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Graphical Abstract Angew. Chem. Int. Ed. 462005

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Contents
The following Communications have been judged by at least two referees to be “very
important papers” and will be published online at www.angewandte.org soon:
S. J. Dalgarno, G. W. V. Cave, J. L. Atwood*
Toward the Isolation of Functional Organic Nanotubes
Y. Nakajima, H. Kameo, H. Suzuki*
Cleavage of the Nitrogen-Hydrogen Bond of Ammonia Induced
by Triruthenium Polyhydrido Clusters
N. Lu,* H. P. S. Kumar, J. L. Fye, J. S. Blanks, J. S. Thrasher,*
H. Willner, H. Oberhammer
The Initial Synthesis of the Long Sought After Compound
Pentafluoronitrosulfane, SF5NO2
G. I. Elliott, J. Velcicky, H. Ishikawa, YongKai Li, D. L. Boger*
Total Synthesis of ( )- and ent-(+ )-Vindorosine: Tandem
Intramolecular Diels-Alder/1,3-Dipolar Cycloaddition of
1,3,4-Oxadiazoles
G. Krebs, L. Hugonet, J. D. Sutherland*
Substrate Ambiguity and Catalytic Promiscuity Within a Bacterial
Proteome Probed by an Easy Phenotypic Screen for Aldehydes
E. /lvarez, M. Paneque,* M. L. Poveda,* N. Rend3n
Formation of Iridabenzenes by Coupling of
Iridacyclopentadienes and Alkenes
Meeting Reviews
D. Whrle
7500
Harry Nursten
reviewed by H. Steinhart
7503
A broad spectrum of valuable cyclic and
acyclic products are available in diastereoand/or enantioselective form by sustainable, organocatalytic processes like the
heterazolium-catalyzed transformations
shown in the scheme. The carbene-mediated generation of activated carboxylate
intermediates provides new possibilities
for the straightforward synthesis of
multifunctionalized compounds.
Macromolecular Metal Complexes: Materials for Various Applications
Books
The Maillard Reaction
Highlights
Organocatalysis
K. Zeitler*
7506 – 7510
Extending Mechanistic Routes in
Heterazolium Catalysis—Promising
Concepts for Versatile Synthetic Methods
Minireviews
Reaction Mechanisms
S. Ma,* Z. Gu
7512 – 7517
1,4-Migration of Rhodium and Palladium
in Catalytic Organometallic Reactions
7488
A key mechanistic step in a number of
rhodium- and palladium-catalyzed reactions is the 1,4-migration of the metal
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
center, which can be understood as the
oxidative addition of the metal into a CH
or CX bond followed by reductive elimination. Although concrete evidence for
the transition state is lacking, the synthetic applications are numerous.
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
Angewandte
Chemie
Reviews
An esthetic example of the wide variety of
biological aerosol particles found in the
atmosphere are the pictured brochosomes, which are released by insects.
Atmospheric chemistry and physics, the
biosphere, the hydrological cycle, climate,
and human health are all strongly influenced by natural and anthropogenic particles in the nanometer to micrometer size
range.
Atmospheric Chemistry
7520 – 7540
U. P3schl*
Atmospheric Aerosols: Composition,
Transformation, Climate and Health
Effects
Communications
The question of coloring: Calculations
present a definite solution to the “coloring
problem” in the MB2C2 phases (M = Mg,
Sc, Ca, Y, Ln; see picture of the four
structure types). Electric-field gradient
tensor components from NMR spectroscopy readily allow differentiation between
the different B/C topologies and give
support to the theoretical results.
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
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
Inclusion Compounds
X. Rocquefelte,* S. E. Boulfelfel,
M. Ben Yahia, J. Bauer, J.-Y. Saillard,*
J.-F. Halet*
7542 – 7545
Structural Preference versus Metal within
the MB2C2 (M = Mg, Sc, Ca, Y, Ln) Phases:
The Coloring Problem Revisited by DFT
Calculations
A void apart! A clathrate based on zinc
octa(2,6-diisopropylphenoxy)phthalocyanine contains solvent-filled voids of
exceptionally large volume (> 8 nm3 ; see
picture for the packing arrangement).
Each nanovoid is enclosed by a cubic
assembly of six phthalocyanine molecules
and contains 18 molecules of water and
an estimated 65 molecules of acetone,
which may be exchanged for methanol or
water molecules without loss of order.
Crystal Engineering
Meacham Ave., Elmont, NY 11003. Periodicals
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
NJ 07030. Annual subscription price for institutions: US$ 5685/5168 (valid for print and
electronic / print or electronic delivery); for
individuals who are personal members of a
national chemical society prices are available
on request. Postage and handling charges
included. All prices are subject to local VAT/
sales tax.
N. B. McKeown,* S. Makhseed,
K. J. Msayib, L.-L. Ooi, M. Helliwell,
J. E. Warren
7546 – 7549
A Phthalocyanine Clathrate of Cubic
Symmetry Containing Interconnected
Solvent-Filled Voids of Nanometer
Dimensions
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7489
Angewandte
Chemie
It’s not how short you make it, it’s how
you make it short! A diverse collection of
compounds with short CC single bonds
whose lengths range from 1.32 P to 1.46 P
have been theoretically designed (see
structure of a “spiderane”). The strategies
for squeezing the CC bonds (encapsulation, strapping back, and stiffening)
allow shorter bonds than hybridization
and conjugative effects alone.
Carbon–Carbon Bonds
A true convert: The carboxylesterase
enzyme R.34 (see picture) can be converted into a triacylglycerol lipase without
modification of the shape, size, or hydrophobicity of the substrate binding site.
The substitution of Asn33 by Asp results
in a salt bridge between the Asp33 and
Arg49, which causes a distortion of the
enzyme structure that makes the catalytic
site more accessible to larger substrates
but also more labile.
Enzyme Mutation
D. R. Huntley,* G. Markopoulos,
P. M. Donovan, L. T. Scott,
R. Hoffmann*
7549 – 7553
Squeezing CC Bonds
D. Reyes-Duarte, J. Polaina,
N. LLpez-CortMs, M. Alcalde, F. J. Plou,
K. Elborough, A. Ballesteros,
K. N. Timmis, P. N. Golyshin,
M. Ferrer*
7553 – 7557
Conversion of a Carboxylesterase into a
Triacylglycerol Lipase by a Random
Mutation
Dual action: An analogue of a natural
hexaketide thioester substrate is incubated with recombinant picromycin/methymycin synthase (PICS) module 6 with its
attached thioesterase (TE). A mixture of
12- and 14-membered-ring macrolactones
10-deoxymethynolide (1) and narbonolide
(2) are generated (see scheme) by competing chain elongation and direct lactonization of the substrate. KS = ketosynthase, AT = methylmalonyl transferase,
ACP = acyl carrier protein, metmal
CoA = methylmalonyl coenzyme A.
Three modes: An iminoferrocenylphosphane ligand stabilizes low-coordinate
and low-valent nickel in [{[h-C5H4CH=N(C6H5)]Fe[h-C5H4P(tBu)2]-N,P}NiICl] (see
figure) and similar complexes. The coordination environment is hemilabile as
exemplified by three different coordination modes: P,N(s)-chelate, P,CN(p)chelate, and P unidentate. These complexes are catalytically active towards
ethylene oligomerization.
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
Biosynthesis
J. Wu, W. He, C. Khosla,
D. E. Cane*
7557 – 7560
Chain Elongation, Macrolactonization,
and Hydrolysis of Natural and Reduced
Hexaketide Substrates by the Picromycin/
Methymycin Polyketide Synthase
Nickel-Catalyzed Oligomerization
Z. Weng, S. Teo, L. L. Koh,
T. S. A. Hor*
7560 – 7564
Ethylene Oligomerization at
Coordinatively and Electronically
Unsaturated Low-Valent Nickel
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7491
Contents
Asymmetric Hydrogenations
C. Moessner, C. Bolm*
7564 – 7567
Diphenylphosphanylsulfoximines as
Ligands in Iridium-Catalyzed Asymmetric
Imine Hydrogenations
Easily accessible phosphine-substituted
sulfoximines 2 have been applied in Ircatalyzed asymmetric hydrogenations of
acylic N-arylated imines 1. The amines 3
are formed under mild conditions in high
yields with excellent ee values.
Caught in a trap! An S-heterocyclic carbene (SHC) with a cyclotetrasilane backbone is generated by a [2þ3] cycloaddition of cyclotetrasilene with CS2 and
trapped with C60 as a chemical probe. It is
demonstrated that photolysis of antidodecaisopropyltricyclo[4.2.0.02,5]octasilane and CS2 in the presence of C60 affords
a methanofullerene (see scheme).
Two paths diverge: Four-component cascades that involve the cycloaddition of
azomethine ylides, azomethine imines, or
nitrones generated in situ, coupled with
allene incorporation, give rise to five new
bonds, two rings, and two to four stereocenters through two possible pathways
(see picture for an example).
Heterocycles
H. Nikawa, T. Nakahodo, T. Tsuchiya,
T. Wakahara, G. M. A. Rahman,
T. Akasaka,* Y. Maeda, M. T. H. Liu,
A. Meguro, S. Kyushin, H. Matsumoto,*
N. Mizorogi, S. Nagase*
7567 – 7570
S-Heterocyclic Carbene with a Disilane
Backbone
Multicomponent Reactions
H. A. Dondas, C. W. G. Fishwick, X. Gai,
R. Grigg,* C. Kilner, N. Dumrongchai,
B. Kongkathip, N. Kongkathip,
C. Polysuk,
V. Sridharan
7570 – 7574
Stereoselective Palladium-Catalyzed
Four-Component Cascade Synthesis of
Pyrrolidinyl-, Pyrazolidinyl-, and
Isoxazolidinyl Isoquinolines
Template Synthesis
T. Magbitang, V. Y. Lee, J. N. Cha,
H.-L. Wang, W. R. Chung, R. D. Miller,
G. Dubois, W. Volksen, H.-C. Kim,*
J. L. Hedrick*
7574 – 7580
Oriented Nanoporous Lamellar
Organosilicates Templated from
Topologically Unsymmetrical DendriticLinear Block Copolymers
7492
www.angewandte.org
Dendrimers between the sheets: Environmentally responsive dendritic-linear
block copolymers, based on poly(ethylene
oxide) and a dendron derived from 2,2’bis(hydroxymethyl)propionic acid (see
structure), were used to organize organosilicate vitrificates into nanostructured
lamellar morphologies. Upon thermolysis
of the template, a perforated porous
lamellar structure (4 nm) between organosilicate sheets (6–9 nm) was obtained.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
Angewandte
Chemie
Sugar on a stick: A DNA template can
bind two complementary oligonucleotides, one derivatized with glyceraldehyde
(blue) and the other with glycolaldehyde
(red), resulting in a cross-aldol reaction
that forms pentose sugars. This reaction
system serves as a model for the RNAcatalyzed synthesis of ribose, which is
Origin of Life
M. Oberhuber, G. F. Joyce*
relevant to a presumed RNA-based metabolism during the early history of life on
Earth.
A DNA-Templated Aldol Reaction as a
Model for the Formation of Pentose
Sugars in the RNA World
Negative beats positive: A channel composed of oligoether chains attached by
amine groups to b-cyclodextrin mediates
the transport of halides across a phospholipid bilayer (see scheme) at faster
rates than those observed for monovalent
cations. Protonation of the amine linkages
likely explains the preferential anion
transport.
Ion Selectivity
Hot spots: The surprising, apparently
catalytic effect of H2 in the dehydrogenation of 1 in supercritical CO2 is the result
of thermal hot spots (see thermal image
of reactor) generated in the catalyst bed by
an initial exothermic hydrogenation. The
localized heating forces the dehydrogenation reaction which also gives the
diene 2 by a route that is potentially much
simpler than the established procedure.
Heterogeneous Catalysis
Very ANDy: A photochromic molecular
switch has been found to act as an AND
Boolean logic gate. The switch takes as
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
7580 – 7583
N. Madhavan, E. C. Robert,
M. S. Gin*
7584 – 7587
A Highly Active Anion-Selective
Aminocyclodextrin Ion Channel
J. R. Hyde,* B. Walsh,
M. Poliakoff*
7588 – 7591
“Hydrogen-Catalyzed” Dehydrogenation:
A Supercritical Conundrum
input both UV light, which causes photoisomerization of a dihydroindolizine to an
open, dipolar form, and an electric field,
which aligns this isomer in solution (see
scheme). The output of the gate is read as
the electric linear dichroism response of
the open isomer. The gate can be reset
with visible light.
Molecular Electronics
J. AndrMasson,* Y. Terazono, B. Albinsson,
T. A. Moore,* A. L. Moore,*
D. Gust*
7591 – 7594
Molecular AND Logic Gate Based on
Electric Dichroism of a Photochromic
Dihydroindolizine
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7493
Contents
Coordination Chemistry
N. Chatterton, Y. BretonniVre, J. PMcaut,
M. Mazzanti*
7595 – 7598
An Efficient Design for the Rigid Assembly
of Four Bidentate Chromophores in
Water-Stable Highly Luminescent
Lanthanide Complexes
A simple bridge solves a difficult architectural problem. Ligand H4tpaen, with an
ethylenediamine backbone that has ten
donor atoms, yields ten-coordinate lanthanide complexes, thus providing highly
effective protection of the metal center
from interaction with the solvent molecules. As a result, the EuIII and TbIII
complexes of (tpaen)4 show a bright and
long-lived luminescence in H2O combined with high solubility and stability.
Expanding rings: An intermediate organorhodium(i) species formed in the RhIcatalyzed reaction of acetylenic b-ketoesters and b-diketones with aryl boronic
acids undergoes intramolecular nucleo-
philic addition to a ketone carbonyl group.
The ensuing ring-opening reaction of the
resulting cyclobutanols results in acyl 1,3migration leading to the development of a
two-carbon-atom ring-expansion reaction.
Ring Expansion
T. Miura, M. Shimada,
M. Murakami*
7598 – 7600
Acyl 1,3-Migration in Rhodium-Catalyzed
Reactions of Acetylenic b-Ketoesters
with Aryl Boronic Acids: Application to
Two-Carbon-Atom Ring Expansions
Surface Chemistry
T. Schalow, M. Laurin, B. Brandt,
S. Schauermann, S. Guimond,
H. Kuhlenbeck, D. E. Starr,
S. K. Shaikhutdinov, J. Libuda,*
H.-J. Freund
7601 – 7605
Oxygen Storage at the Metal/Oxide
Interface of Catalyst Nanoparticles
Carbohydrate Synthesis
M. S. M. Timmer, A. Adibekian,
P. H. Seeberger*
7605 – 7607
Short De Novo Synthesis of Fully
Functionalized Uronic Acid
Monosaccharides
7494
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Holding its breath: Small Pd particles on
an Fe3O4 support reversibly store large
quantities of oxygen in the form of a thin
Pd oxide layer at the particle/support
interface. Oxygen from this reservoir can
be released during oxidation reactions, as
shown by a combination of molecular
beam methods, scanning tunneling
microscopy, and photoelectron spectroscopy.
Short and Sweet: A convergent route
leads to orthogonally protected d-glucuronic and l-iduronic acid thioglycoside
building blocks, commonly used in
heparin oligosaccharide assembly (see
scheme). Rapid access to substantial
quantities of these key intermediates
feeds the growing need for monosaccharide building blocks for use in the
assembly of bioactive oligosaccharides.
PG = protecting group.
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
Angewandte
Chemie
Four reaction parameters and their effects
on the formation of cobalt succinate
phases were studied by high-throughput
methods. In addition to identifying two
new phases, we show that higher reaction
temperatures lead to products containing
less water, more basic conditions favor
increasingly condensed M-O-M networks
(see phase diagram), and depending on
the reaction time the products are formed
under either kinetic or thermodynamic
control.
High-Throughput Methods
On the dot: Efficient energy transfer from
Tb complexes to quantum dots with an
extremely large F3rster radius of 81 P is
achieved by formation of a streptavidin–
biotin coupled donor–acceptor complex.
The long luminescence lifetime of the Tb
donor and the high absorption of the
quantum dots make this couple a powerful tool for analyzing biological and biochemical interactions.
Bioanalysis
P. M. Forster, N. Stock,*
A. K. Cheetham*
7608 – 7611
A High-Throughput Investigation of the
Role of pH, Temperature, Concentration,
and Time on the Synthesis of Hybrid
Inorganic–Organic Materials
N. Hildebrandt,* L. J. CharbonniVre,*
M. Beck, R. F. Ziessel,
H.-G. L3hmannsr3ben
7612 – 7615
Quantum Dots as Efficient Energy
Acceptors in a Time-Resolved
Fluoroimmunoassay
Solid-State Structures
A new form of P: The crystal structure of a
fibrous type of red phosphorus was solved
using single-crystal X-ray diffraction
methods and transmission electron
microscopy. It consists of double tubes
(see picture) and is closely related to the
structure of Hittorf’s phosphorus. Density
functional calculations confirm the
experimental results.
M. Ruck,* D. Hoppe, B. Wahl, P. Simon,
Y. Wang, G. Seifert
7616 – 7619
Fibrous Red Phosphorus
Kinetic Resolution
S. Rendler, G. Auer,
M. Oestreich*
Fishing for enantiomers: A novel kinetic
resolution of racemic alcohols capable of
two-point binding makes use of silanes
with silicon-centered chirality. This strategy is based on a diastereoselective
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
dehydrogenative silicon–oxygen coupling
under copper catalysis (see scheme). The
resolving silane is completely recovered
without erosion of stereochemical information at silicon.
7620 – 7624
Kinetic Resolution of Chiral Secondary
Alcohols by Dehydrogenative Coupling
with Recyclable Silicon-Stereogenic
Silanes
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7495
Contents
Antitumor Agents
S. Dziadek, D. Kowalczyk,
H. Kunz*
7624 – 7630
Synthetic Vaccines Consisting of TumorAssociated MUC1 Glycopeptide Antigens
and Bovine Serum Albumin
Sweet medicine: The mucin MUC1 is
highly overexpressed on epithelial tumor
cells. Glycopeptides 1 (from the repeating
unit of MUC1) carrying various important
sialylated tumor-associated carbohydrate
antigens R were synthesized and coupled
to bovine serum albumin (to generate
anticancer vaccines) and to microtiter
plates (to test the selectivity of the
immune response).
On target: With the fully synthetic vaccine
1 consisting of a tumor-associated sialylTn glycopeptide antigen from the epithelial mucin MUC1 and a T-cell epitope from
ovalbumin, a strong, highly specific
immune response (IgG) directed against
the glycopeptide antigen was induced in a
mouse thereby realizing the most important requirement for the development of
synthetic vaccines for the initiation of the
body’s own immune defense against
tumors.
Catching proteins: Proteins from a protein–DNA microarray can be directly
detected by using MALDI mass spectrometry. Capture proteins are attached to
silicon chips in a highly selective and
reversible way by DNA-directed immobilization (see picture). The analyte proteins
bound specifically to their partners on the
microarray can be detected from cell
lysates.
Antitumor Agents
S. Dziadek, A. Hobel, E. Schmitt,
H. Kunz*
7630 – 7635
A Fully Synthetic Vaccine Consisting of a
Tumor-Associated Glycopeptide Antigen
and a T-Cell Epitope for the Induction of a
Highly Specific Humoral Immune
Response
Bioanalysis
C. F. W. Becker,* R. Wacker, W. Bouschen,
R. Seidel, B. Kolaric, P. Lang, H. Schroeder,
O. MXller, C. M. Niemeyer, B. Spengler,
R. S. Goody, M. Engelhard* 7635 – 7639
Direct Readout of Protein–Protein
Interactions by Mass Spectrometry from
Protein–DNA Microarrays
Cluster Compounds
A. Karpov, M. Jansen*
7639 – 7643
[Tl8]6 in Cs8Tl8O: A Naked Eight-Vertex
closo-Deltaeder as a Cluster Anion
7496
www.angewandte.org
Structures to count on: The title compound crystallizes in a unique crystalstructure type which can be regarded as a
rock-salt derivative composed of a suboxide group [OCs6+2]6+ (yellow) and a
novel thallium cluster [Tl8]6 (blue). The
valence electron count of the eight-vertex
cluster obeys the Wade–Mingos condensation rules when considering it as a
condensation of an octahedron with two
tetrahedra.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
Angewandte
Chemie
Service
Angew. Chem. Int. Ed. 2005, 44, 7488 – 7497
Keywords
7644
Authors
7645
Angewandte’s Sister Journals
7646
Preview
7647
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7497
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