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Graphical Abstract Angew. Chem. Int. Ed. 472006

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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:
E. Terreno, C. Cabella, C. Carrera, D. D. Castelli, R. Mazzon,
S. Rollet, J. Stancanello, M. Visigalli, S. Aime*
From "Spherical" to "Osmotically Shrinked" Paramagnetic
Liposomes: An Improved Generation of LIPOCEST MRI Agents
with Highly Shifted Water Protons
W. H. Bernskoetter, E. Lobovsky, P. J. Chirik*
Nitrogen?Carbon Bond Formation from N2 and CO2 Promoted by
a Hafnocene Dinitrogen Complex Leads to the Liberation of a
Substituted Hydrazine
J. A. Teprovich, Jr., E. Prasad,* R. A. Flowers II*
Solvation-Controlled Luminescence of SmII Complexes
Y. Xiong, J. M. McLellan, Y. Yin, Y. Xia*
Synthesis of Palladium Icosahedrons with a Twinned Structure
by Blocking Oxidative Etching with Citric Acid or Citrate Ion
X. Liu, L. Shi, W. Niu, H. Li, G. Xu*
Environmentally Friendly and Highly Sensitive Ruthenium(II)
Tris(2,2'-bipyridyl) Electrochemiluminescent System Using
2-(Dibutylamino)ethanol as Co-reactant
L.-M. Yan, A. Velkova, M. Tatarek-Nossol, E. Andreetto,
A. Kapurniotu*
Designed IAPP Mimic Blocks Ab Cytotoxic Self-Assembly:
Cross-Suppression of Amyloid Toxicity of Ab and IAPP Suggests
a Molecular Link between Alzheimer's Disease and Type 2
Polymer Chemistry:
J. M. J. Frchet awarded
H.-J. Freund honored
Carbohydrate Chemistry:
Prize to P. Sina y?
Soft Matter
Gerhard Gompper, Michael Schick
reviewed by M. Ballauff
Introduction to Microfluidics
Patrick Tabeling
reviewed by K. Jacobs
C. Palomo,* A. Mielgo
7876 ? 7880
Diarylprolinol Ethers: Expanding the
Potential of Enamine/Iminium-Ion
Organocatalysts based on diarylprolinol
ethers mediate a broad range of reactions
involving enamine or iminium-ion activation or a combination of both. The reactions are characterized by efficient steric
control of the approach of the respective
electrophile/nucleophile to the enamine/
iminium-ion counterpart, thus complementing reactions involving hydrogenbond donors as directing key elements.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
Coordinating anions: The coordination
chemistry of anions with amide-based
ligands is described on the basis of
crystallographic data for simple anions of
five different shapes: spherical, linear, Vshaped, trigonal planar, and tetrahedral.
Binding data are also provided where
available. The examples are arranged
according to coordination number and
geometry, and correlations are made to
transition-metal coordination complexes.
Anion Coordination
S. O. Kang, R. A. Begum,
K. Bowman-James*
7882 ? 7894
Amide-Based Ligands for Anion
Gold fever: Gold, long considered an
immutable nonreactive metal, can in fact
display remarkable catalytic activity as
both a homogeneous and a heterogeneous catalyst when present as soluble
complexes of gold(I), gold(III), or highly
dispersed nanocrystals (see examples of
the range of compounds that can be
Gold Catalysis
A. S. K. Hashmi,*
G. J. Hutchings*
7896 ? 7936
Gold Catalysis
Lanthanide Silicates
Chiral microporous lanthanide silicates
Na3[(Y,Ln)Si3O9]и3 H2O (1; Ln = Eu, Tb, Er,
Ce) have enantiomeric domains that can
be discriminated by means of Eu3+ photoluminescence spectroscopy. In the framework of 1 (see picture), (Si3O9)Ц spiral
chains interconnect the {(Y,Ln)O6} octahedra, and channels along [100] contain
Na+ ions and water molecules. Color
code: {(Y,Ln)O6} yellow; {SiO4} green;
O red; Na purple; H white.
For the USA and Canada:
Edition (ISSN 1433-7851) is published weekly
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Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
D. Ananias, F. A. Almeida Paz,
L. D. Carlos, C. F. G. C. Geraldes,
J. Rocha*
7938 ? 7942
Optical Detection of Solid-State Chiral
Structures with Unpolarized Light and in
the Absence of External Fields
Meacham Ave., Elmont, NY 11003. Periodicals
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sales tax.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Natural Products
Going to trial: From about 350 active
epothilone analogues synthesized by a
highly convergent synthesis, one (ZKEPO, see picture) has been chosen for
clinical development on the basis of its
outstanding preclinical data. This compound exhibits higher activity and efficacy
than taxanes (e.g. paclitaxel) and secondgeneration epothilones, a fast and efficient cellular uptake, no recognition by
efflux mechanisms, and an improved
therapeutic window.
U. Klar,* B. Buchmann, W. Schwede,
W. Skuballa, J. Hoffmann,
R. B. Lichtner
7942 ? 7948
Total Synthesis and Antitumor Activity of
ZK-EPO: The First Fully Synthetic
Epothilone in Clinical Development
Macrocycle Synthesis
A wheel surprise: Reaction of resorcinol
and 1,5-pentanedial in ethanol at 80 8C for
48 h in the presence of HCl surprisingly
afforded a soluble cyclic oligomer in high
yield (83 %) under thermodynamic control. Single-crystal X-ray analysis revealed
a waterwheel-like structure with a large
hydrophobic hole through the center (see
picture). A carboxylic ester derivative of
the compound was shown to be highly
selective for Rb+ ions.
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
H. Kudo, R. Hayashi, K. Mitani,
T. Yokozawa, N. C. Kasuga,
T. Nishikubo*
7948 ? 7952
Molecular Waterwheel (Noria) from a
Simple Condensation of Resorcinol and
an Alkanedial
The series of events that occur in the
catalytic cycle of matrix metalloproteinases were modeled on the basis of X-ray
crystal structures of the active, uninhibited enzymes and of the same enzymes
following the hydrolysis of a peptide
substrate. After the peptide bond has
been broken, both peptide fragments
remain bound to the protein initially (see
structure of the active-site cavity of the
enzyme MMP-12 immediately after
substrate hydrolysis).
Enzyme Mechanisms
A quick plunge: By using lateral flow
devices as a platform to separate
aptamer-assembled nanoparticle (NP)
aggregates, highly sensitive and selective
colorimetric sensors were constructed
that mimic litmus paper tests. Detection
of cocaine in serum was also realized.
I. Bertini,* V. Calderone, M. Fragai,
C. Luchinat, M. Maletta,
K. J. Yeo
7952 ? 7955
Snapshots of the Reaction Mechanism of
Matrix Metalloproteinases
J. Liu, D. Mazumdar, Y. Lu* 7955 ? 7959
A Simple and Sensitive ?Dipstick? Test in
Serum Based on Lateral Flow Separation
of Aptamer-Linked Nanostructures
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Protein Analysis
Photoluminescence quenching of dextranconjugated quantum dots (dex-QDs) by
gold nanoparticles conjugated with concanavalin A (conA-AuNPs) can be prevented by adding a glycoprotein, which
inhibits the association of dex-QDs with
conA-AuNPs (see scheme). This phenomenon can be used as an analytical tool
for the detection of protein glycosylation.
PL = photoluminescence.
E. Oh, D. Lee, Y. P. Kim, S. Y. Cha,
D. B. Oh, H. A. Kang, J. Kim,
H. S. Kim*
7959 ? 7963
Nanoparticle-Based Energy Transfer for
Rapid and Simple Detection of Protein
Host?Guest Systems
J. Wang, D. Wang,* N. S. Sobal, M. Giersig,
M. Jiang, H. MQhwald
7963 ? 7966
Stepwise Directing of Nanocrystals to
Self-Assemble at Water/Oil Interfaces
Crystal Design
M. Wenger, J. Bernstein*
7966 ? 7969
Designing a Cocrystal of g-Amino Butyric
Included in the meeting: The specific
inclusion of adamantane by cyclodextrins
is used to direct nanocrystals to selfassemble into macroscopic monolayers at
the water/oil interface. The use of functionalized cyclodextrins allows stepwise
interfacial self-assembly of different
nanocrystals into macroscopic heterogeneous multilayers (see picture).
It takes two: The possibility of developing
a strategy for the controlled preparation of
cocrystals (see picture) with a predesigned structure is demonstrated. It relies
on recognizing and utilizing a specific
hydrogen-bond pattern, defined in graphset notation (R24(8)), as a supramolecular
synthon for the systematic generation of
individual four-molecule clusters.
H. Nuss, M. Jansen*
7969 ? 7972
Cs5([12]crown-4)2(O3)5 : A Supramolecular
Compound Containing the Confined
Ozonide Partial Structure 11{Cs8(O3)10}2
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Rod-shaped: The supramolecular ozonide
Cs5([12]crown-4)2(O3)5 contains a
distorted tetragonal packing of
rods separated by
[Cs([12]crown-4)2]+ units (see picture;
Cs blue, C gray, O red). This packing
arrangement leads to the shortest intermolecular OиииO distance yet observed
between adjacent ozonide ions in the
solid state.
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
A. K. Sahoo, S. Mori, H. Shinokubo,*
A. Osuka*
7972 ? 7975
Going round the outside: The palladiumcatalyzed coupling of meso-bromoporphyrins with a variety of internal alkynes
efficiently provides peripherally cyclopentadiene-fused porphyrins. This modification has a significant impact on the
electronic system of the porphyrin rings
(see scheme), which results in non-porphyrin-like absorption spectra and narrower HOMO?LUMO gaps. Oxidation of
the outer C=C bond is facilitated by the
induced strain.
An attractive model: The iron complex
shown on the left models the 2-His-1carboxylate active sites of Rieske dioxygenases both in terms of structure and
function. 18O-labeling studies of olefin
dihydroxylation support the involvement
of a high-valent iron-oxo species.
Share and share alike: Chlorophylls are
appended to rigid linkers with threefold
symmetry. The efficiency of both energy
and charge transfer between the chlorophylls is controlled by the structure of the
central linker. Direct chlorophyll?ethynyl
linkage facilitates charge sharing between
all three chlorophylls on the EPR/ENDOR
timescale (107 Hz). ENDOR = electron
nuclear double resonance.
Whole scheme of things: The kinetics and
efficiency of photoinduced hole transport
across DNA A tracts with 1?7 base pairs
have been determined from femtosecond
transient absorption spectroscopic data.
These values are strongly distance dependent over the first four base pairs, but
are relatively insensitive to distance at
longer distances. These kinetic results
(&, &) parallel the DNA-strand-cleavage
results of Giese et al. (*, *).
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
Facile Peripheral Functionalization of
Porphyrins by Pd-Catalyzed [3■2]
Annulation with Alkynes
Enzyme Models
P. D. Oldenburg, C.-Y. Ke, A. A. Tipton,
A. A. Shteinman, L. Que, Jr.* 7975 ? 7978
A Structural and Functional Model for
Dioxygenases with a 2-His-1-carboxylate
Electron Transfer
R. F. Kelley, M. J. Tauber,
M. R. Wasielewski*
7979 ? 7982
Linker-Controlled Energy and Charge
Transfer within Chlorophyll Trefoils
Electron Transfer
F. D. Lewis,* H. Zhu, P. Daublain,
B. Cohen,
M. R. Wasielewski*
7982 ? 7985
Hole Mobility in DNA A Tracts
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Enantiomeric Enrichment
Solubility and enantiomeric excess: A
general model based on simple solubility
concepts rationalizes the value of the ee at
the eutectic for a wide range of chiral
substances including amino acids and
common chiral ligands. A novel crystal
structure in which one CHCl3 molecule is
incorporated in a highly insoluble
(a = 0.002) proline racemate explains the
strong asymmetric amplification observed
in the proline/CHCl3 system.
M. Klussmann,* A. J. P. White,
A. Armstrong,
D. G. Blackmond*
7985 ? 7989
Rationalization and Prediction of Solution
Enantiomeric Excess in Ternary Phase
Asymmetric Catalysis
M. Klussmann, S. P. Mathew, H. Iwamura,
D. H. Wells, Jr., A. Armstrong,
D. G. Blackmond*
7989 ? 7992
Kinetic Rationalization of Nonlinear
Effects in Asymmetric Catalysis Based on
Phase Behavior
A model of proline as a ?kinetic conglomerate? can rationalize both the nonlinear effect in proline-catalyzed aldol
reactions observed in early studies and
the linearity observed more recently, in a
manner that remains compatible with the
currently accepted one-proline reaction
mechanism. Care must be taken to distinguish between equilibrium and kinetic
effects in heterogeneous systems?and to
separate these physical influences from
nonlinear effects of a true chemical origin.
Asymmetric Catalysis
R. Matsubara, S. Kobayashi* 7993 ? 7995
Catalytic Asymmetric Amination of
A little catalyst goes a long way: The title
reaction was attained using a chiral CuIIdiamine complex as catalyst. Azodicarboxylates react with various enecarbamates derived from aromatic and aliphatic ketones and aldehydes to provide
Laser Switching of Ring Currents
M. Kanno, H. Kono,
Y. Fujimura*
7995 ? 7998
Control of p-Electron Rotation in Chiral
Aromatic Molecules by Nonhelical Laser
acylimines in good yields with high enantioselectivity. The catalyst loading necessary for high enantioselectivity was generally low, with 0.2 mol % catalyst sufficient in some cases.
Turning on the ring current: p Electrons in
a chiral aromatic molecule, such as
dichloro(3,6)pyrazinophanes (see
scheme), can be rotated along the aromatic ring by linearly polarized laser
pulses. Selective generation of an
(approximate) angular momentum
eigenstate consisting of optically allowed,
quasi-degenerate p-electronic excited
states is responsible for the rotation. The
direction of the photoinduced ring current
is controllable in each enantiomer.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
The combined advantages of layered
double-hydroxide catalysts and rare-earth
compounds are found in the layered rareearth hydroxides [R4(OH)10(H2O)4]nAn
(R = Y, Dy, Ho, Yb; A = organic anion).
These crystalline materials (see structure)
comprise rigid organic anions (balls and
sticks) intercalated between inorganic
layers (polyhedra). They are selective
heterogeneous catalysts for hydrodesulfurization and sulfide oxidation.
Layered Compounds
F. GUndara, J. Perles, N. Snejko,
M. Iglesias, B. GVmez-Lor,
E. Gutirrez-Puebla,*
M. A. Monge*
7998 ? 8001
Layered Rare-Earth Hydroxides: A Class of
Pillared Crystalline Compounds for
Intercalation Chemistry
Core?Shell Nanoparticles
Pouring in: The picture shows an STEM
image of 7-nm Au-InAs metal?semiconductor hybrid nanoparticles where a gold
core (yellow) is surrounded by an amorphous InAs shell (pink). These nanoparticles form by diffusion of Au into InAs
T. Mokari, A. Aharoni, I. Popov,
U. Banin*
8001 ? 8005
Diffusion of Gold into InAs Nanocrystals
Without protection: a-Keto aziridines
have been formed in a novel aminepromoted direct aziridination of chalcones using an aminimide generated
in situ from a tertiary amine and Omesitylenesulfonylhydroxylamine (MSH)
in the presence of base (see scheme). The
aziridination proceeds well using a catalytic amount of the tertiary amine. Furthermore, nonracemic aziridines are
obtained using a chiral amine.
Small Ring Systems
Y.-M. Shen, M.-X. Zhao, J. Xu,
8005 ? 8008
Y. Shi*
An Amine-Promoted Aziridination of
X. Jiang, X. Cheng, S. Ma*
Come on allenes: [2■2] Cycloadditions of
1,5-bisallenyl compounds were realized in
controllable head-to-head and tail-to-tail
manners, resulting in the formation of
[3.2.0] and [5.2.0] bicyclic compounds,
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
respectively (see scheme). The bicyclic
compounds include double bonds suitable for further elaboration and thus these
reactions may be powerful tools in organic
8009 ? 8013
Controllable [2■2] Cycloadditions of
1,5-Bisallenyl-Substituted Compounds
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
W. CantXn, A. Corma,* M. J. DXaz-CabaYas,
J. L. JordU, M. Moliner,
F. Rey
8013 ? 8015
Synthesis and Characterization of the AllSilica Pure Polymorph C and an Enriched
Polymorph B Intergrowth of Zeolite Beta
Previously elusive, the all-silica pure
polymorph C of zeolite beta and a
material enriched with polymorph B (see
picture) are prepared by high-throughput
(HT) synthesis in the presence of a
cationic organic structure-directing agent
(SDA). The presence of K+ ions is essential for the formation of these materials;
furthermore, a high ratio of OH ions to
silicon atoms favors the crystallization of
polymorph C.
Action by the para: Evaluation of the nitrogroup-forming N-oxygenase AurF in vivo,
in vitro, and immobilized as a fusion
protein with simply H2O2 as oxidant
(peroxide shunt) reveals para-regioselective oxygenation of aromatic amines (see
scheme). This effect includes the selective
oxygenation of diamino compounds.
R. Winkler, M. E. A. Richter, U. KnZpfer,
D. Merten, C. Hertweck*
8016 ? 8018
Regio- and Chemoselective Enzymatic
N-Oxygenation In Vivo, In Vitro, and
in Flow
Natural Products Synthesis
C. H. Kim, H. J. An, W. K. Shin, W. Yu,
S. K. Woo, S. K. Jung,
E. Lee*
8019 ? 8021
Total Synthesis of ()-Amphidinolide E
The unique structural features of the
cytotoxic marine macrolide ()-amphidinolide E make it an intriguing synthetic
target. Its total synthesis has now been
completed by employing a radical cyclization of a b-alkoxy acrylate to form the
oxolane ring, a Kocienski?Julia olefination
to create the E C=C bond, and a lactonization reaction to close the macrocyclic
DNA Detection
B.-A. Du, Z.-P. Li,* C.-H. Liu 8022 ? 8025
One-Step Homogeneous Detection of
DNA Hybridization with Gold
Nanoparticle Probes by Using a Linear
Light-Scattering Technique
Matchmaker, matchmaker: A gold-nanoparticle-based light-scattering assay has
been developed for sensitive detection of
DNA hybridization. The assay relies on the
enhancement of light scattering that originates from the aggregation of oligonu-
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
cleotide-functionalized gold nanoparticles
directed by the target DNA. The assay also
exhibits a high degree of discrimination
between perfectly matched target DNA
and targets with single base-pair
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
Synthetic Methods
T. J. Donohoe,* G. H. Churchill,
K. M. P. Wheelhouse (ne Gosby),
P. A. Glossop
8025 ? 8028
A new pathway for oxidative cyclization:
N-protected a-amino alcohols with distal
alkene units cyclize with complete stereoselectivity and stereospecificity to cispyrrolidines, dependent on the substitution pattern of the starting material. In
addition to providing nitrogen- and
oxygen-containing heterocycles in good to
excellent yields, the catalyst loadings can
be reduced to just 0.2 mol % osmium.
TMO = Me3NO, TFA = trifluoroacetic
acid, Ts = toluene-4-sulfonyl.
Stereoselective Synthesis of Pyrrolidines:
Catalytic Oxidative Cyclizations Mediated
by Osmium
Natural Products Synthesis
J. Chen, X. Chen, M. Willot,
J. Zhu*
8028 ? 8032
Asymmetric Total Syntheses of
Ecteinascidin 597 and Ecteinascidin 583
The limited availability of bioactive natural
products for pharmaceutical studies and
drug development is a problem that can
be solved, in principle, by total synthesis.
The potent antitumor marine natural
products ecteinascidin 597 (1) and ecteinascidin 583 (2) have now been synthesized from readily accessible starting
materials in a highly convergent and
stereoselective fashion (see scheme).
Porphyrin Aggregation
C. Escudero, J. Crusats,* I. DXez-Prez,
Z. El-Hachemi, J. M. RibV* 8032 ? 8035
Stir it up! Comparison of the evolution
with time of J-aggregates of the title
porphyrin in stagnant and vortex-stirred
solutions showed that chiral-sign selection is due to the action of hydrodynamic
gradients (shear flows) on particle folding.
Brownian dynamics (stagnant solution)
result in irregularly folded mesophases,
whereas hydrodynamic gradients (vortex
stirring) lead to long-order folding and
formation of helical ribbons (see picture).
Folding and Hydrodynamic Forces in
J-Aggregates of 5-Phenyl-10,15,20-tris(4-sulfophenyl)porphyrin
Cluster Compounds
L. Kienle, H. Mattausch,
A. Simon*
A discovery in the electron microscope:
New rare earth clusters with variable sizes
containing one to ten condensed octahedra of rare earth metals were found. These
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
cluster compounds exhibit a surprising
parallelism with the structural chemistry
of reduced oxomolybdates.
8036 ? 8038
Searched For and Found: Analogies
between Reduced Oxomolybdates and
Cluster Compounds of Rare Earth Metals
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Low-Valent Carbon
A combined experimental/theoretical
study gives strong evidence that carbodiphosphoranes are divalent carbon(0)
compounds. The calculations show that
carbodiphosphoranes have two lone pairs
of electrons (see picture), which give rise
to unusual properties as confirmed by
experiment. The synthesis of a triply
charged molecules in which two protonated carbodiphosphoranes serve as donor
ligands to an Ag+ center supports the
bonding model.
R. Tonner, F. [xler, B. NeumZller,*
W. Petz,* G. Frenking*
8038 ? 8042
Carbodiphosphoranes: The Chemistry of
Divalent Carbon(0)
Nanowires and Nanotubes
L. Zhao, M. Yosef, E. Pippel,
H. Hofmeister, M. Steinhart, U. GQsele,
S. Schlecht*
8042 ? 8045
?Four Birds with One Stone?: Synthesis of
Nanostructures of ZnTe, Te, ZnAl2O4, and
Te/ZnAl2O4 from a Single-Source
Four shape-defined anisotropic nanostructures: Single-crystalline nanowires of
ZnTe and elemental tellurium, core?shell
structures of the type Te/ZnAl2O4 (see
picture), and nanotubes of zinc spinel
ZnAl2O4 could selectively be produced
from [Zn(TePh)2(tmeda)] (tmeda =
as a single-source precursor. Porous alumina templates with a pore diameter of
25 nm were used both as shape-defining
molds and chemical reactants.
Functionalized Polymers
S. Hilf, E. Berger-Nicoletti, R. H. Grubbs,
A. F. M. Kilbinger*
8045 ? 8048
Monofunctional Metathesis Polymers via
Sacrificial Diblock Copolymers
A small price to pay: The second block of a
diblock copolymer is ?sacrificed? in order
to leave behind a monofunctionalized
metathesis polymer with a hydroxy end
group. By incorporation of a dioxepine
Catalytic Diboration
H. Braunschweig,* T. Kupfer, M. Lutz,
K. Radacki, F. Seeler,
R. Sigritz
8048 ? 8051
Metal-Mediated Diboration of Alkynes
with [2]Borametalloarenophanes under
Stoichiometric, Homogeneous, and
Heterogeneous Conditions
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
unit into the copolymer, a breaking point
is created between the block to be endfunctionalized and the block to be
and ansa-[2]boraferroarenophane were
treated with alkynes in the presence of
catalytic amounts of platinum or palladium/charcoal (see example) to afford the
corresponding ansa-bis(boryl)alkenes in
excellent yields and without detectable
side products. The use of Pt and Pd are
the first examples of diboration reactions
of alkynes to be conducted under heterogeneous conditions.
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
Capsular heterodimers are formed exclusively from a tetra(tosylurea)calix[4]arene
(blue) and tetrakis(3,5-dibutenyloxyphenylurea)- or tetrakis(dipentenyloxyphenylurea)calix[4]arenes (red). Metathesis
between the prearranged alkenyl groups
and subsequent hydrogenation leads to
mechanically interlocked capsules which
can neither dissociate nor release the
included guest(s) owing to their fourfold
[2]rotaxane structure.
The core of the matter: Reactions of
Ag(PhCO2) with (Me2N)C6H4(SSiMe3)
and E(SiMe3)2 (E = S, Se) lead to three
clusters with new silver chalcogenide
cores. For example, the core of
[Ag88Se12(SC6H4NMe2)63(PPh3)6] (see picture) consists of bent hexagonal layers of
selenium and sulfur atoms (yellow), with
interstitial silver atoms (blue). The inorganic cores of the clusters are surrounded
by organic shells.
The self-activated silyl-assisted polyoniosubstitution (SASAPOS) protocol allows
the synthesis of the first representatives of
1,2-bisonio-1,2-bis(dialkylamino)ethenes (see picture; DMAP = 4-dimethylaminopyridine). Depending on the onio
substituent L, one of two types of structures with different stereoelectronic
configurations is adopted.
Supporting information is available on the WWW
(see article for access details).
O. Molokanova, M. O. Vysotsky,* Y. Cao,
I. Thondorf, V. BQhmer*
8051 ? 8055
Fourfold [2]Rotaxanes of Calix[4]arenes by
Ring Closure
Cluster Compounds
S. Chitsaz, D. Fenske,
O. Fuhr*
8055 ? 8059
Silver Chalcogenide Clusters with
Dimethylanilinomercapto Ligands:
Syntheses and Crystal Structures of
[Ag76Se13(SC6H4NMe2)50(PPh3)6.5], and
R. Weiss,* S. M. Huber, F. W. Heinemann,
P. Audebert, F. G. PZhlhofer 8059 ? 8062
Structure, Stereoelectronics, and
Synthetic Potential of
A video clip is available as Supporting Information
on the WWW (see article for access details).
Sister Journals
Angew. Chem. Int. Ed. 2006, 45, 7858 ? 7870
8063 ? 8065
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Intramolecular CH Activation by an
Open-Shell Cobalt(III) Imido Complex
D. T. Shay, G. P. A. Yap, L. N. Zakharov,
A. L. Rheingold, K. H. Theopold*
In this Communication, the imido complex [TptBu,MeCo=NAd] (1) was incorrectly
characterized as a paramagnetic compound with a spin ground state of S = 1. Further
investigation has now revealed that this compound, like all other known Co(III) imido
complexes, has a spin ground state of S = 0 and is diamagnetic at low temperatures.
However, at T > 280 K, 1 undergoes a spin crossover to a thermally accessible openshell state. All the experimental observations reported in the original Communication
remain unchanged, but their interpretation is more complicated than originally realized.
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200462529
Configurationally Stable Molecular
Propellers: First Resolution of Residual
T. Benincori, G. Celentano, T. Pilati,
A. Ponti, S. Rizzo, F. Sannicol\*
Angew. Chem. 2006, 45
Since publication of their Communication, it has been brought to the authors? attention
that the resolution of a carbon-centered propeller was previously reported (Reference [1]). The authors apologize for this oversight and would like to amend the title of
their Communication to read as ?Configurationally Stable Molecular Propellers: The
Resolution of Phosphorus-Centered Residual Enantiomers?.
[1] C. Foces-Foces, F. H. Cano, M. Martnez-Ripoll, R. Faure, C. Roussel, R. M. Claramunt,
C. Lpez, D. Sanz, J. Elguero, Tetrahedron: Asymmetry 1990, 1, 65.
DOI 10.1002/anie.200601869
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