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Graphical Abstract Angew. Chem. Int. Ed. 192006

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The following Communications have been judged by at least two referees to be ?very
important papers? and will be published online at soon:
C. Burke, Y. Shi*
Regio- and Enantioselective Epoxidation of Dienes by a Chiral
Dioxirane: Synthesis of Optically Active Vinyl cis-Epoxides
Cheuk-W. So, H. Roesky,* J. Magull, R. Oswald
Synthesis and Characterization of [{PhC(NtBu)2}SiCl]: A Stable
Monomeric Chlorosilylene
S. Harder,* J. Brettar
Rational Design of a Well-Defined Soluble Calcium Hydride
H. Yu, S. Huang, H. Chokhawala, M. Sun, H. Zheng, Xi 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
V. Lavallo, Y. Canac, B. Donnadieu, W. Schoeller, G. Bertrand*
CO Fixation to Stable Acyclic and Cyclic Alkyl Amino Carbenes:
Stable Amino Ketenes with a Small HOMO?LUMO Gap
D. Rohde, C.-J. Yan, Hui-J. Yan, Li-J. Wan*
From Lamellar to Hexagonal Self-Assembly of Bis(dioxaborin)
Meeting Reviews
Natural Products Research: Renaissance with Strengthened Integration of Biology
and Chemistry
W. Maison
TTF Chemistry
Jun-ichi Yamada, Toyonari Sugimoto
reviewed by C. Rovira
Principles of Inorganic Materials Design
John N. Lalena, David A. Cleary
reviewed by L. Qi
Bond Theory
U. Radius,* F. Breher*
3006 ? 3010
To Boldly Pass the Metal?Metal
Quadruple Bond
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
The metal?metal quintuple bond: Minimizing the number of sterically demanding ligands increases the number of
valence orbitals available to form metal?
metal bonds. Following this concept,
Power et al. have recently synthesized and
structurally characterized a dinuclear
chromium?chromium-bonded complex
with one ligand per metal atom (see
picture) featuring a metal?metal quintuple bond. Driving this concept to an
extreme, even larger bond orders than five
should be feasible.
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
How high is high and how low is low?
With respect to transition-metal complexes of different coordination numbers
and stereochemistry, high-, low-, and
intermediate-spin states may mean
different things. The hybridization of the
d orbitals, similar to the deformation of a
balloon subjected to pressure (see picture), provides a rationale for the splitting
of the d manifold and, hence, for the
allowed spin states in a given complex.
Spin Configurations
S. Alvarez,* J. Cirera
3012 ? 3020
How High the Spin? Allowed and
Forbidden Spin States in Transition-Metal
Electrostatic effects in proteins are complicated: The charged groups form a
network of interactions in which the
members can influence each other at long
distances. Sets of derivatives in which
variable numbers of charges are removed
or added by chemical reactions (protein
charge ladders) together with capillary
electrophoresis comprise a tool with
which to examine the character of this
I. Gitlin, J. D. Carbeck,
G. M. Whitesides*
3022 ? 3060
Why Are Proteins Charged? Networks of
Charge?Charge Interactions in Proteins
Measured by Charge Ladders and
Capillary Electrophoresis
Merge, mix, split, and transport are the
main manipulation steps used for on-chip
droplet-based DNA purification (see
figure). The system is able to extract
genomic material from dilute raw cell
samples by using the actuation of magnetic microparticles within the droplets
through a matrix of coils.
For the USA and Canada:
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Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
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U. Lehmann,* C. Vandevyver,
V. K. Parashar, M. A. M. Gijs 3062 ? 3067
Droplet-Based DNA Purification in a
Magnetic Lab-on-a-Chip
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.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Out of the brew! Four new antibiotics were
isolated from a fermentation broth of
Steptomyces lydicus (strain HKI0343). The
13-membered-ring peptides (see formula,
XY: CH2NH, CH=NH; R1, R2: H, OH)
are cyclized through a lactone function at
serine and also contain the nonproteinogenic amino acid piperazic acid (or a
derivative thereof). The peptides show
promising activity against various mycobacteria without being cytotoxic.
X. Huang, E. Roemer, I. Sattler,*
U. Moellmann, A. Christner,
S. Grabley
3067 ? 3072
Lydiamycins A?D: Cyclodepsipetides with
Antimycobacterial Properties
Asymmetric Catalysis
U. Kazmaier,* D. Stolz
3072 ? 3075
Regio- and Stereoselective RhodiumCatalyzed Allylic Alkylations of Chelated
Rehabilitated: The rhodium-catalyzed
allylic alkylation is indeed a viable alternative to the better-known palladiumcatalyzed version. Rhodium complexes
show a different regioselectivity and have
a low tendency for isomerization. The
allylations proceed with excellent chirality
transfer for both branched and linear
products (see scheme; Tfa = trifluoroacetyl).
CH Insertion
U. Biermann, R. Koch,
J. O. Metzger*
Tying the knot: In analogy to singlet
carbenes, vinyl cations insert into CH
bonds in a concerted intramolecular
reaction, as shown by experimental
investigations and quantum mechanical
calculations. This reaction is useful for the
synthesis of cyclopentane derivatives.
3076 ? 3079
Intramolecular Concerted Insertion of
Vinyl Cations into CH Bonds:
Hydroalkylating Cyclization of Alkynes
with Alkyl Chloroformates To Give
Organolithium Compounds
J. Paradies, G. Erker,*
R. FrJhlich
Li and light: Alkenyl-substituted lithium
cyclopentadienides, which are in equilibrium with the substituted lithocene anion
structure 1, undergo a photochemical
[2� cycloaddition to yield selectively the
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
carbon?carbon coupling product 2. This is
a rare case of organic functional-group
chemistry for a reactive organolithium
3079 ? 3082
Functional-Group Chemistry of
Organolithium Compounds:
Photochemical [2� Cycloaddition of
Alkenyl-Substituted Lithium
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Inorganic Polymers
The simplest side group: The first example
of a completely H-substituted polyphosphazene I is obtained by the polycondensation of (Me2N)2PNH2 in solution at low
temperature. NMR investigations and
light-scattering experiments substantiate
the constitution of the polymer. The
conformation and a reaction pathway to I
are proposed on the basis of ab initio
M. Raab, G. Schick, R. Fondermann,
M. Dolg, W. Henze, U. Weynand,
R. M. Gschwind, K. Fischer, M. Schmidt,
E. Niecke*
3083 ? 3086
A PH-Functionalized Polyphosphazene:
A Macromolecule with a Highly Flexible
Chemical Memory
A. Kaminaga, V. K. Vanag,
I. R. Epstein*
A face to remember: A photoimprinted
image in a reactive microemulsion
persisted for more than an hour. Such
localized patterns in reaction?diffusion
systems could find application in
memory-storage devices. The picture
shows the image of a face immediately
following illumination (a) and after 1 h
(b). The area at the right shows the
evolution of a spontaneous Turing
3087 ? 3089
A Reaction?Diffusion Memory Device
F.-S. Xiao,* L. Wang, C. Yin, K. Lin, Y. Di,
J. Li, R. Xu, D. S. Su, R. SchlJgl, T. Yokoi,
3090 ? 3093
T. Tatsumi
Catalytic Properties of Hierarchical
Mesoporous Zeolites Templated with a
Mixture of Small Organic Ammonium
Salts and Mesoscale Cationic Polymers
Holey zeolites! Hierarchical mesoporous
zeolites (see SEM image) were prepared
by a one-step hydrothermal reaction using
both a small organic ammonium salt and
a mesoscale cationic polymer as templates. The zeolites thus obtained reveal
excellent catalytic properties relative to
conventional zeolites, indicating the
importance of their mesoporous structure
for industrial catalysis.
Chiral Ionic Liquids
S. Luo,* X. Mi, L. Zhang, S. Liu, H. Xu,
J.-P. Cheng*
3093 ? 3097
Functionalized Chiral Ionic Liquids as
Highly Efficient Asymmetric
Organocatalysts for Michael Addition to
Catalytic combination: By combining the
advantages of organocatalysts and ionic
liquids, a functionalized chiral ionic liquid
such as 1 can act as a highly efficient and
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
reusable organocatalyst for the asymmetric Michael addition reaction of ketones
and aldehydes with nitroalkenes.
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
Bimetallic Complexes
M. Fang, N. D. Jones, R. Lukowski,
J. Tjathas, M. J. Ferguson,
R. G. Cavell*
3097 ? 3101
Metals helping metals: The bimetallic
spirocyclic bridged-carbene complex 1
reacts almost quantitatively with CO by
formal ?insertion? into the RhC(Li) bond
to form the dimeric complex 2, the first
example of a m2,h2-(O,C) lithium?rhodium
ketene complex (see scheme). Complex 2
reacts with water to transform the ketene
ligand into a methine group by CO
A Bimetallic, Coordinated-Ketene
Complex Formed from a Bimetallic
Lithium?Carbon Spirocycle by LithiumMediated Insertion of CO into a
Rhodium?Carbon Bond
Microscale Synthesis
G. A. Gro�,* G. Mayer, J. Albert, D. Riester,
J. Osterodt, H. Wurziger,
A. Schober*
3102 ? 3106
Miniature labs: A microstructured silicon
wafer was used as a microreactor array for
single-bead synthesis on a nanovolume
scale. Products were prepared by combinatorial synthesis and spatially encoded
by their position in the array. Threecomponent Biginelli condensations were
carried out at 100 8C for 14 h and therefore
required the development of a specially
sealed reactor device.
Spatially Encoded Single-Bead Biginelli
Synthesis in a Microstructured Silicon
Heterogeneous Catalysis
Exceptional activity in carbon oxidation is
displayed by a zeolite-supported ruthenium catalyst (see diagram; Y = carbon
weight loss) that unlike platinum catalysts
does not require the presence of NOx in
the gas stream. This catalyst opens up a
new route for catalytic soot oxidation in
diesel engine exhaust filters.
K. Villani, C. E. A. Kirschhock, D. Liang,
G. Van Tendeloo,
J. A. Martens*
3106 ? 3109
Catalytic Carbon Oxidation Over
Ruthenium-Based Catalysts
Asymmetric Synthesis
B. M. Trost,* R. N. Bream,
J. Xu
Excellent yields and enantioselectivities
were achieved for the palladium-catalyzed
asymmetric allylic alkylation of vinylogous
thioesters. The close-to-neutral reaction
conditions ensure that this reaction can
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
tolerate a wide range of functionalities.
Furthermore, this approach provides a
convenient protocol for the synthesis of
synthetically important a,a- and g,g-disubstituted cycloalkenones.
3109 ? 3112
Asymmetric Allylic Alkylation of Cyclic
Vinylogous Esters and Thioesters by PdCatalyzed Decarboxylation of Enol
Carbonate and b-Ketoester Substrates
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Noncovalent Interactions
On the rung way: Concerted self-organization of an a,w-bis(triphenylenetetrahydroxy)disiloxane through p?p-stacking
and H-bonding interactions generates a
supramolecular channel in which silanol
groups are entrapped between two
hydrophobic columns. Ordered polycondensation leads to a high-molecularweight, soluble, ladder cis-isotactic polysilsesquioxane (see picture).
X. Zhang, P. Xie,* Z. Shen, J. Jiang, C. Zhu,
H. Li, T. Zhang, C. C. Han, L. Wan, S. Yan,*
R. Zhang*
3112 ? 3116
Confined Synthesis of a cis-Isotactic
Ladder Polysilsesquioxane by Using a pStacking and H-Bonding Superstructure
Synthetic Methods
N. T. McDougal,
S. E. Schaus*
3117 ? 3119
Highly Diastereoselective Synthesis of
Bicyclo[3.2.1]octenones through
Phosphine-Mediated Condensations of
Fuel Cells
S. Yamazaki,* T. Ioroi, Y. Yamada,
K. Yasuda, T. Kobayashi
3120 ? 3122
A Direct CO Polymer Electrolyte
Membrane Fuel Cell
Making rings: A highly diastereoselective
synthesis of bicyclo[3.2.1]octenones from
1,4-dien-3-ones occurs through a domino
A good source of energy: The reformation
of hydrocarbons generates CO as well as
H2. Despite its high reducing activity, CO
is not suitable as a fuel in polymer
electrolyte membrane fuel cells (PEMFCs)
because it is a strong poison for the Pt
catalyst used as the anode. A new fuel cell
has now been developed with a rhodium
octaethylporphyrin ([Rh(oep)]) anode
catalyst that uses neat CO as a fuel, and
delivers high performance (see graph).
Molecular Recognition
S. Le Gac, J. Marrot, O. Reinaud,*
I. Jabin*
3123 ? 3126
Allosterically Coupled Double Induced Fit
for 1��Self-Assembly of a
Calix[6]trisamine, a Calix[6]trisacid, and
Their Guests
phosphine-mediated formal [4�
cycloaddition followed by an intramolecular Wittig olefination.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Special guests: A cooperative double
induced-fit process leads to the 1��self-assembly of quaternary complexes
comprising two complementary calix[6]arene-based hosts and their specific
guests (see picture). The guests direct
self-assembly by shaping their hosts. Such
allosteric control involves multiple recognition levels reminiscent of those in
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
Open channels: Chemical modulators are
developed to convert a naturally occurring
channel protein into a pH-actuated nanovalve. The pH interval, sensitivity, and
activation of the valve by channel opening
are tunable through the design of the
modulators. The valve is useful for
releasing or mixing the contents of liposomes at a desired location, time, and
dosage, for example, in micro/nanosensory and delivery devices (see picture).
A rare methyleneimine complex of ruthenium(ii), cis-[Ru(NH=CH2)(NCCH3)(bpy)2]2+ (see structure), was obtained
from the reaction of cis-[Ru(N3)2(bpy)2]稨2O (bpy = 2,2?-bipyridine) with
CH3I in CH3CN at room temperature in
the dark. The reaction of such azido
complexes will be useful in the synthesis
of nitrogen-containing ligands.
A. KoQer, M. Walko, E. Bulten, E. Halza,
B. L. Feringa,* W. Meijberg* 3126 ? 3130
Rationally Designed Chemical Modulators
Convert a Bacterial Channel Protein into a
pH-Sensory Valve
H. Nagao,* T. Kikuchi, M. Inukai, A. Ueda,
T. Oi, N. Suzuki,
M. Yamasaki
3131 ? 3133
Formation of a Methyleneimine Moiety by
Reaction of a RuII-Coordinated Azide Ion
with Methyl Iodide
Methanol-to-Olefin Process
D. M. Marcus, K. A. McLachlan,
M. A. Wildman, J. O. Ehresmann,
P. W. Kletnieks, J. F. Haw*
3133 ? 3136
Pool view preferred: In agreement with
recent theoretical work, a new line of
experimental evidence was obtained in
support of the controversial claim that
direct mechanisms do not couple methanol to ethylene in the catalyzed methanol-
to-olefin process. The results preclude
carbene routes and oxonium ylide
mechanisms, among others (see picture),
in favor of the hydrocarbon pool
Experimental Evidence from
H/D Exchange Studies for the Failure of
Direct CC Coupling Mechanisms in
the Methanol-to-Olefin Process Catalyzed
by HSAPO-34
Biological Chemistry
M. M. Ali, M. Oishi, F. Nagatsugi, K. Mori,
Y. Nagasaki, K. Kataoka,
S. Sasaki*
3136 ? 3140
One mismatch is discriminated in a target
mRNA sequence by an inducible alkylation system based on sulfide precursors
to the nucleoside 2-amino-6-vinylpurine
(see scheme). The reactive oligonucleotides were delivered into the cell as
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
poly(ethylene glycol) (PEG) conjugates in
polyion-complex (PIC) micelles and
showed antisense activity of high selectivity and greater potency than that of the
natural antisense oligonucleotide.
Intracellular Inducible Alkylation System
That Exhibits Antisense Effects with
Greater Potency and Selectivity than the
Natural Oligonucleotide
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Iodine helps: Aldehydes acylate arenes
upon treatment at low temperature
with IPy2BF4 and HBF4. This reaction is
exploited in a novel intramolecular
approach to the preparation of benzocyclic ketones (see scheme). A plausible
mechanistic rational is also given.
J. Barluenga,* M. Trincado, E. Rubio,
J. M. GonzSlez
3140 ? 3143
Direct Intramolecular Arylation of
Aldehydes Promoted by Reaction with
IPy2BF4/HBF4 : Synthesis of Benzocyclic
Molecular Logic Gates
Logical progression: Optoelectronic XOR
and INH logic gates based on two light
inputs and an electrical output were
demonstrated using a nanocrystalline
TiO2 dye-sensitized solar cell. The GrTtzeltype cell was generated using a ruthenium
complex as dye, with reverse injection of
electrons at the semiconductor/dye
interface (see picture).
L. F. O. Furtado, A. D. P. Alexiou,
L. GonQalves, H. E. Toma,*
K. Araki*
3143 ? 3146
TiO2-Based Light-Driven XOR/INH Logic
Nucleophilic Reactions
H. Morimoto, S. H. Wiedemann,
A. Yamaguchi, S. Harada, Z. Chen,
S. Matsunaga,*
M. Shibasaki*
3146 ? 3150
Trichloromethyl Ketones as Synthetically
Versatile Donors: Application in Direct
Catalytic Mannich-Type Reactions and the
Stereoselective Synthesis of Azetidines
Chemical transformers! Catalytic nucleophilic activation of trichloromethyl
ketones allows applications in intermolecular carbon?carbon bond-forming
reactions. Mannich adducts such as
azetidines can be obtained from the
primary products in high yield and syn
selectivity. PG = protecting group.
Expanded Porphyrins
X. Zhu, S. Fu, W.-K. Wong,* J.-P. Guo,
W.-Y. Wong
3150 ? 3154
A Near-Infrared-Fluorescent
Chemodosimeter for Mercuric Ion Based
on an Expanded Porphyrin
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Running rings around mercuric ions: A
[26]hexaphyrin(, comprising an
a,a?-bipyrrole unit and four pyrrolic and
five pentafluorophenyl rings, was prepared and characterized by X-ray crystallography (see picture; N blue, F green,
C black). The expanded porphyrin displays
near-infrared luminescence above 900 nm
and may serve as a highly sensitive and
selective chemodosimeter for Hg2+ ions.
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
Synthetic Methods
M. P. Cassidy, J. Raushel,
V. V. Fokin*
A direct, simple, and efficient route from
terminal alkynes to amides is achieved by
their copper(i)-catalyzed reaction with
sulfonyl azides (see scheme). The reac-
tion proceeds with the in situ generation
of copper(i) acetylides and represents a
one-step formal oxidative hydration of a
triple bond.
3154 ? 3157
Practical Synthesis of Amides from In Situ
Generated Copper(i) Acetylides and
Sulfonyl Azides
Synthetic Methods
M. Whiting, V. V. Fokin*
Selective conversion, take three: Densely
functionalized azetidine derivatives are
formed in an experimentally simple threecomponent catalytic procedure through
the highly selective reaction of readily
available terminal alkynes under mild
conditions (see scheme). The azetidinimine products are remarkably stable to a
wide range of reaction conditions and
readily undergo further functionalization.
3157 ? 3161
Copper-Catalyzed Reaction Cascade:
Direct Conversion of Alkynes into
T. J. Harris, G. von Maltzahn, A. M. Derfus,
E. Ruoslahti, S. N. Bhatia* 3161 ? 3165
Proteolytic Actuation of Nanoparticle
Sleeping giant: Inorganic nanoparticles
are synthesized to exist in a latent form
until proteolytic activation drives them to
self-assemble into nanostructures with
amplified magnetic properties. Binding of
complimentary Fe3O4 nanoparticles is
blocked by the attachment of inhibitory
polymers that may be removed by proteases involved in cancer-cell invasion and
DNA Carriers
G. Han, C.-C. You, B. J. Kim, R. S. Turingan,
N. S. Forbes, C. T. Martin,
V. M. Rotello*
3165 ? 3169
Light-Regulated Release of DNA and Its
Delivery to Nuclei by Means of Photolabile
Gold Nanoparticles
Light and life: A photolabile gold nanoparticle has been constructed to serve as a
DNA carrier. UV irradiation causes the
reversal of the nanoparticle surface
charge, resulting in effective DNA release
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
and reactivation of suppressed DNA
transcription in vitro. This effect was also
observed in living cells, together with
efficient internalization of DNA into the
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Molecular Electronics
A. Wakamiya, T. Taniguchi,
S. Yamaguchi*
3170 ? 3173
Intramolecular B?N Coordination as a
Scaffold for Electron-Transporting
Materials: Synthesis and Properties of
Boryl-Substituted Thienylthiazoles
Fluorescence Spectroscopy
A. Cannizzo, F. van Mourik, W. Gawelda,
G. Zgrablic, C. Bressler,
M. Chergui*
3174 ? 3176
Broadband Femtosecond Fluorescence
Spectroscopy of [Ru(bpy)3]2+
Stacking the deck: Incorporation of boryl
groups into the thienylthiazole system
fixes the p-conjugated framework in a
planar fashion by intramolecular B?N
coordination. The dimer of boryl-substituted thienylthiazole forms a unique
packing structure with offset face-to-face
p stacking (see picture; B orange, N blue,
S yellow, C turquoise) and films of it show
high electron mobility.
It?s sizzling! Femtosecond fluorescenceupconversion studies of aqueous
[Ru(bpy)3]2+ show a short-lived vibrationally hot emission of the singlet metal-toligand charge-transfer state, with an
ultrafast intersystem crossing ( 10 fs)
to the triplet state at constant energy
(the colors indicate the luminescence
Host?Guest Chemistry
C.-F. Lin, Y.-H. Liu, C.-C. Lai, S.-M. Peng,
S.-H. Chiu*
3176 ? 3181
Precise Facial Control in Threading Guests
into a Molecular Cage and the Formation
of a Turtlelike Supramolecular Complex
Caught in a cage: Two different thread
components and a molecular cage
generate different [2]pseudorotaxane-like
complexes, which represent a new type of
molecular machinery. An unprecedented
type of molecular motion is generated by
the addition of K+ ions and [2,2,2]cryptand
units to this mixture and their removal
from it, in which the rodlike components
penetrate the molecular cage alternately
through its different faces.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 2988 ? 2998
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