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Graphical Abstract Angew. Chem. Int. Ed. 182006

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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:
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. Bang, B. Pentelute, S. H. Kent*
Kinetically Controlled Ligation for the Convergent Chemical
Synthesis of Proteins
D. Rohde, C.-J. Yan, H.-J. Yan, L.-J. Wan*
From Lamellar to Hexagonal Self-Assembly of Bis(dioxaborin)
H. Chen, Z. Ouyang, R. G. Cooks*
Thermal Production and Reactions of Organic Ions at
Atmospheric Pressure
T. Adler, N. Borho, M. Reiher, M. Suhm*
Chirality-Induced Hydrogen-Bond Topology Switch: Tetrameric
Methyl Lactate Clusters in the Gas Phase
Y. Sawada, K. Matsumoto, S. Kondo, H. Watanabe, T. Ozawa,
K. Suzuki, B. Saito, T. Katsuki*
Titanium/Salan-Catalyzed Asymmetric Epoxidation with
Aqueous Hydrogen Peroxide as the Oxidant
Organic Chemistry:
Danishefsky Honored
Prize to Carell
Polymer Chemistry:
Rieger and Luinstra Awarded
reviewed by W. Marx
Citation Analysis in Research Evaluation
Henk F. Moed
Contracted Porphyrins
T. Torres*
2834 – 2837
From Subphthalocyanines to
Homogeneous Catalysis
O. Reiser*
2838 – 2840
Palladium-Catalyzed Coupling Reactions
for the Stereoselective Synthesis of Triand Tetrasubstituted Alkenes
Contracting porphyrins: An important
step on the way to the as-yet unrealized
contracted porphyrin, the so-called subporphyrin, is a tribenzosubporphyrin (see
structure). The new system, which is
closely related to boronsubphthalocyanines, comprises a 14-p-electron aromatic
core and adopts a nonplanar bowl-shaped
Making advances: Efficient strategies
relying on palladium-catalyzed cross-coupling reactions are now available for the
assembly of tri- and tetrasubstituted
alkenes with excellent stereocontrol (see
scheme; Y = Hal, X = ZnHal or MgHal;
other variants: Y = BR2, X = I).
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
Gas-Phase Reactions
It’s amongst the stars: Over the past two
decades, it has become possible to measure rate constants for elementary gasphase reactions at temperatures as low as
10 K, largely by using the CRESU (CinHtique de RHaction en Ecoulement Supersonique Uniforme) technique (experimental setup shown). The factors that
determine the reaction rates and the
implications in the chemistry of interstellar clouds are reviewed.
2842 – 2861
I. W. M. Smith*
Reactions at Very Low Temperatures:
Gas Kinetics at a New Frontier
It isn’t natural: TRI peptides can selectively control the coordination number of
a metal center by changing only one of the
amino acids in the primary sequence.
Replacement of the cysteine residue with
penicillamine leads to a three-coordinate
complex CdIIS3, whereas substitution of
alanine for leucine gives four-coordinate
CdS3O (see scheme).
K.-H. Lee, C. Cabello, L. Hemmingsen,
E. N. G. Marsh,
V. L. Pecoraro*
2864 – 2868
Using Nonnatural Amino Acids to Control
Metal-Coordination Number in ThreeStranded Coiled Coils
Ionic Resins
C. Thiot, M. Schmutz, A. Wagner,*
C. Mioskowski*
2868 – 2871
A highly polar micro-environment, which
is suitable for efficient metal scavenging
and heterogeneous catalyst preparation,
is provided by polyionic gel beads 1 (see
scheme). These heterogeneous media
enable easy product isolation and catalyst
recycling. As an example, a Pd-soaked
ionic gel 2 is shown to transform into a
highly efficient and recyclable catalyst 3 in
the Suzuki cross-coupling reaction.
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Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
Polyionic Gels: Efficient Heterogeneous
Media for Metal Scavenging and Catalysis
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2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Lewiński,* W. Bury, I. Justyniak,*
J. Lipkowski
2872 – 2875
Efficient Route to Tetramethylalumoxane
and Carboxylate Alumoxanes through the
Alkylation of Phthalic Acid
Spaced out: The macrocyclic carboxylatesubstituted alumoxane 1 and coordination polymer 2 were obtained by stepwise
treatment of phthalic acid with AlMe3 and
1,2-bis(4-pyridyl)ethane. In this non-
hydrolytic route to alumoxane derivatives,
the selective formation of 1 or 2 is
determined by the stoichiometric amount
of AlMe3 employed.
Gone fishing: Unidirectionally oriented
CaCO3 crystalline films have been prepared on chitin matrices in the presence
of calcification-associated peptide (CAP1), which was isolated from the exoskeleton of the red swamp crayfish. The interactions of CAP-1 with the matrix and the
acidic nature of the peptide lead to a
filmlike assembly of CaCO3 nanocrystals
through transformation of amorphous
calcium carbonate (see picture).
Sensing DNA with RNA: Simple and
sensitive DNA sensing was achieved by
using an RNA probe which is composed
of a molecular-beacon-like cis-repressing
sequence and a gene for the reporter
protein. The RNase H activity coupled
molecular-beacon–mRNA system enabled
visible sensing of the target nucleotide
sequence in a cell-free translation solution
(see picture).
Natural cellulose sheets can be used as
substrates for protein immobilization.
Individual cellulose nanofibers are first
coated with ultrathin titania layers to
enable the chemisorption of biotin, and
then streptavidin is anchored. The sheets
have a high binding capacity for biomolecules (see the fluorescence micrographs)
without deterioration of their mechanical
and water-absorbing properties.
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
A. Sugawara, T. Nishimura, Y. Yamamoto,
H. Inoue, H. Nagasawa,
T. Kato*
2876 – 2879
Self-Organization of Oriented Calcium
Carbonate/Polymer Composites: Effects
of a Matrix Peptide Isolated from the
Exoskeleton of a Crayfish
DNA Sensing
A. Narita, K. Ogawa, S. Sando,*
Y. Aoyama*
2879 – 2883
Visible Sensing of Nucleic Acid Sequences
with a Genetically Encodable Unmodified
RNA Probe
Protein Immobilization
J. Huang, I. Ichinose,*
T. Kunitake
2883 – 2886
Biomolecular Modification of Hierarchical
Cellulose Fibers through Titania
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Cluster Catalysis
M. B. Thathagar, J. E. ten Elshof,
G. Rothenberg*
2886 – 2890
Pd Nanoclusters in C C Coupling
Reactions: Proof of Leaching
Anion Binding
M. Mascal*
2890 – 2893
Precedent and Theory Unite in the
Hypothesis of a Highly Selective Fluoride
Formamide Hydrolysis
J. Blumberger,* B. Ensing,
M. L. Klein
2893 – 2897
Formamide Hydrolysis in Alkaline
Aqueous Solution: Insight from
Ab Initio Metadynamics Calculations
A simple experiment based on exclusion
of Pd nanoclusters was used to identify
the true catalytic species in cluster-catalyzed Heck cross-couplings. A special
reactor was used in which two compartments are separated by a nanoporous
membrane that allows the passage of Pd
atoms and ions but not of Pd nanoclusters (see picture). The results show that
the real catalysts in the Heck coupling of
n-butyl acrylate with iodobenzene are
species leached from the Pd nanoclusters.
What is the active nucleophile in the
alkaline hydrolysis of formamide: the
hydroxide ion or a water molecule in its
first solvation shell? To allow the two
mechanisms in question to be distinguished, a 2D free-energy surface was
computed (see picture) using Car–Parrinello metadynamics simulation. The
results show that direct nucleophilic
attack by a hydroxide ion is the preferred
V. Stamenkovic, B. S. Mun,
K. J. J. Mayrhofer, P. N. Ross,
N. M. Markovic, J. Rossmeisl, J. Greeley,
J. K. Nørskov*
2897 – 2901
Changing the Activity of Electrocatalysts
for Oxygen Reduction by Tuning the
Surface Electronic Structure
Room for a small one: A series of
[1,3,5]cyclophane-based receptors
incorporating triazine, cyanuric acid, or
boroxine rings are predicted to strongly
complex fluoride ions by a combination of
anion–p interactions and ion-pair reinforced hydrogen bonding, while sizeexcluding the larger chloride anion. The
top view of a calculated structure of the
triazine cage with an included fluoride ion
is shown.
Oxygen Reduction Reaction
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Going platinum: The theoretical description of electrocatalytic phenomena is
extremely challenging. A simple, density
functional theory based model has been
developed that is able to give a semiquantitative description of the reaction
kinetics for the electrocatalytic oxygen
reduction on several platinum binary
alloys, Pt3M (see graph).
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
Synthetic Methods
Facing facts: Control of the configuration
of the propargylic center in 1 is essential
for the facial selectivity observed in the Pt-,
Au-, or Cu-catalyzed enyne cycloisomerization. This route has been used for the
stereoselective synthesis of the naturally
occurring sesquiterpene ( )-cubebol (2).
2901 – 2904
C. Fehr,* J. Galindo
Synthesis of ( )-Cubebol by FaceSelective Platinum-, Gold-, or CopperCatalyzed Cycloisomerization: Evidence
for Chirality Transfer
Palladium Catalysis
M. M. Konnick, B. A. Gandhi, I. A. Guzei,
S. S. Stahl*
2904 – 2907
A critical step: The reaction of molecular
oxygen with a reduced palladium species
represents the key step in Pd-catalyzed
aerobic oxidation reactions. New PdII–
hydride complexes 1 have been prepared
which react with molecular oxygen to
produce PdII–hydroperoxide adducts 2.
Carboxylic acid catalysis of this reaction
has important implications for Pd-catalyzed aerobic oxidation reactions.
Reaction of Molecular Oxygen with a PdII–
Hydride To Produce a PdII–
Hydroperoxide: Acid Catalysis and
Implications for Pd-Catalyzed Aerobic
Oxidation Reactions
Delivery vehicles: Novel guanidine-containing “transporters” constructed on a
dimeric inositol scaffold show significant
translocation across the cell membrane
and the blood–brain barrier, as well as
unique in vitro and in vivo distributions.
Doxorubicin was efficiently delivered to
mouse-brain tissue by conjugating the
compound with such a transporter (see
the fluorescence microscopy image).
Cell-Penetrating Molecules
K. K. Maiti, O.-Y. Jeon, W. S. Lee, D.-C. Kim,
K.-T. Kim, T. Takeuchi, S. Futaki,
S.-K. Chung*
2907 – 2912
Design, Synthesis, and MembraneTranslocation Studies of Inositol-Based
The final synthetic challenges associated
with sarain A have been overcome, thus
leading to its first total synthesis. Critical
to success was a late-stage intramolecular
Stille coupling to construct the unsaturated macrocyclic ring and introduce the
skipped triene functionality of the natural
N. K. Garg, S. Hiebert,
L. E. Overman*
2912 – 2915
Total Synthesis of ( )-Sarain A
Organic Synthesis
N. Yin, G. Wang, M. Qian,
E. Negishi*
Piecing them together: The side chains of
mycolactones A and B are synthesized
with a high degree of stereoselectivity. The
components of the side chains are prepared separately, then combined through
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
Pd-catalyzed cross-coupling (see scheme;
Z1 = tert-butyldimethylsilyl, Z2 = methoxymethyl, TBAF = tetra-n-butylammonium
2916 – 2920
Stereoselective Synthesis of the Side
Chains of Mycolactones A and B Featuring
Stepwise Double Substitutions of 1,1Dibromo-1-alkenes
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
H. Zhang, H. P. Xia,* G. M. He, T. B. Wen,
L. Gong, G. C. Jia*
2920 – 2923
Synthesis and Characterization of Stable
A rare breed: Although many stable
metallabenzene derivatives with a metal
atom from the third transition series are
known, those with a metal atom from the
first and the second transition series are
rare. Air-stable ruthenabenzenes (e.g. 1
and 2) have now been isolated and
Helicene Synthesis
Metathesis with a twist! A ring-closingmetathesis strategy has been developed
for the preparation of various substituted
[5]helicene motifs and [6]- and [7]helicenes. The two optimized protocols
include one method that utilizes the
Grubbs second-generation catalyst under
microwave-irradiation conditions and
another that employs a modified Grubbs–
Hoveyda catalyst at 40 8C in a sealed
reaction vessel. (Mes = mesityl)
S. K. Collins,* A. Grandbois, M. P. Vachon,
2923 – 2926
Preparation of Helicenes through Olefin
R. Waterman, T. D. Tilley*
Bringing together: Zirconium and hafnium d0 metallocene complexes catalyze
the dehydrocoupling of the stibines
MesSbH2 (Mes = mesityl) and dmpSbH2
(dmp = 2,6-dimesitylphenyl) to Sb4Mes4
and (dmp)Sb=Sb(dmp), respectively, with
liberation of H2. Kinetic analysis shows
that thermal decomposition of hafnium
stibide complexes proceeds through ahydrogen migration and stibinidene elimination.
2926 – 2929
Catalytic Antimony–Antimony Bond
Formation through Stibinidene
Elimination from Zirconocene and
Hafnocene Complexes
Organic Oxidants
Not just a pretty oxidant! IBX (1-Hydroxy1,2-benziodoxol-3(1H)-on-1-oxide), an
important oxidant in organic synthesis, is
shown to be relatively acidic on the
organic scale. The pKa value and proton
affinity of IBX were determined both
in silico and in vitro. This acidity could
explain the non-oxidation processes
mediated by IBX.
M. J. Gallen, R. Goumont, T. Clark,
F. Terrier, C. M. Williams*
2929 – 2934
o-Iodoxybenzoic Acid (IBX): pKa and
Proton-Affinity Analysis
S. Bhattacharya,* A. Srivastava,
A. Pal
2934 – 2937
Modulation of Viscoelastic Properties of
Physical Gels by Nanoparticle Doping:
Influence of the Nanoparticle Capping
Cap in hand: The viscoelastic properties
of low-molecular-mass organogelator–
gold nanoparticle (LMOG–Au NP) composites can be modulated by the capping
agent on the nanoparticle. The interactions between the LMOG and Au NP
depend on the ability of ligands to interdigitate within the gel aggregates (see
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
K. Komeyama,* T. Morimoto,
K. Takaki*
2938 – 2941
A new catalytic activity of iron salts for
intramolecular hydroamination is
revealed. A number of aminoolefins
underwent the reaction under mild conditions to form the corresponding pyr-
rolidine derivatives in good yield. The
reaction displayed good functional-group
compatibility and resistance to air and
moisture. (Ts = e-toluenesulfonyl)
A Simple and Efficient Iron-Catalyzed
Intramolecular Hydroamination of
Unactivated Olefins
The first reversible and regiospecific H/D
exchange promoted by CuI proceeds in
weakly coordinating deuterated “acidic”
solvents, such as [D6]acetone or
[D4]methanol (see scheme). The kinetics
of the reaction have been studied in both
directions (H/D and D/H exchange) by 1H
and 2H NMR spectroscopy, and a molecular mechanism is proposed that is in
accordance with all experimental and
theoretical data.
Isotope Exchange
A rare twist: A new class of mixed gpeptides, derived from dipeptide repeats
with alternating C-linked carbo-g4-amino
acids and g-aminobutyric acid have shown
the presence of left-handed 9-helices in
solution with CDCl3 (see superimposition
of 15 minimum-energy structures of a
Remember this: The conjugated copolymer PFOxPy, which contains both electron-donor and -acceptor groups, exhibits
dynamic random access memory behavior
in the sandwich structure ITO/PFOxPy/Al
(see picture). The device is characterized
by low read, write, and erase voltages, a
high ON/OFF current ratio (up to 106),
stable ON and OFF states under a
constant stress of 1 V, and up to 108
read cycles at a read voltage of 1 V.
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
X. Ribas,* R. Xifra, T. Parella, A. Poater,
M. SolS,* A. Llobet*
2941 – 2944
Regiospecific C H Bond Activation:
Reversible H/D Exchange Promoted by
CuI Complexes with Triazamacrocyclic
Peptide Structures
G. V. M. Sharma,* P. Jayaprakash,
K. Narsimulu, A. Ravi Sankar,
K. Ravinder Reddy, P. Radha Krishna,
A. C. Kunwar*
2944 – 2947
A Left-Handed 9-Helix in g-Peptides:
Synthesis and Conformational Studies of
Oligomers with Dipeptide Repeats of
C-Linked Carbo-g4-amino Acids and
g-Aminobutyric Acid
Polymer-Based Dynamic Memory
Q.-D. Ling, Y. Song, S.-L. Lim, E. Y.-H. Teo,
Y.-P. Tan, C. Zhu, D. S. H. Chan,
D.-L. Kwong, E.-T. Kang,*
K.-G. Neoh
2947 – 2951
A Dynamic Random Access Memory
Based on a Conjugated Copolymer
Containing Electron-Donor and -Acceptor
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
b-Hydroxy Esters
P. G. Cozzi*
2951 – 2954
A Catalytic, Me2Zn-Mediated,
Enantioselective Reformatsky Reaction
with Ketones
Kill two birds with one … Salen! A catalytic
and practical Me2Zn-mediated enantioselective Reformatsky reaction promoted by
[ClMn(salen)] with a ketone as the electrophile is presented (see scheme). The
broad scope and simple nature of this
G. Wulff,* B.-O. Chong,
U. Kolb
procedure, which allows the use of commercially available starting materials and
leads to useful building blocks containing
quaternary stereocenters, make it extremely attractive. (salen = N,N’-ethylenebis(salicylideneamine).)
Copy cats! Soluble single-molecule nanogels (see STEM micrograph; scalebar = 20 nm) with a densely packed
structure are prepared by a new method,
and for the first time efficient molecular
imprinting is possible. These nanogels
with defined molecular weights of, for
example, 40 000 Da, low polydispersities,
and on average one active site per particle
proved to be catalytically active enzyme
2955 – 2958
Soluble Single-Molecule Nanogels of
Controlled Structure as a Matrix for
Efficient Artificial Enzymes
A. Krasovskiy, V. Krasovskaya,
P. Knochel*
2958 – 2961
Mixed Mg/Li Amides of the Type
R2NMgCl·LiCl as Highly Efficient Bases for
the Regioselective Generation of
Functionalized Aryl and Heteroaryl
Magnesium Compounds
Quantum Dynamics
I. Barth, J. Manz*
2962 – 2965
Periodic Electron Circulation Induced by
Circularly Polarized Laser Pulses:
Quantum Model Simulations for Mg
Two are better than one: Mixed lithiummagnesium complexes of the type
R2NMgCl·LiCl are kinetically highly active
bases that convert a range of polyfunc-
tional aromatic and heteroaromatic substrates into the corresponding magnesiated derivatives with high regioselectivity.
What goes round comes round! Quantum
dynamical simulations predict that ultrashort circularly polarized laser pulses can
selectively induce the circulation of electrons in a ring-shaped molecule—with
near equal laser and electron periods
below one femtosecond (see figure).
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
”Systematic errors”, namely, oxygen
vacancy sites in ZnO, are the active
centers for the hydrogenation of CO to
give methanol. Nanocrystalline ZnO with
a high density of oxygen vacancies was
prepared from special organometallic
precursors, and its catalytic properties for
methanol synthesis were studied.
Heterogeneous Catalysis
Hard-core visualization: Bilayer hockeypuck micelles are formed in nonpolar
solvents from “sticky” rod–coil block
copolymers based on oligo(p-benzamide)s. Images obtained by scanning
force microscopy (SFM) give insight into
the structure of the anisotropic micellar
core. The picture shows a model (left) and
an SFM image (right) of the micelle
consisting of an aramide core and a
poly(ethylene glycol) corona.
Block Copolymers
S. Polarz,* J. Strunk, V. Ischenko,
M. W. E. van den Berg, O. Hinrichsen,*
M. Muhler, M. Driess
2965 – 2969
On the Role of Oxygen Defects in the
Catalytic Performance of Zinc Oxide
T. W. Schleuss, R. Abbel, M. Gross,
D. Schollmeyer, H. Frey, M. Maskos,
R. Berger,
A. F. M. Kilbinger*
2969 – 2975
Hockey-Puck Micelles from Oligo(p-benzamide)-b-PEG Rod–Coil Block
Intramolecular Sensitization
D. WVll, J. Smirnova, W. Pfleiderer,
U. E. Steiner*
2975 – 2978
Brought to light: The light sensitivity of
photolabile protecting groups of the
nitrophenylpropoxycarbonyl (NPPOC)
type was enhanced by up to a factor of 25.
This was achieved by covalently linking the
protecting group to a sensitizer with a
much better absorptivity and the ability to
transfer its electronic excitation to the
protecting group (see scheme).
Highly Efficient Photolabile Protecting
Groups with Intramolecular Energy
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
A Highly Enantio- and Diastereoselective
Cu-Catalyzed 1,3-Dipolar Cycloaddition of
Azomethine Ylides with Nitroalkenes
In this Communication, the structures of (S,Rphos,R)-3 g and (S,Sphos,R)-3 h given in
Equation (1) should be as follows:
X.-X. Yan, Q. Peng, Y. Zhang,
K. Zhang, W. Hong, X.-L. Hou,*
Y.-D. Wu
Angew. Chem. Int. Ed. 2006, 45
DOI 10.1002/anie.200503672
Additionally, in Figure 1 the upper structure is that of endo-4 k while the lower structure
is that of exo-4 k. The authors apologize for the oversight.
For more information on
ChemMedChem see
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 2818 – 2828
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