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Graphical Abstract Angew. Chem. Int. Ed. 472003

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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.
A. Albinati, P. Leoni,* L. Marchetti, S. Rizzato:
Assembling Metal Clusters with Covalent Linkers: Synthesis and
Structure of a Quasi-Planar Pt18 Dendrimer Containing Five
Clusters Connected by s-Alkynyl Spacers
DOI: 10.1002/anie.200352954
Published online: November 24, 2003
N. Schiefenh"vel, H.-J. Himmel, M. Binnewies*:
Plasmachemistry: N2(SiCl3)4?A Tetrakissilylhydrazine as an
Unexpected Product of the Reaction between N2 and SiCl4
DOI: 10.1002/anie.200352575
Published online: November 24, 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.
News
R. Noyori, A. Mller, and W. A. Herrmann honored
5790
Books
Magnetic Materials
5791
Nicola Spaldin
reviewed by S. Decurtins
Textures of Liquid Crystals
5791
Ingo Dierking
reviewed by M. Hird
Highlights
Amino Acid Synthesis
N. Sewald*
Unusual representatives of the synthetically attractive b-amino acids can be
accessed by two novel synthetic routes.
The synthesis of b2,3- and b2,3,3-amino
acids (A and B, respectively) involves a
diastereoselective 1,3-dipolar cycloaddition, whereas b2-amino acids C are
obtained by enantioselective CuI-catalyzed
conjugate addition of dialkyl zinc compounds to nitroalkenes.
5794 ? 5795
Synthetic Routes towards Enantiomerically Pure b-Amino Acids
Nanotechnology
C. M. Niemeyer*
5796 ? 5800
Functional Hybrid Devices of Proteins and
Inorganic Nanoparticles
The combination of inorganic nanoparticles with biological functionality, such as
the ATP-triggered release of CdS nanoparticles from inclusion complexes with
chaperonins (see schematic illustration),
5780
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
opens up innovative approaches to novel
hybrid devices applicable in biomedical
sensing and the fabrication of advanced
functional materials.
Angew. Chem. Int. Ed. 2003, 42, 5780 ? 5786
Angewandte
Chemie
Reviews
Lipid membranes
W. H. Binder,* V. Barragan,
F. M. Menger
Barriers with function: Domains and rafts
play an important role in the amazing
behavior of lipid membranes. The phase
separation of mixed lipid membranes (see
scheme) generates a new hierarchy of
membrane organization within lipid and
polymer vesicles. The biological impact of
this structuring as well as the chemical
background is described.
5802 ? 5827
Domains and Rafts in Lipid Membranes
Communications
Chemoselective coupling: The Staudinger
ligation between azide-functionalized
small molecules and a phosphane-modified glass surface offers a new immobilization strategy for the preparation of drug
arrays through the formation of a
thermodynamically stable amide (see
scheme).
Microarrays
The electronic resistance of an electrodemolecule-electrode device strongly
depends on the relative position of the
anchor group in the molecular structure.
The molecular rod, immobilized through
two sulfur groups in the meta position on
a pair of electrodes (see picture), displays
a considerably increased resistance com-
Electron Transport Mechanism
M. K?hn, R. Wacker, C. Peters,
H. Schr?der, L. Soul@re, R. Breinbauer,*
C. M. Niemeyer,*
H. Waldmann*
5830 ? 5834
Staudinger Ligation: A New Immobilization Strategy for the Preparation of SmallMolecule Arrays
M. Mayor,* H. B. Weber,* J. Reichert,
M. Elbing, C. von HBnisch, D. Beckmann,
M. Fischer
5834 ? 5838
pared to the rod with the sulfur groups in
the para position.
Electric Current through a Molecular
Rod?Relevance of the Position of the
Anchor Groups
Plant Acids
F. W. Lichtenthaler,* K. Nakamura,
J. Klotz
5838 ? 5843
The synthesis of dihydropyrans with the
d-xylo (1), d-ribo, l-arabino, and d-lyxo (2)
configuration by one-carbon-atom homologation of d-mannose or d-galactose,
terminal oxidation, and directed b elimination revealed ()-daucic acid isolated
from carrots to be 2, rather than 1 as
previously thought. The identical configuration of 2 and KDO 8-P (3) and available
biosynthetic information about chelidonic
acid (4) suggest a KDO 8-P based pathway for the generation of 2 and 4 in plants.
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Angew. Chem. Int. Ed. 2003, 42, 5780 ? 5786
www.angewandte.org
()-Daucic Acid: Revision of Configuration, Synthesis, and Biosynthetic Implications
delivery); for individuals who are personal
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5781
Contents
Azide Complexes (1)
Very sensitive materials: Tellurium tetraazide, Te(N3)4, was prepared directly from
TeF4 and Me3SiN3 as an extremely sensitive solid; azidation of a pentafluorotellurate(iv) anion gave the pentaazidotellurate(iv) anion. The crystal structure of
the pyridinium salt [pyH][Te(N3)5] consists
of [Te(N3)5] units, considerably distorted
from ideal square-pyramidal symmetry,
that are linked through Te贩種 interactions
(see picture).
T. M. Klap?tke,* B. Krumm, P. Mayer,
I. Schwab
5843 ? 5846
Binary Tellurium(iv) Azides: Te(N3)4 and
[Te(N3)5]
Azide Complexes (2)
Highly explosive Te(N3)4 was prepared by
the fluoride-ion-catalyzed reaction of TeF6
and Me3SiN3, and converted to the more
stable [P(C6H5)4]2[Te(N3)6] salt by reaction
with [P(C6H5)4]N3. The sterically active free
valence-electron pair at the Te center
strongly distorts the structure of the
[Te(N3)6]2 ion from the predicted ideal S6
symmetry (see picture). Evidence for the
formation of the [Te(N3)5] ion is also
presented.
R. Haiges, J. A. Boatz, A. Vij, M. Gerken,
S. Schneider, T. Schroer,
K. O. Christe*
5847 ? 5851
Polyazide Chemistry: Preparation and
Characterization of Te(N3)4 and
[P(C6H5)4]2[Te(N3)6] and Evidence for
[N(CH3)4][Te(N3)5]
Surface UV/Vis Spectroscopy
V. A. de la PeMa O?Shea,
M. Capel-Sanchez, G. Blanco-Brieva,
J. M. Campos-Martin,
J. L. G. Fierro*
5851 ? 5854
The Usefulness of Time-Dependent
Density Functional Theory to Describe the
Electronic Spectra of Ti-Containing
Catalysts
A good correlation between the experimental UV/Vis spectra of titanium-containing catalysts and the photophysical
properties calculated using time-dependent density functional theory (TD-DFT)
has been found for a ligand to metal
charge transfer (LMCT) from an oxygen
atom to a TiIV ion (see scheme). This
finding makes the TD-DFT methodology
an excellent tool to generate and interpret
the electronic spectra of isolated atoms
on the surface of heteroatom-containing
inorganic substrates.
A testing ground for cyclopentannulation
strategies: the triquinane natural product
hirsutene is obtained through the intramolecular organocatalytic [3� cycload-
dition of the 1,7-enyne (E)-1 . The cycloaddition is stereospecific: reaction of the
corresponding Z isomer provides the
epimeric diquinane.
Natural Product Synthesis
J.-C. Wang, M. J. Krische*
5855 ? 5857
Intramolecular Organocatalytic [3�
Dipolar Cycloaddition: Stereospecific
Cycloaddition and the Total Synthesis of
( )-Hirsutene
5782
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 5780 ? 5786
Angewandte
Chemie
Sweetness and light: A fluorescent thinfilm hydrogel that contains a covalently
bound boronic-acid-functional quencher
(Q) and a fluorescent dye (F; see Figure)
continuously senses glucose under physiological conditions through binding of
the sugar (S) to a labeled receptor (R).
Carbohydrate Sensors
J. T. Suri, D. B. Cordes, F. E. Cappuccio,
R. A. Wessling,
B. Singaram*
5857 ? 5859
Continuous Glucose Sensing with a
Fluorescent Thin-Film Hydrogel
Carbene Complexes
J. Barluenga,* I. PPrez-SQnchez, E. Rubio,
J. FlRrez
5860 ? 5863
From three simple starting materials, the
diastereoselective synthesis of pentasubstituted cyclopentanols or tetrasubstituted cyclohexane-1,4-diols can be
controlled by the appropriate choice of
lithium enolate (see scheme). The overall
one-pot transformation leads to the formation of up to five new CC bonds and
up to four contiguous stereogenic centers.
Three/Four/Five-Component Diastereoselective Cyclization of Fischer Carbene
Complexes, Lithium Enolates, and Allylmagnesium Bromide
Solid-State Structures
The importance of the thiadiazole ring:
While electrostatic interactions between
the thiadiazole rings is responsible for the
2D close packing in the solid-state structure of tetrakis(thiadiazole)porphyrazine
(TTDPzH2, see X-ray crystal structure), the
formation of a coordination bond between
the ring and the cobalt ion results in the
cobalt derivative TTDPzCo having a chain
structure.
M. Fujimori, Y. Suzuki, H. Yoshikawa,
K. Awaga*
5863 ? 5865
Packing Motifs in Porphyrazine Macrocycles Carrying Peripherally Annulated
Thiadiazole Rings: Crystal Growths of
Metal-Free and Cobalt Tetrakis(1,2,5-thiadiazole)porphyrazines
Addition reactions
M. Utsunomiya, M. Kawatsura,
J. F. Hartwig*
5865 ? 5868
Mildly acidic OH groups undergo transition-metal-catalyzed reversible addition
across the C糃 bonds of cyclic and acyclic
dienes. For example, the simple complex
Angew. Chem. Int. Ed. 2003, 42, 5780 ? 5786
[Pd(PPh3)4] (1 mol %) effectively catalyzes
both the forward addition of phenol
across dienes and the reverse elimination
of phenol from allylic ethers (see scheme).
www.angewandte.org
Palladium-Catalyzed Equilibrium Addition
of Acidic OH Groups across Dienes
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5783
Contents
Asymmetric Catalysis
T. Ooi, D. Sakai, M. Takeuchi, E. Tayama,
K. Maruoka*
5868 ? 5870
Practical Asymmetric Synthesis of Vicinal
Diamines through the Catalytic Highly
Enantioselective Alkylation of Glycine
Amide Derivatives
Phase-transfer catalysis (PTC) by a
designer chiral quaternary ammonium
bromide facilitated the direct, highly
enantioselective introduction of a wide
variety of substituents including cycloalkyl
side chains at the a position of the
prochiral glycine amide derivative 1. A
general, practical procedure for the
asymmetric synthesis of structurally
diverse monosubstituted vicinal diamines
of type 2 is presented. Dpm = diphenylmethyl.
Chiral N-heterocyclic carbene ligands
based on [2.2]paracyclophanes form
complexes with rhodium. These catalysts
can be used in the high-yielding and
enantioselective asymmetric conjugate
addition of arylboron compounds to cyclic
and acyclic enones (see scheme).
A versatile glycosylation reaction is used
to establish the process of sulfoxide
covalent catalysis. Hemiacetals are activated by benzenesulfonic anhydride and a
dialkyl sulfoxide catalyst, nBu2SO, for
coupling with various nucleophiles (Nu;
see scheme, TTBP = 2,4,6-tri-tert-butylpyridine). The sulfoxide catalyst functions
uniquely in three capacities, first as an O
nucleophile, then as a S+ electrophile, and
finally as a leaving group to fulfill turnover.
Rh-Catalyzed 1,4-Additions
Y. Ma, C. Song, C. Ma, Z. Sun, Q. Chai,
M. B. Andrus*
5871 ? 5874
Asymmetric Addition of Aryl Boron
Reagents to Enones with Rhodium
Dicyclophane Imidazolium Carbene
Catalysis
Covalent Catalysis
T. A. Boebel, D. Y. Gin*
5874 ? 5877
Sulfoxide Covalent Catalysis: Application
to Glycosidic Bond Formation
Hydrogen Shifts
R. Hoffmann,*
D. J. Tantillo*
5877 ? 5882
Breaking Down Barriers: The Liaison
Between Sigmatropic Shifts, Electrocyclic
Reactions, and Three-Center Cations
5784
Almost indistinguishable transition-state
(TS) geometries, which differ only by the
presence or absence of a simple proton,
were found for electrocyclic and sigmatropic rearrangements with the same
electron count (see picture).
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 5780 ? 5786
Angewandte
Chemie
Synthesis of Oligonucleotides
J. Kim, J. M. Gil,
M. M. Greenberg*
Selective introduction of damage: The
C4?-position of DNA serves as the site of
attack for a number of DNA damaging
agents, including bleomycin. The C4?abasic site is a major product found in
damaged DNA following abstraction of
the hydrogen atom from this position. The
first general method for the synthesis of
oligonucleotides 1 containing the C4?abasic site at defined positions is described (see scheme). This method should
facilitate physicochemical, biochemical,
and biological studies on this commonly
formed DNA lesion.
5882 ? 5885
Synthesis and Characterization of Oligonucleotides Containing the C4?-Oxidized
Abasic Site Produced by Bleomycin and
Other DNA Damaging Agents
Molecular Shuttles
G. Bottari, F. Dehez, D. A. Leigh,*
P. J. Nash, E. M. PPrez, J. K. Y. Wong,
F. Zerbetto*
5886 ? 5889
Entropy-Driven Translational Isomerism:
A Tristable Molecular Shuttle
Two?s company but three?s allowed! An
entropy-driven tristable molecular shuttle
has been developed, where shuttling
between two of three stations is brought
about through a photochemical isomer-
ization, but a further stable co-conformation is unexpectedly observed simply
upon changing the temperature (the picture shows the molecular shuttle in one of
the three possible co-conformations).
Coordination Isomers
M. Woods, Z. Kovacs, S. Zhang,
A. D. Sherry*
5889 ? 5892
Towards the Rational Design of Magnetic
Resonance Imaging Contrast Agents:
Isolation of the Two Coordination Isomers
of Lanthanide DOTA-Type Complexes
Controlling water exchange: Square antiprism (SAP; left) and twisted square
antiprism (TSAP; right) coordination isomers of LnIIIDOTA-type complexes
(DOTA = 1,4,7,10-tetraazacyclododecane1,4,7,10-tetraacetic acid) may be isolated
Angew. Chem. Int. Ed. 2003, 42, 5780 ? 5786
by choosing substituents on the ring and
arms with identical chirality for the TSAP
isomer, or with opposite chirality for the
SAP isomer. The water exchange rates of
the complexes differ by an order of
magnitude.
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5785
Contents
Nucleic Acids
P. S. Pallan, C. J. Wilds, Z. Wawrzak,
R. Krishnamurthy, A. Eschenmoser,
M. Egli*
5893 ? 5895
Why Does TNA Cross-Pair More Strongly
with RNA Than with DNA? An Answer
From X-ray Analysis
Electron Transfer
M. A. O?Neill, H.-C. Becker, C. Wan,
J. K. Barton,* A. H. Zewail* 5896 ? 5900
Ultrafast Dynamics in DNA-Mediated
Electron Transfer: Base Gating and the
Role of Temperature
The TNA twist: l-a-threofuranosyl (3?!2?)
nucleic acid (TNA) residues adopt a C4?exo pucker when incorporated into an A(left) or a B-form DNA duplex (right). The
resulting intranucleotide P贩稰 distance in
TNA is very similar to that in RNA
(represented by a C3?-endo puckered adenosine residue; green). The structural
data explain earlier observations that TNA
hydridizes more stably with RNA than
with DNA and that RNA constitutes the
better template for ligating TNA fragments.
The ultrafast dynamics of electron transfer
(ET) between bases in DNA have been
determined to elucidate the critical role of
base-pair gating on the timescale of the
electron transport and the temperature
dependence of the rates. ET occurs only
through DNA duplexes that adopt a
specific, well-coupled alignment of bases
(ET-active; see picture). Descriptions of
ET dynamics must include fluctuations of
DNA bases.
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
Keywords
5904
Authors
5905
Angewandte?s
Sister Journals
5786
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5902 ? 5903
Vacancies
5787
Preview
5907
Angew. Chem. Int. Ed. 2003, 42, 5780 ? 5786
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