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Graphical Abstract Angew. Chem. Int. Ed. 42005

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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:
H. Braunschweig,* K. Radacki, D. Rais, G. R. Whittell
The First Boryl-Bridged Complex: An Unprecedented
Coordination Mode of the BR2 Ligand
D. Enders,* C. Grondal
Direct Organocatalytic de novo Synthesis of Carbohydrates
T. Fink, H. Bruggesser, J.-L. Reymond*
Virtual Exploration of the Small-Molecule Chemical Universe
Below 160 Daltons
S. Kobayashi,* K. Arai, H. Shimizu, Y. Ihori, H. Ishitani,
Y. Yamashita
A Bimetallic Chiral Niobium Complex for Lewis Acid Catalyzed
Enantioselective Reactions: Design of a Tridentate Ligand and
Elucidation of the Catalyst Structure
C. Whitehouse,* J. Fang, A. Aggeli, M. Bell, R. Brydson,
C. W. G. Fishwick, J. Henderson, C. M. Knobler, R. W. Owens,
N. H. Thomson, D. A. Smith, N. Boden*
Adsorption and Self-Assembly of Peptides on Mica Substrates
You Seok Seo, C. Lee, K. H. Lee, K. B. Yoon*
1:1 and 2:1 Charge-Transfer Interactions between Aromatic
Hydrocarbons and Dry Titanium Dioxide
News
R. Zare Receives Teaching Award
510
Distinction for G. Hfle
510
Franco-Spanish Prize to E. Carmona
510
Books
Chemoinformatics
Jrgen Bajorath
reviewed by G. Schneider
511
Chemical Biology
Herbert Waldmann, Petra Janning
reviewed by H. Breyhan, T. Kolter
511
Highlights
Silicon Compounds
M. Weidenbruch*
514 – 516
Molecules with a Genuine Si Si Triple
Bond and a Stable Derivative of [SiH]+
Bye bye multiple-bond rule: Recent successes in silicon chemistry are the siliconcontaining compounds 1, which has a Si
Si triple bond, and the [(Me5C5)Si]+ ion 2,
which is a stable derivative of the [HSi]+
ion. Both species are also notable from a
bond-theory point of view and can be
regarded as valuable starting materials for
synthetic organosilicon chemistry.
Reviews
Analytical Methods
Y. Cohen,* L. Avram, L. Frish
520 – 554
Diffusion NMR Spectroscopy in Supramolecular and Combinatorial Chemistry:
An Old Parameter—New Insights
498
Finger on the pulse: Diffusion NMR
spectroscopy, based on pulse gradient
spin echo NMR experiments, is a valuable
method for mapping molecular interactions at the molecular level in supramolecular and combinatorial chemistry.
The decay of the NMR signals also
enables, for example, information on the
intermolecular interactions in host–guest
systems to be obtained (see picture; G is
the pulsed gradient strength).
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 43, 498 – 506
Angewandte
Chemie
Communications
Zeolite Synthesis
Metal incorporation and synthesis of MFI
zeolites with microwave irradiation result
in crystal stacking in one direction to form
a fibrous morphology (see images of the
Ti-MFI zeolite). These materials display
several interesting physicochemical properties including lower packing density and
higher hydrophobicity than their nonfibrous counterparts, and as a result,
enhanced catalytic properties and
increased shape-selective adsorption.
Y. K. Hwang, J.-S. Chang,* S.-E. Park,*
D. S. Kim, Y.-U. Kwon, S. H. Jhung,
J.-S. Hwang, M. S. Park
556 – 560
Microwave Fabrication of MFI Zeolite
Crystals with a Fibrous Morphology and
Their Applications
Single-Molecule Studies
Real-time measurement of the catalysis
and substrate kinetics of a single-enzyme
hydrolysis reaction is demonstrated with
confocal fluorescence microscopy (CFM;
see picture, green = CFM beam). A single
lipase is shown to have a broad range of
conformations; each conformation contributes to the overall enzymatic activity,
an observation that is often masked by
ensemble measurements.
K. Velonia,* O. Flomenbom, D. Loos,
S. Masuo, M. Cotlet, Y. Engelborghs,
J. Hofkens,* A. E. Rowan,* J. Klafter,
R. J. M. Nolte,
F. C. de Schryver
560 – 564
Single-Enzyme Kinetics of CALB-Catalyzed
Hydrolysis
Membranes
Z.-Y. Yang,* R. G. Rajendran
564 – 567
Excellent thermal stability and mechanical
properties are exhibited by high-protonconductive membranes synthesized by a
facile copolymerization of tetrafluoro-
Copolymerization of Ethylene, Tetrafluoroethylene, and an Olefin-Containing
ethylene, ethylene, and CH2=CHCF2CF2O- Fluorosulfonyl Fluoride: Synthesis of
CF2CF2SO2F (see scheme and AFM image). High-Proton-Conductive Membranes for
These membranes have been successfully Fuel-Cell Applications
used in a direct MeOH fuel cell.
For the USA and Canada:
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and electronic / print or electronic delivery); for
individuals who are personal members of a
Angew. Chem. Int. Ed. 2005, 43, 498 – 506
www.angewandte.org
national chemical society, or whose institution
already subscribes, or who are retired or selfemployed consultants, print only: US$ 394.00.
Postage and handling charges included. All
Wiley-VCH prices are exclusive VAT.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
499
Angewandte
Chemie
Silicates
Unlike any other known crystalline silicate, the reduced nitridosilicate SrSi6N8
contains Si Si single bonds (see picture).
The Si Si distance is 235 pm, which
precisely matches that in diamond-type
silicon. The Si Si unit is embedded in a
framework of corner-sharing SiN4 tetrahedra. Thus, Si4+ and Si3+ coexist within
the same framework structure.
F. Stadler, O. Oeckler, J. Senker,
H. A. Hppe, P. Kroll,
W. Schnick*
567 – 570
SrSi6N8—A Reduced Nitridosilicate with a
Si Si Bond
Biomolecular Interactions
Specificity in weak biomolecular interactions: A novel technique, cold-spray ionization, can detect the weak but specific
noncovalent binding of carbohydrates to
proteins, water, and to other carbohydrate
molecules. It allows the determination of
dissociation constants and can assist in
computer simulations of putative receptor–ligand binding environments (see
picture).
S.-I. Nishimura,* N. Nagahori, K. Takaya,
Y. Tachibana, N. Miura,
K. Monde
571 – 575
Direct Observation of Sugar–Protein,
Sugar–Sugar, and Sugar–Water
Complexes by Cold-Spray Ionization
Time-of-Flight Mass Spectrometry
Nanomaterials
A strong blue emission is observed for
hybrid Ce3+/Ce4+ cerium phosphate
nanotubes, whereas Ce3+ phosphate
nanowires exhibit a characteristic doublepeak UV luminescence (see picture).
These cerium phosphate systems were
obtained by annealing novel cerium(iv)
phosphate nanotubes at different
temperatures.
C. Tang,* Y. Bando, D. Golberg,
R. Ma
576 – 579
Cerium Phosphate Nanotubes: Synthesis,
Valence State, and Optical Properties
Natural Products Synthesis
G. L. Nattrass, E. Dez, M. M. McLachlan,
D. J. Dixon, S. V. Ley*
580 – 584
Orthogonal and modular templating is an
effective basis for the preparation of the
biologically active annonaceous acetogenin 10-hydroxyasimicin (1). The versatile tartrate-derived 2,3-butanediacetal
Angew. Chem. Int. Ed. 2005, 43, 498 – 506
building block together with a highly
diastereoselective hetero-Diels–Alder
approach to the butenolide unit were
usefully employed in this novel
synthetic route.
www.angewandte.org
The Total Synthesis of the Annonaceous
Acetogenin 10-Hydroxyasimicin
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
501
Contents
Bioinorganic Chemistry
M. R. Bukowski, H. L. Halfen,
T. A. van den Berg, J. A. Halfen,*
L. Que, Jr.*
584 – 587
Spin-State Rationale for the
Peroxo-Stabilizing Role of the Thiolate
Ligand in Superoxide Reductase
Anti-push: The axial thiolate ligand stabilizes high-spin FeIII-OOR species (see
picture) such as those found in superoxide reductase. This situation is in contrast to the “push effect” observed in
structurally similar low-spin FeIII-OOR
systems, including cytochrome P450,
which promote O O bond cleavage.
These results show how very similar
enzyme-active sites can carry out two
very different functions.
Antitumor Agents
D. Castoldi, L. Caggiano, L. Panigada,
O. Sharon, A. M. Costa,
C. Gennari*
588 – 591
A Formal Total Synthesis of Eleutherobin
Through an Unprecedented Kinetically
Controlled Ring-Closing-Metathesis Reaction of a Densely Functionalized Diene
The key step in a formal total synthesis of
eleutherobin was an unprecedented kinetically controlled RCM reaction of a densely functionalized diene 1 bearing two
PMP-protected allylic alcohols in the presence of a second-generation Grubbs
catalyst. Subsequent isomerization of the
E 10-membered enedione 2 to the more
stable Z isomer and cleavage of the MOM
protecting group led to the known
precursor 3. MOM = methoxymethyl;
PMP = p-methoxyphenyl.
Dramatic differences are found in the
temperatures at which Bergman cyclizations occur when MoIV–enedithiolate–
enediyne complexes are used (see
scheme; S: yellow, Mo: red), and this can
be directly attributed to a long-range
electronic polarization effect of the metal
center. Ligand-to-metal charge transfer
within the C2S4 substructure and differential charge repulsion in the transition
state lead to a lowering of the barrier to
cyclization.
Out with the old, in with the new: Novel
1,8-naphthyridine C-nucleosides, Na-NO
and Na-ON (see formulae), were synthesized through Heck coupling reactions.
Oligodeoxynucleotides containing the NaNO and Na-ON nucleosides formed extremely stable duplexes by the base-pairing
motifs Na-NO :Im-ON and Na-ON :Im-NO.
Metal-Induced Cyclization
S. Bhattacharyya, M. Pink, M.-H. Baik,*
J. M. Zaleski*
592 – 595
A Unique Approach to Metal-Induced
Bergman Cyclization: Long-Range
Enediyne Activation by Ligand-to-Metal
Charge Transfer
Nonnatural Nucleotides
S. Hikishima, N. Minakawa,* K. Kuramoto,
Y. Fujisawa, M. Ogawa,
A. Matsuda*
596 – 598
Synthesis of 1,8-Naphthyridine C-Nucleosides and Their Base-Pairing Properties in
Oligodeoxynucleotides: Thermally Stable
Naphthyridine:Imidazopyridopyrimidine
Base-Pairing Motifs
502
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2005, 43, 498 – 506
Angewandte
Chemie
Crystal Engineering
Through the reduction of micrometersized silver phosphate crystals with a
perfect rhombododecahedral shape by a
reaction/diffusion process to hierarchical,
rhombododecahedral silver cages (see
picture): The controlled self-assembly of
silver particles around the precursor crystal surfaces leads to the formation of
morphology-preserved single- or doublewalled silver cages constructed from different building units.
J. Yang, L. Qi,* C. Lu, J. Ma,
H. Cheng
598 – 603
Morphosynthesis of Rhombododecahedral Silver Cages by Self-Assembly
Coupled with Precursor Crystal
Templating
The deuteration of water produces the
conformational change shown in the
figure in the anisole···water complex. The
value of the q angle decreases from 138 to
1288, and the secondary interaction
O···HMe is replaced by O···HPh.
A concise route to the heptacyclic indole
alkaloid stephacidin A (1) includes a
simple method for the gram-scale
synthesis of substituted tryptophans, a
remarkable indole annulation, and the
first enolate coupling of an amide to an
ester. This synthesis secures the relative
configuration of the natural product and
paves a potential path to several of its
congeners.
Molecular Dynamics
B. M. Giuliano, W. Caminati*
603 – 606
Isotopomeric Conformational Change in
Anisole–Water
Natural Products Synthesis
P. S. Baran,* C. A. Guerrero,
N. B. Ambhaikar,
B. D. Hafensteiner
606 – 609
Short, Enantioselective Total Synthesis of
Stephacidin A
Synthetic Methods
P. S. Baran,* J. M. Richter,
D. W. Lin
An odd couple: The union of pyrroles and
carbonyl compounds (ketones, amides,
esters, lactones, lactams, see scheme) is
described, and by the use of an intramolecular variant of this new method, the
nonsteroidal, anti-inflammatory drug (S)-
ketorolac has been prepared in a short
enantioselective synthesis. Mechanistic
underpinnings of this reaction, which
couples unfunctionalized C(sp2) and
C(sp3) atoms, are also discussed.
Direct Coupling of Pyrroles with Carbonyl
Compounds: Short Enantioselective
Synthesis of (S)-Ketorolac
Organic Synthesis
An environmentally friendly reaction that
excludes the potential contamination of
the products by metal impurities is
reported. In this reaction, optically active
aldoximes and nitriles are prepared from
chiral nitroalkanes (see scheme). The
methodology described expands the possibilities available for the conversion of
nitroalkanes into valuable targets.
Angew. Chem. Int. Ed. 2005, 43, 498 – 506
609 – 612
C. Czekelius, E. M. Carreira*
612 – 615
Convenient Transformation of Optically
Active Nitroalkanes into Chiral Aldoximes
and Nitriles
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
503
Contents
Peptide Enrichment
Y. Zhang, X. Wang, W. Shan, B. Wu, H. Fan,
X. Yu, Y. Tang,* P. Yang*
615 – 617
Enrichment of Low-Abundance Peptides
and Proteins on Zeolite Nanocrystals for
Direct MALDI-TOF MS Analysis
Concentrated efforts: A zeolite-nanocrystal-mediated enrichment procedure that
doubles as a desalting step allows lowabundance proteins to be readily detected
with MALDI-TOF MS (see picture). Mass
spectral signal-to-noise ratios are greatly
improved for a wide range of peptides,
which underscores the potential of this
procedure to boost proteomics research.
A high-yielding preparation of homoallylic
sulfones 2 entails the treatment of allylic
tosylacetate esters 1 with stoichiometric
or substoichiometric quantities of BSA
and substoichiometric quantities of KOAc
under conventional thermal or microwave
conditions. A possible mechanism
involves silyl ketene acetal formation,
[3,3]-sigmatropic rearrangement, and
desilylation-decarboxylation.
BSA = N,O-bis(trimethylsilyl)acetamide;
Ts = p-toluenesulfonyl.
Oligonucleotides immobilized in SAMs
(self-assembled monolayers) with a passifying surface layer, prepared from thermally smoothed gold surfaces and disulfides, allow the direct detection of
bound strands by MALDI-TOF mass
spectrometry. The binding of perfectly
matched (PM) and mismatched (MM)
DNA targets is observed (see picture).
The extent to which cross-hybridization
occurs depends on the type and position
of the mismatch.
The intervention of crown ethers or achiral
quaternary ammonium salts as achiral
phase-transfer catalysts (PTCs, see
scheme) in a chiral PTC system leads to
dramatic rate enhancements in the
asymmetric alkylation of glycine
derivatives.
Homoallylic Sulfones
D. Bourgeois, D. Craig,* N. P. King,
D. M. Mountford
618 – 621
Synthesis of Homoallylic Sulfones
through a Decarboxylative Claisen
Rearrangement Reaction
DNA Assays
U. Plutowski, C. Richert*
621 – 625
A Direct Glimpse of Cross-Hybridization:
Background-Passified Microarrays That
Allow Mass-Spectrometric Detection of
Captured Oligonucleotides
Phase-Transfer Catalysis
S. Shirakawa, K. Yamamoto, M. Kitamura,
T. Ooi, K. Maruoka*
625 – 628
Dramatic Rate Enhancement of
Asymmetric Phase-Transfer-Catalyzed
Alkylations
504
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2005, 43, 498 – 506
Angewandte
Chemie
Size matters: The adsorption of trans-2pentene on Pd/Al2O3 model catalysts
exhibits site-specific behavior, which
results in a strong increase in hydrogenation activity within the 1–5-nm particle
size range, in contrast to ethene hydrogenation (see figure). The size effects are
explained by the reactions proceeding via
di-s-bonded pentene, which is favored on
the terrace sites of large particles, and
p-bonded ethene.
A. M. Doyle, S. K. Shaikhutdinov,*
H.-J. Freund
629 – 631
Surface-Bonded Precursor Determines
Particle Size Effects for Alkene
Hydrogenation on Palladium
Metallocenes
Away from the fold: Insertion of the
terminal alkyne PhCH2C2H (2) into the
folded C3B2 heterocycle (R2 = CH2SiMe3,
Me) of the formal 16-valence-electron
complexes 1 gives the 18-valence-electron
boron-containing ruthenocene analogues
3 with a 4-borataborepine as 6p-electron
ligand. Side products 4 and C6H3(CH2Ph)3
are detected by mass spectrometry. Compound 4 is formed directly as the only
product when 1 is treated with R2C2
(R = Et, p-tolyl).
Y. Nie, H. Pritzkow, C. Hu, T. Oeser,
B. Bach, T. Mller, W. Siebert* 632 – 634
Ruthenocene Analogues with a Novel C5B2
Ligand: (h7-4-Borataborepine)(h5-pentamethylcyclopentadienyl)ruthenium
Complexes
Lots, fast: Benzo[c]phenanthridine derivatives are prepared efficiently by the
reaction of aldehydes and 2-methylbenzonitrile in the presence of potassium tertbutanolate, followed by dehydration (see
scheme). Some of these compounds
demonstrate excellent cytostatic
activity, and it is possible to introduce
substituents directly into the basic
molecular ring system.
B. Clement,* M. Weide, U. Wolschendorf,
I. Kock
635 – 638
A Two-Step Synthesis of Cytostatically
Active Benzo[c]phenanthridine
Derivatives
A striking similarity to the structure of
mother-of-pearl (nacre) is displayed by the
crystal architecture of highly oriented
laminated CaCO3 coatings (see scanning
electron microscope image ), which were
prepared by a multistep procedure. A
novel retardance imaging system (LCPolScope) was employed to characterize
the crystal texture of the polycrystalline
thin films.
Angew. Chem. Int. Ed. 2005, 43, 498 – 506
Hydrogenation
www.angewandte.org
Biomineralization
D. Volkmer,* M. Harms, L. Gower,
A. Ziegler
639 – 644
Morphosynthesis of Nacre-Type Laminated CaCO3 Thin Films and Coatings
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
505
Contents
Service
Keywords
646
Authors
647
Angewandte’s Sister Journals 648 – 649
Preview
651
Corrigendum
*
Mass Spectrometric Studies of DNA
Adducts from a Reaction with
Terpenoids**
W. Schrader,* S. Dring,
W. Joppek
The structural formula of the N7-guanine adduct in the Table of Contents for this
Communication contains an error. The correct structral formula is given below.
6657–6660
Angew. Chem. Int. Ed. 2004, 43
DOI 10.1002/anie.200461022
An Unusual Cyclization in a Bis(cysteinyl-S) The authors wish to add the following sentence to the Acknowledgements: B. . and
Diiron Complex Related to the Active Site L. S. thank the Swedish Energy Agency and the Swedish Research Council for financial
of Fe-Only Hydrogenases**
support.
C. He, M. Wang,* X. Zhang, Z. Wang,
C. Chen, J. Liu, B. kermark,
L. Sun*
3571–3574
Angew. Chem. Int. Ed. 2004, 43
DOI 10.1002/anie.200453961
506
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2005, 43, 498 – 506
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