Structure of Bromotris(1-norbornyl)nickel(iv)
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
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delivery); for individuals who are personal
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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
2563
Contents
OAc
O
Biosynthesis of Alkylpyridines
OH
A. Cutignano, A. Tramice, S. De Caro,
G. Villani, G. Cimino,
A. Fontana*
2633 – 2636
Biogenesis of 3-Alkylpyridine Alkaloids in
the Marine Mollusc Haminoea Orbignyana
Single-Site/Dispersed-Metal Catalyst
C. Bianchini,* V. Dal Santo, A. Meli,
S. Moneti, M. Moreno, W. Oberhauser,
R. Psaro, L. Sordelli,
F. Vizza
2636 – 2639
Hydrogenation of Arenes over Catalysts
that Combine a Metal Phase and a Grafted
Metal Complex: Role of the Single-Site
Catalyst
N
acetate
N
Fruits of the sea: Alkylpyridine alkaloids
are a family of marine natural products,
the structures of which are all related to
each other by the presence of a biogenetically common motif, an alkyl chain linked
CN
CHO
+ CH (CN)
2639 – 2644
2
CN
2
Basically, a good catalyst: The introduction of NHx species into the framework of
mesoporous silicas results in silicon oxynitride materials and generates basic
sites, which exhibit considerable catalytic
activity for the Knoevenagel condensation
Self-Healing Systems
H 2O
2644 – 2647
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
reaction (see scheme). The well-ordered
mesoporous oxynitrides have a high surface area and pore volume and are
attractive as alternative basic catalysts,
especially for large-molecule transformations.
The organization of the vertebrate spine
was the source of the concepts used to
design self-healing structures. These
structures comprise mm-sized beads selfassembled on elastomeric threads and
connected by solder joints. The structures
spontaneously realign and heal (top) after
breaking and dislocation (bottom).
Self-Healing Systems Having a Design
Stimulated by the Vertebrate Spine
2564
+
Mesoporous
silicon oxynitride
Highly Ordered Mesoporous Silicon
Oxynitride Materials as Base Catalysts
M. Boncheva,
G. M. Whitesides*
to C-3 of a six-membered nitrogen heterocycle. We report the first experimental
evidence for the biosynthesis of alkylpyridines (see scheme).
Cooperating catalysts: The combined
single-site/dispersed-metal catalyst
[Rh(cod)(sulphos)]–Pd0/SiO2 (cod =
cyclooctadiene; sulphos =
O3S(C6H4)CH2C(CH2PPh2)3) is more
efficient than the dispersed-metal catalyst
Pd0/SiO2 for the hydrogenation of arenes
to cycloalkanes. The grafted rhodium
moieties and the palladium particles in
[Rh(cod)(sulphos)]–Pd0/SiO2 cooperate
to speed up the hydrogenation of arenes
(see scheme).
Mesoporous Basic Catalysts
Y. Xia, R. Mokaya*
+
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Angew. Chem. Int. Ed. 2003, 42, 2562 – 2568
Angewandte
Chemie
Cyclizations of Allenenes
H. Ohno, K. Miyamura, Y. Takeoka,
T. Tanaka*
2647 – 2650
Tri- and tetracyclic heterocycles were
formed through the tandem cyclization of
allenenes 1 upon treatment with an aryl
iodide, potassium carbonate, and catalytic [Pd(PPh3)4] (see scheme). The reac-
Catecholborane
tivity of the palladium(ii) intermediates
could be controlled by substitution (R’) at
the olefin terminus (Mts = 2,4,6-trimethylphenylsulfonyl).
When complexed to transition-metal
atoms, the zwitterionic ligand phenyl{bis(triphenylphosphanemethylenido)}borane behaves like a neutral analogue of
the h3-allyl ligand. Syntheses and X-ray
crystal structures of the ligand and its
complexes with ZrCl4 and PdCl2
(depicted) are described (Pd = cyan,
B = yellow, P = pink, Cl = green,
C = white).
A Zwitterionic Chelating Ligand
A Suzuki–Miyaura coupling reaction to
form C1 C20, macrolactamization at
N9 C10, and a mild decarboxylative anti
elimination to selectively introduce the
(Z)-1-propenylamide are key steps in a
highly convergent and completely stereoselective synthesis of the potent proteasome inhibitor TMC-95A (see structure).
Natural Product Synthesis
Phenyl{bis(triphenylphosphanemethylenido)}borane: A Zwitterionic Chelating
Ligand Exhibiting Allyl-Type Coordination
M. Inoue,* H. Sakazaki, H. Furuyama,
M. Hirama*
2654 – 2657
Total Synthesis of TMC-95A
A.-P. Schaffner, P. Renaud*
process (see scheme). This hydroallylation of alkenes proved to be general for a
wide range of alkenes and allyl sulfones.
2658 – 2660
Tin-Free Radical Allylation of
B-Alkylcatecholboranes
Anionic Gallium Carbene Analogue
The first covalently bonded metal complexes derived from an anionic gallium
carbene analogue (see picture) show
remarkable thermal stability in the solid
state. This fact suggests that gallium(i)
heterocycles should prove to be versatile
ligands towards both main-group and
transition-metal fragments.
Angew. Chem. Int. Ed. 2003, 42, 2562 – 2568
F. Jiang, P. J. Shapiro,* F. Fahs,
B. Twamley
2651 – 2653
Hydroallylation of Alkenes
SO2Ph
SO2Ph
SO2Ph
Organoboranes, prepared in situ by
hydroboration of olefins with catecholborane, are efficiently allylated with allyl
sulfones by a radical fragmentation
Palladium(0)-Catalyzed Tandem
Cyclization of Allenenes
R. J. Baker, C. Jones,* M. Kloth,
2660 – 2663
J. A. Platts
Synthesis and Structural Characterization
of Thermally Stable Group 13 Hydride
Complexes Derived from a Gallium(i)
Carbene Analogue
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2565
Contents
Containers for Cations
Ru
[CpCo(CN)3]+
[Cp*Ru(MeCN)3]+
S. C. N. Hsu, M. Ramesh, J. H. Espenson,
T. B. Rauchfuss*
2663 – 2666
EtNH3+
Cp
Co
Cp Co
Ru
Membership Rules for a Molecular Box:
The Admission Process and Protection
Provided to Guest Molecules
+
Cp*
Co
Ru
Cp Co +
Ru Cp*
Ru
Viruslike DNA Particles
+
+
Co
Cp
Cp*
Cp
=–C≡N
Co
Cp
= N2H5+, MeNH3+, NH4+, Cs+, K+, Rb+, Tl+
the box (see scheme). The box exhibits the
highest formation constant known for Cs+
ions. Once inside, ions are insulated from
chemical attack, such as amine-deprotonation or H–D exchange.
A synthetic viruslike particle: Monomolecular condensation of a gene into a 30nm particle was performed by the DNAtemplated air oxidation of a cationic thiol
detergent to a gemini lipid (depicted in
yellow). A folic acid coating was added (in
the form of the DNA-binding folate-containing compounds represented schematically by 2) and the resulting DNA
particles 1 were shown to be nanometric
and stable, and to enter cells through the
folic acid receptor.
G. Zuber,* L. Zammut-Italiano, E. Dauty,
J.-P. Behr
2666 – 2669
Targeted Gene Delivery to Cancer Cells:
Directed Assembly of Nanometric DNA
Particles Coated with Folic Acid
Metal–Organic Network Assembly
Impressive iron networks: Two-dimensional metal–organic coordination networks have been prepared by the vacuum
deposition of organic polytopic linkers
and metal atoms on a copper surface.
This unprecedented technique enabled
the modular assembly of open Fe–carboxylate grids (see image, Fe atoms in
green) that possess regularly spaced,
identically shaped cavities. The structure
and composition of the networks can
be tuned by controlling the deposition
parameters.
A. Dmitriev, H. Spillmann, N. Lin,*
J. V. Barth,* K. Kern*
2670 – 2673
Modular Assembly of Two-Dimensional
Metal–Organic Coordination Networks at
a Metal Surface
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Cp*
Ru Cp*
Co
Cp*
Crate chemistry: The inclusion dynamics
of molecular boxes has been studied by
virtue of the synthesis of the voided
ionophilic packing crate [{CpCo(CN)3}4(Cp*Ru)4] (Cp = C5H5 Cp* = C5Me5).
Numerous ions can then be inserted into
2566
Ru
Co
Ru
Cp
Cp*
Cp
Cp*
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Angew. Chem. Int. Ed. 2003, 42, 2562 – 2568
Angewandte
Chemie
Matrix Metalloproteinases
A helicoidal filament results from the
approach of the N-terminus of the
mutated variant of the catalytic domain of
MMP-12 with the catalytic zinc center of
another molecule (see X-ray structure);
adjacent filaments are arranged in double
helices. The N-terminal fragment is proposed to be analogous to an N-terminal
polypeptide product after cleavage.
Crystals yield two contrasting structures,
in which the NH3+ ion is either triply
hydrogen bonded, or only exhibits
van der Waals interactions.
I. Bertini,* V. Calderone, M. Fragai,
C. Luchinat, S. Mangani,
B. Terni
2673 – 2676
X-ray Structures of Binary and Ternary
Enzyme-Product-Inhibitor Complexes of
Matrix Metalloproteinases
Perylene-Derived Dyes
L. H. Gade,* C. H. Galka, R. M. Williams,*
L. De Cola, M. McPartlin, B. Dong,
L. Chi
2677 – 2681
Synthesis, Photophysical Properties, and
Nanocrystal Formation of a New Class of
Tetra-N-Substituted Perylenes
A new class of perylene-derived dyes,
tetra(carboxamido)perylenes, has been
obtained by a generally applicable synthetic method. Derivative A is shown to
form nanocrystalline aggregates in DMSO
which display significantly modified photophysical behavior with respect to the
monomer and were studied by using
atomic force microscopy techniques.
One-Pot Sequential Reactions
Y. Nishibayashi, M. Yoshikawa, Y. Inada,
M. D. Milton, M. Hidai,*
S. Uemura*
2681 – 2684
Two cats. in the same pot: The two
catalysts [Cp*RuCl(m2-SMe)2RuCp*Cl] (1)
and PtCl2 (2) promote a sequence of
catalytic cycles in the same medium. Trior tetrasubstituted furans or pyrroles are
afforded in moderate to good yields with
Angew. Chem. Int. Ed. 2003, 42, 2562 – 2568
high regioselectivities from the catalyzed
reactions of propargylic alcohols with
ketones or with ketones and anilines,
respectively (see scheme; cats. = catalysts).
www.angewandte.org
Novel Ruthenium- and PlatinumCatalyzed Sequential Reactions:
Synthesis of Tri- and Tetrasubstituted
Furans and Pyrroles from Propargylic
Alcohols and Ketones
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2567
Contents
Ferrous Complexes
O. L. Sydora, P. T. Wolczanski,*
E. B. Lobkovsky
2685 – 2687
Ferrous Wheels, Ellipse [(tBu3SiS)FeX]n,
and Cube [(tBu3SiS)Fe(CCSitBu3)]4
The shapes of things to come: The use of
the extremely bulky tBu3SiS ligand has
enabled the synthesis of rare ferrous
wheels (depicted), a unique ellipse, and
an uncommon ferrous cube based on
tetrahedral coordination. Fe = red,
Cl = green, S = orange, Si = blue, C = gray.
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.
Service
2568
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Keywords
2688
Authors
2689
Vacancies
2569
Preview
2691
Angew. Chem. Int. Ed. 2003, 42, 2562 – 2568
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