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Graphical Abstract Angew. Chem. Int. Ed. 222006

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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:
C. Burke, Y. Shi*
Regio- and Enantioselective Epoxidation of Dienes by a Chiral
Dioxirane: Synthesis of Optically Active Vinyl cis-Epoxides
C.-W. So, H. Roesky,* J. Magull, R. Oswald
Synthesis and Characterization of [{PhC(NtBu)2}SiCl]: A Stable
Monomeric Chlorosilylene
H. Yu, S. Huang, H. Chokhawala, M. Sun, H. Zheng, X. Chen*
Highly Efficient Chemoenzymatic Synthesis of Naturally
Occurring and Non-Natural a2,6-Linked Sialosides: A
P. damsela a2,6-Sialyltransferase with Extremely Flexible Donor
Substrate Specificity
D. Rohde, C.-J. Yan, H.-J. Yan, L.-J. Wan*
From Lamellar to Hexagonal Self-Assembly of Bis(dioxaborin)
Molecules
Meeting Reviews
The Many Facets of Photochemistry
J. Mattay
3570
3572
Books
Bioorganometallics
Grard Jaouen
reviewed by B. Lippert
Artificial Photosynthesis
Anthony F. Collings, Christa Critchley
reviewed by L. Hammarstrm, O. Johansson,
A. Magnuson
3573
Highlights
Molecular Capsules
L. Cronin*
Capsule “hotels” for molecular guests:
The binding, release, and even reaction of
guests within the cavities of inorganic
cages or capsules (see picture) can be
performed with an unprecedented level of
control. In view of this host–guest
chemistry, such functional frameworks are
promising in catalysis and for model
studies of ion channels in biological
membranes.
3576 – 3578
Inorganic Molecular Capsules:
From Structure to Function
Aryne Insertions
D. Pe%a,* D. Prez,
E. Guiti(n*
3579 – 3581
Insertion of Arynes into s Bonds
3558
Enjoying a revival: Following a quiet
period, numerous reports have recently
appeared regarding the insertion of arynes
into s bonds (see scheme) as a result of
milder, high-yielding methods for generating arynes and the introduction of
palladium catalysis into aryne chemistry.
The methodology shows promise as a
means of preparing complex ortho-disubstituted arenes.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
Angewandte
Chemie
Reviews
Full of energy: Energetic ionic salts offer
many advantages over traditional molecular energetic compounds. Nitrogencontaining cations and anions contribute
to higher heats of formation and higher
densities, and the low amounts of carbon
and hydrogen also allows for a good
oxygen balance. Because a higher percentage of the decomposition products
will be dinitrogen, these nitrogen-rich
compounds are promising high-energetic
materials.
Explosives
R. P. Singh, R. D. Verma, D. T. Meshri,
J. M. Shreeve*
3584 – 3601
Energetic Nitrogen-Rich Salts and Ionic
Liquids
Communications
The spin reveals all: Electron paramagnetic resonance spectroscopy reveals the
formation of a nickel–alkyl bond in the
active site of methyl-coenzyme M reductase (MCR), the key enzyme of methanogenesis, when active MCRred1 reacts with
the irreversible inhibitor 3-bromopropane
sulfonate to form the MCRBPS species.
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
D. Hinderberger, R. P. Piskorski,
M. Goenrich, R. K. Thauer, A. Schweiger,
J. Harmer,* B. Jaun*
3602 – 3607
A Nickel–Alkyl Bond in an Inactivated
State of the Enzyme Catalyzing Methane
Formation
Carbohydrate Microarrays
Hip hip array: Lectins are involved in a
wide range of biological processes and are
used frequently as tools for basic and
applied research. Through the use of a
carbohydrate microarray, high-throughput
analysis of lectin specificity was carried
out on 24 different lectins. Many of the
carbohydrate ligands identified for the
lectins were unexpected based on previous information.
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
Bioinorganic Chemistry
J. C. Manimala, T. A. Roach, Z. Li,
J. C. Gildersleeve*
3607 – 3610
High-Throughput Carbohydrate
Microarray Analysis of 24 Lectins
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,
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national chemical society prices are available
on request. Postage and handling charges
included. All prices are subject to local VAT/
sales tax.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3559
Angewandte
Chemie
Peptide Nanofilaments
F. Zhang, H.-N. Du, Z.-X. Zhang, L.-N. Ji,
H.-T. Li, L. Tang, H.-B. Wang, C.-H. Fan,
H.-J. Xu, Y. Zhang,* J. Hu, H.-Y. Hu,
J.-H. He*
3611 – 3613
Taking a stand: Self-assembled peptide
aggregates adopt interfacial orientations
in which they either lie horizontally (on
highly ordered pyrolytic graphite, hydrophobic) or are oriented upright (on mica,
hydrophilic) to form nanofilaments with
different heights. This process is controlled by the interfacial hydrophobic or
electrostatic interactions.
Epitaxial Growth of Peptide
Nanofilaments on Inorganic Surfaces:
Effects of Interfacial Hydrophobicity/
Hydrophilicity
Support system: The stability of a LaPO4supported Au nanocatalyst for CO oxidation exceeds that of Au nanocatalysts with
oxide supports. Activation is achieved by
high-temperature calcination under an
oxidative atmosphere (see transmission
electron microscopy image of crystalline
Au nanoparticles on hexagonal LaPO4).
The use of phosphates as supports for
highly active gold catalysts opens up new
routes in the search for ultrastable and
sinter-resistant catalysts.
Nanoparticle Catalyst
Order from chaos: Microfluidic chaotic
mixing shows a significant improvement
in the equilibration time of hybridization
in DNA microarrays over conventional
techniques. These results illustrate a new
concept for performing kinetics studies in
microfluidic devices.
W. F. Yan, S. Brown, Z. W. Pan,
S. M. Mahurin, S. H. Overbury,
S. Dai*
3614 – 3618
Ultrastable Gold Nanocatalyst Supported
by Nanosized Non-Oxide Substrate
DNA Microarrays
J. Liu, B. A. Williams, R. M. Gwirtz,
3618 – 3623
B. J. Wold, S. Quake*
Enhanced Signals and Fast Nucleic Acid
Hybridization By Microfluidic Chaotic
Mixing
Nucleic Acids
C. Dupouy, N. Ich-Tarrat, M.-P. Durrieu,
F. Rodriguez, J.-M. Escudier,*
A. Vigroux*
3623 – 3627
Constrained nucleic acids (a,b-D-CNAs)
have an ethylene bridge that locks the a
and b backbone torsion angles of DNA in
the canonical (gauche(),trans) conformation, as in B-form DNA (see picture),
or in the noncanonical (gauche(þ),trans)
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
conformation. Canonical a,b-D-CNAs
enhance the duplex-forming ability of
oligonucleotides with complementary
DNA, while noncanonical a,b-D-CNAs
stabilize distorted B-DNA structures.
Watson–Crick Base-Pairing Properties of
Nucleic Acid Analogues with
Stereocontrolled a and b Torsion Angles
(a,b-D-CNAs)
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3561
Contents
Competition: A combination of 31P NMR
spectroscopic and calculational studies
have shown that nucleophilic substitution
in the phosphorus–carbon cage compound ClP3(CtBu)2 occurs through competing SN2- and AE’-type reaction pathways (see scheme for model compound
ClP3(CH)2). The AE’ mechanism results in
the formation of a C2v-symmetric intermediate prior to release of the chloride
ion.
Mechanistic Studies
C. Fish, M. Green,* R. J. Kilby,
J. M. Lynam,* J. E. McGrady,*
D. A. Pantazis, C. A. Russell,*
A. C. Whitwood,
C. E. Willans
3628 – 3631
A New Reaction Pathway in
Organophosphorus Chemistry:
Competing SN2 and AE’ Pathways for
Nucleophilic Attack at a Phosphorus–
Carbon Cage Compound
Nanotechnology
Q. Xu, J. Bao, F. Capasso,
G. M. Whitesides*
Down to the wire: A top-down technique
that combines photolithography, thin-film
metal deposition, and thin-film sectioning
has been developed to fabricate patterned
arrays of gold nanowires of uniform,
controllable length, width, and height. A
systematic study of the dependence of the
surface plasmon resonance (see picture)
on the geometry of these wires is presented.
3631 – 3635
Surface Plasmon Resonances of FreeStanding Gold Nanowires Fabricated by
Nanoskiving
Multicomponent Reactions
N. Kumagai, G. Muncipinto,
S. L. Schreiber*
3635 – 3638
Short Synthesis of Skeletally and
Stereochemically Diverse Small Molecules
by Coupling Petasis Condensation
Reactions to Cyclization Reactions
An efficient synthetic pathway to skeletally
and stereochemically diverse molecules is
described. Densely functionalized amino
alcohols were readily synthesized through
a Petasis three-component, boronic acid
Porphyrins
Y. J. Li, X. F. Li, Y. L. Li,* H. B. Liu, S. Wang,
H. Y. Gan, J. Li, N. Wang, X. R. He,
D. B. Zhu*
3639 – 3643
Controlled Self-Assembly Behavior of an
Amphiphilic Bisporphyrin–Bipyridinium–
Palladium Complex: From Multibilayer
Vesicles to Hollow Capsules
3562
www.angewandte.org
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Mannich reaction. Their intramolecular
cyclization provided a collection of diverse
single-isomer compounds with 15 different types of skeletons in three to five
steps.
Gas-filled: Porphyrin-based amphiphiles
can self-assemble into multibilayer vesicles. These vesicles can be converted into
hollow capsules and wormlike structures
(see picture) by controlling the release
rate of methanol encapsulated through
changing the heating temperature and
pattern.
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
Angewandte
Chemie
Molecular Tubes
Food for tubes: Cyclophane-type macrocycles are used as building blocks for the
formation of tubular structures. The
inclusion properties of these molecules
are studied, and the “cyclophane in
cyclophane” 1 was characterized by X-ray
crystallography.
T. Iwanaga, R. Nakamoto, M. Yasutake,
H. Takemura, K. Sako,
T. Shinmyozu*
3643 – 3647
Cyclophanes within Cyclophanes: The
Synthesis of a Pyromellitic Diimide-Based
Macrocycle as a Structural Unit in a
Molecular Tube and Its Inclusion
Phenomena
Synthetic Methods
N. Marion, S. DMez-Gonz(lez,
P. de Frmont, A. R. Noble,
S. P. Nolan*
3647 – 3650
Dignified auration: The rearrangement of
phenylpropargyl acetates to substituted
indenes is catalyzed by [AuI(NHC)] complexes (see scheme, NHC = N-heterocyclic carbene) under extremely mild reaction
conditions. This chemoselective transfor-
mation involves 1,3-migration of the acetate group and is proposed to proceed
through an allene intermediate. TMS =
trimethylsilyl, TBS = tert-butyldimethylsilyl.
AuI-Catalyzed Tandem
[3,3] Rearrangement–Intramolecular
Hydroarylation: Mild and Efficient
Formation of Substituted Indenes
Natural Product Synthesis
Q. Wang, Q. Huang, B. Chen, J. Lu,
H. Wang, X. She,* X. Pan* 3651 – 3653
A general strategy for the synthesis of
hexahydrodibenzopyrans (HHDBPs) is
illustrated in the enantioselective total
synthesis of (þ)-machaeriol D. In the key
step, an SN2’ reaction of an aryl cyanocuprate with a silyl enol ether of an
optically active a,b-epoxycyclohexanone
enabled the construction of the four
stereocenters of the natural product with
high regio- and stereoselectivity (see
scheme; R = methoxymethyl). TMS = trimethylsilyl, TBS = tert-butyldimethylsilyl.
Giant holes: Macroporous solids with
high electrical conductivity and adjustable
pore sizes can be synthesized by the
covalent cross-linking of LiMo3Se3 nanowires with citrate-stabilized Ag nanoparticles (see picture, cit = citrate). The ease
of synthesis and the possibilities for
functionalization with redox-active groups
make these xerogels potentially useful in
applications such as batteries, capacitors,
and electrochemical catalysts.
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
Total Synthesis of (þ)-Machaeriol D with
a Key Regio- and Stereoselective SN2’
Reaction
Porous Solids
N. N. Akl, O. Trofymluk, X. Qi, J. Y. Kim,
F. E. Osterloh,*
A. Navrotsky*
3653 – 3656
A Nanowire–Nanoparticle Cross-Linking
Approach to Highly Porous Electrically
Conducting Solids
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3563
Contents
Analytical Methods
H. Chen, Z. Ouyang,
R. G. Cooks*
The heat is on: Thermal ionization of a
variety of organic salts including ionic
liquids and transition-metal salts occurs
at atmospheric pressure. This thermal
method allows for the study of ion–
molecule reactions; for example, the fast
selective desorption and derivatization of
d-lysine occurs when thermally generated
pyrylium ions react with solid lysine under
ambient conditions (see picture).
3656 – 3660
Thermal Production and Reactions of
Organic Ions at Atmospheric Pressure
CN-Coupled Azolyl Nucleosides
P. Lagisetty, L. M. Russon,
M. K. Lakshman*
3660 – 3663
A General Synthesis of C6-Azolyl Purine
Nucleosides
Hydrogen-Storage Materials
J. M. Bellosta von Colbe, W. Schmidt,
M. Felderhoff, B. Bogdanović,
F. SchSth*
3663 – 3665
Hydrogen-Isotope Scrambling on Doped
Sodium Alanate
Selective DNA Cleavage
B. Breiner, J. C. Schlatterer,
S. V. Kovalenko, N. L. Greenbaum,
I. V. Alabugin*
3666 – 3670
Protected 32P-Labels in
Deoxyribonucleotides: Investigation of
Sequence Selectivity of DNA
Photocleavage by Enediyne–, Fulvene–,
and Acetylene–Lysine Conjugates
3564
www.angewandte.org
Catalysis by a Pd–Xantphos complex
allows the synthesis of unusual symmetrical and unsymmetrical nucleoside
dimers (see structure; R’ = OR, H). Various azolyl units can be introduced at the
C6 position of purine nucleosides,
including systems such as melatonin and
an amino acid. Bromo- and chloropurine
ribo- and 2’-deoxyribonucleosides are
effective substrates for this CN(sp2)
bond-forming reaction.
Titanium facilitates hydrogen dissociation
at the surface of sodium alanate, an
extensively studied hydrogen-storage
material, and diffusion of hydrogen into
the bulk, according to hydrogen-isotope
scrambling experiments on Ti-doped
NaAlH4 (see picture). Kinetics studies
indicate that the rate-limiting step of the
charging/discharging process appears to
be mass transfer into the solid.
Finding a compromise: The sequence
selectivity of DNA photocleavage by enediyne–, acetylene–, and fulvene–lysine
conjugates was investigated by using
labeled DNA oligomers. Since the external
32
P label was removed by these photocleavers, the label was protected by
translocation inside the oligomer (see
figure). The selectivity of cleavage is
controlled by a compromise between AT
selectivity for binding and G selectivity for
electron transfer.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
Angewandte
Chemie
Porphyrinoids
Short and to the point: A three-centered
hydrogen bond is present in 6,16-dimesityl-11-phenylsubpyriporphyrin, a non-aromatic free-base triphyrin(1.1.1)-related
molecule. X-ray crystal structural analysis
shows this compound contains the
shortest known N···N distance (2.370 X)
for two N atoms involved in hydrogen
bonding. The molecule also acts as a
ligand, as shown by the formation of a
boron complex.
R. Myśliborski, L. Latos-Grażyński,*
L. Szterenberg, T. Lis
3670 – 3674
Subpyriporphyrin—A [14]Triphyrin(1.1.1)
Homologue with an Embedded Pyridine
Moiety
Green Solvents
Wrapping up water: Two non-fluorinated
CO2-philic surfactants are used to generate water in carbon dioxide microemulsion dispersions. Detailed analyses of
high-pressure small-angle neutron scattering data provide evidence for formation
of spherical D2O nanodroplets (red), stabilized by surfactant interfacial monolayers (lines), and dispersed in
CO2 (yellow in the schematic scattering
length density (sld) profile).
J. Eastoe,* S. Gold, S. Rogers, P. Wyatt,
D. C. Steytler, A. Gurgel, R. K. Heenan,
X. Fan, E. J. Beckman,
R. M. Enick
3675 – 3677
Designed CO2-Philes Stabilize Water-inCarbon Dioxide Microemulsions
Asymmetric Synthesis
A. Tessier, J. Pytkowicz,
T. Brigaud*
A bit on the side: Extremely high diastereoselectivities (> 99 % de) were attained
in the a-alkylation and -allylation of
amides by using a trifluoromethylated
(sphere) oxazolidine as a chiral auxiliary.
Reductive cleavage of the amide bond led
to the recovery of this fluorinated chiral
auxiliary in high yield.
3677 – 3681
Chiral 4-Phenyl-2-trifluoromethyloxazolidine: A High-Performance Chiral
Auxiliary for the Alkylation of Amides
Brønsted Acid Catalysis
M. Rueping,* A. P. Antonchick,
T. Theissmann
3683 – 3686
A categorical success: A Brønsted acid
catalyzed cascade transfer hydrogenation
provides direct access to 2-aryl- and 2alkyl-substituted tetrahydroquinolines
with excellent enantioselectivities under
mild conditions and using very low
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
amounts of catalyst (see scheme). The
best results were achieved with the binol
phosphate catalyst, where Ar = 9-phenanthryl, used successfully in the Strecker
reaction.
A Highly Enantioselective Brønsted Acid
Catalyzed Cascade Reaction:
Organocatalytic Transfer Hydrogenation
of Quinolines and their Application in the
Synthesis of Alkaloids
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3565
Contents
Asymmetric Synthesis
D. Soorukram, P. Knochel*
3686 – 3689
Copper-Catalyzed Preparation of Ketones
Bearing a Stereogenic Center in a Position
Chiral Solvents
R. Gausepohl, P. Buskens, J. Kleinen,
A. Bruckmann, C. W. Lehmann,
J. Klankermayer, W. Leitner* 3689 – 3692
Highly Enantioselective Aza-Baylis–
Hillman Reaction in a Chiral Reaction
Medium
Heterogeneous Catalysis
T. Schalow, B. Brandt, D. E. Starr,
M. Laurin, S. K. Shaikhutdinov,
S. Schauermann, J. Libuda,*
H.-J. Freund
3693 – 3697
Size-Dependent Oxidation Mechanism of
Supported Pd Nanoparticles
Ionic Liquids
T. KZddermann, C. Wertz, A. Heintz,
3697 – 3702
R. Ludwig*
The Association of Water in Ionic Liquids:
A Reliable Measure of Polarity
3566
www.angewandte.org
A highly enantioselective synthesis of aalkylated and -arylated ketones can be
achieved by using a reaction sequence
consisting of a stereoselective anti-SN2’
allylic substitution in the presence of
CuCN·2 LiCl following by the oxidation of
an intermediate cycloalkenyl lithium species using (Me3SiO)2 or (MeO)3B/
NaBO3·4 H2O.
Let’s twist again! The first highly enantioselective asymmetric reaction in which
a chiral reaction medium is the sole
source of chirality is presented. The azaBaylis–Hillman reaction in an ionic liquid
with a chiral anion, whose design is based
on mechanistic insights, gave products
with up to 84 % ee.
The oxidation and reduction of Fe3O4supported Pd nanoparticles is strongly
size-dependent and implies that the oxidation mechanism is controlled by the
metal oxide interface. Molecular beam
experiments and scanning tunneling
microscopy indicate that this size dependence gives rise to a pronounced maximum of the oxygen-storage capacity as a
function of metal loading.
Water molecules can be used as a sensitive probe for measuring the polarity of
ionic liquids (ILs). A combination of FTIR
spectroscopy and DFT calculations was
used to determine the molecular state of
water in ILs. The picture shows a possible
configuration of H2O in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (red O, white H, blue N, black C,
yellow S, shaded yellow F).
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
Angewandte
Chemie
A heart of gold: The reaction of silylated
arsenic derivatives with gold(i) phosphine
complexes produces gold–arsenic clusters, such as [Au19(AsnPr)8(dppe)6]3+
(dppe = Ph2P(CH2)2PPh2). This complex
cation (see picture; Au gold, As blue,
P violet) can be described as two crossing
Au9As4 chains (red and green), and
contains a gold octahedron centered by a
gold atom.
The magnificent VII? High-level quantum
chemical calculations show iridium in
oxidation state + VII to be a viable
synthetic target, whereas higher oxidation
states of this element appear unlikely.
With the theoretically predicted IrVII and
HgIV included, a linear descent of maximum oxidation states from Os to Hg is
found in the 5d series (see Figure:
* highest experimentally known values,
~ probably incorrect experimental
assignments, and & most likely predicted
values).
Cluster Compounds
P. Sevillano, O. Fuhr, M. Kattannek,
P. Nava, O. Hampe, S. Lebedkin,
R. Ahlrichs, D. Fenske,*
M. M. Kappes
3702 – 3708
The Phosphine-Stabilized Gold–Arsenic
Clusters [Au19(AsnPr)8(dppe)6]Cl3,
[Au10(AsnPr)4(dppe)4]Cl2,
[Au17(AsnPr)6(As2nPr2)(dppm)6]Cl3, and
[Au10(AsPh)4(dppe)4]Cl2 : Synthesis,
Characterization, and DFT Calculations
High Oxidation States
S. Riedel, M. Kaupp*
3708 – 3711
Revising the Highest Oxidation States of
the 5d Elements: The Case of
Iridium(+VII)
Service
Keywords
3712
Authors
3713
Vacancies
Preview
3574, A31
3715
For more information on
ChemMedChem see
www.chemmedchem.org
Angew. Chem. Int. Ed. 2006, 45, 3558 – 3567
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3567
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