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Graphical Abstract Angew. Chem. Int. Ed. 272004

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The following Communications are available online (in Wiley InterScience). You can find them, as
well as forthcoming Reviews, Highlights, and Essays, at, under Early View.
K. C. Nicolaou,* T. V. Koftis, S. Vyskocil, G. Petrovic, T. Ling,
Y. M. A. Yamada, W. Tang, M. O. Frederick:
Structural Revision and Total Synthesis of Azaspiracid-1, Part 2:
Definition of the ABCD Domain and Total Synthesis
DOI: 10.1002/anie.200460696
Published online: June 29, 2004
M. Johnsson,* S. Lidin, K. W. Trnroos, H.-B. B!rgi, P. Millet:
Host–Guest Compounds in the Family of Tellurium–Nickel
DOI: 10.1002/anie.200460001
Published online: June 23, 2004
K. C. Nicolaou,* S. Vyskocil, T. V. Koftis, Y. M. A. Yamada, T. Ling,
D. Y.-K. Chen, W. Tang, G. Petrovic, M. O. Frederick, Y. Li,
M. Satake*:
Structural Revision and Total Synthesis of Azaspiracid-1, Part 1:
Intelligence Gathering and Tentative Proposal
DOI: 10.1002/anie.200460695
Published online: June 25, 2004
Articles judged by the referees or the editor as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editorial office in its final form. As long as there is no page number available these articles should
be cited in the following manner:
Author(s), Angew. Chem. Int. Ed., online publication date, DOI.
Chemical Society of Japan
3508 – 3509
Molecular Biology in Medicinal
Theodor Dingermann, Dieter Steinhilber,
Gerd Folkers
reviewed by R. Breinbauer
Physics and Chemistry of
Hans-J%rgen Butt, Karlheinz Graf,
Michael Kappl
reviewed by M. Steinhart
William Illsey Atkinson
reviewed by R. N. Zare
Endogenous Ozone
H. Sies*
Ozone as an endogenous compound? The
discovery of 5,6-secosterol, a characteristic product of the in vitro ozonolysis of
cholesterol, in atherosclerotic tissue (see
picture) suggests that ozone is formed by
biochemical processes. This and other
typical products of oxidation may serve as
indicators (“biomarkers”) of endogenous
3514 – 3515
Ozone in Arteriosclerotic Plaques:
Searching for the “Smoking Gun”
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 3500 – 3506
Sigmatropic Rearrangement
J. Gonda*
3516 – 3524
The Belluš–Claisen Rearrangement
Now a quarter of a century since its
serendipitous discovery, the Belluš–
Claisen rearrangement of ketenes with
allylic ethers, amines, and thioethers has
been developed into a simple and reliable
[3,3] bond reorganization reaction. This
rearrangement, which proceeds via a
zwitterionic intermediate, is especially
powerful for the ring expansion of cyclic
allylic substrates by four carbon atoms
(see scheme). R1, R2 = alkyl, Cl.
Enzyme Chemistry
A diverse range of biomolecules, including
steroids and glycosaminoglycans, are
sulfonated enzymatically by the
cosubstrate PAPS in the presence of
sulfotransferases (see scheme). As these
enzymes have been implicated in several
crucial pathophysiological events
(regulation of estrogen sulfate synthesis
and leukocyte adhesion, viral entry) they
have emerged as promising therapeutic
E. Chapman, M. D. Best, S. R. Hanson,
C.-H. Wong*
3526 – 3548
Sulfotransferases: Structure, Mechanism,
Biological Activity, Inhibition, and
Synthetic Utility
DNA Structures
A DNA aptamer structure is the basis of a
molecular machine that can be instructed
to grab or release the human bloodclotting factor a-thrombin, depending on
the operator DNA sequence addressing it.
In the picture the aptamer structure,
which assumes a conformation characterized by two stacked guanine quadruplex structures, is linked to thrombin (gray
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Angew. Chem. Int. Ed. 2004, 43, 3500 – 3506
W. U. Dittmer, A. Reuter,
F. C. Simmel*
3550 – 3553
A DNA-Based Machine That Can Cyclically
Bind and Release Thrombin
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Y. Chen, M. Wang, C. Mao*
3554 – 3557
An Autonomous DNA Nanomotor
Powered by a DNA Enzyme
Host–Guest Chemistry
M. A. C. Broeren, J. L. J. van Dongen,
M. Pittelkow, J. B. Christensen,
M. H. P. van Genderen,
E. W. Meijer*
3557 – 3562
The power of life: An autonomous DNA
nanomotor powered by an RNA-cleaving
DNA enzyme (see figure) has been constructed that works in the same way as
cellular protein motors: it continuously
extracts chemical energy from fuel molecules to power mechanical motions. The
fuel for the DNA nanomotor is the RNA
substrate of the DNA enzyme.
Selective guest ejection: Up to eight guest
molecules are assembled at the periphery
of a third-generation dendrimer. Collisioninduced dissociation mass spectrometry
has demonstrated that the guests are
removed very selectively in a one-by-one
manner (see spectrum).
Multivalency in the Gas Phase: The
Study of Dendritic Aggregates by Mass
Reduced Pyrochlores
G. D. Blundred, C. A. Bridges,
M. J. Rosseinsky*
3562 – 3565
New Oxidation States and Defect
Chemistry in the Pyrochlore Structure
NMR Spectroscopy
C. Gardiennet, F. Marica, X. Assfeld,
P. Tekely*
3565 – 3568
Exploiting the Joint Action of Chemical
Shielding and Heteronuclear Dipolar
Interactions To Probe the Geometries of
Strongly Hydrogen-Bonded Silanols
Titanium(iii) pyrochlores with TiIII centers
at up to 90 % of the B sites of the A2B2O6O’
pyrochlore structure (see picture; blue:
BO6, green: A, red: O’), which is wellknown for supporting high oxidation
states at the octahedral B sites, were
obtained by the low-temperature reduction of lanthanide pyrochlores Ln2Ti2O7
with CaH2. This leads to significant rearrangement of the anion sublattice and
introduces antisite disorder between the
two distinct cation arrays.
Magic probes: The geometry of strongly
hydrogen bonded silanols in octosilicate
can be probed by exploiting the 1H NMR
distance correlations together with the
joint effects of 29Si chemical shielding and
dipolar 1H–29Si interactions. Dipolarmodulated, slow magic-angle spinning
Si NMR spectra allow the determination
of Si···H distances, the magnitude of the
Si chemical-shielding tensor, and its
orientation in the molecular frame.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 3500 – 3506
Stable oil-in-water emulsions are obtained
in alkaline solution in the absence of any
conventional surfactant. The oil droplets
are charged by hydroxide ions (see picture). The surface charge density is
obtained by measuring the size of the
emulsion droplets by electroacoustics and
the quantity of NaOH required to keep the
pH constant during homogenization.
Surfactant-Free Emulsions
J. K. Beattie,*
A. M. Djerdjev
3568 – 3571
The Pristine Oil/Water Interface:
Surfactant-Free Hydroxide-Charged
Bioinorganic Chemistry
Classical organometallic chemistry was
used to prepare the dinuclear iron complex 1 with two protected cysteinyl-S
ligands. Oxidative addition of the thiol to
[Fe3(CO)12] gave complex 1, which undergoes an unusual intramolecular nucleophilic cyclization with inversion of the
configuration to form the chiral carbonbridged diiron complex 2.
C. He, M. Wang,* X. Zhang, Z. Wang,
C. Chen, J. Liu, B. Qkermark,
L. Sun*
3571 – 3574
An Unusual Cyclization in a Bis(cysteinylS) Diiron Complex Related to the Active
Site of Fe-Only Hydrogenases
X.-B. Lu,* Y. Wang
Excellent activity and selectivity in the
copolymerization of CO2 with epoxides at
extremely mild temperature and pressure
are observed in the presence of binary
nucleophile–electrophile catalyst systems
based on chiral [(salcy)CoiiiX] complexes
and quaternary ammonium salts (see
scheme). Completely alternating
copolymers are obtained with > 95 %
head-to-tail linkages.
An infinite network is formed by the
hydrogen bonding of a cluster of 12
hydrogen-bonded water molecules (see
picture) to the secondary amino nitrogen
atoms of a laterally nonsymmetric azacryptand. This mode of association had
not previously been predicted or found
Angew. Chem. Int. Ed. 2004, 43, 3500 – 3506
3574 – 3577
Highly Active, Binary Catalyst Systems for
the Alternating Copolymerization of CO2
and Epoxides under Mild Conditions
S. K. Ghosh,
P. K. Bharadwaj*
3577 – 3580
A Dodecameric Water Cluster Built
around a Cyclic Quasiplanar Hexameric
Core in an Organic Supramolecular
Complex of a Cryptand
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Coupling Reactions
A. SuSrez, G. C. Fu*
3580 – 3582
A Straightforward and Mild Synthesis of
Functionalized 3-Alkynoates
Diazoacetates in coupling reactions: CuI
serves as an effective catalyst for coupling
terminal alkynes with diazo compounds
to generate 3-alkynoates (see scheme).
This method is efficient (1:1 ratio of
Strained Molecules
Spontaneous trimerization of fluoro(triisopropylsilyl)acetylene, prepared from
1,1-difluoroethylene in one step, gives the
corresponding fluorinated Dewar benzene
derivative, whose structure was determined by X-ray diffraction (see picture).
T. Hanamoto,* Y. Koga, T. Kawanami,
H. Furuno, J. Inanaga
3582 – 3584
Crystal Structure of a Dewar Benzene
Derivative Formed from Fluoro(triisopropylsilyl)acetylene
Homogeneous Catalysis
W. Baratta,* P. Da Ros, A. Del Zotto,
A. Sechi, E. Zangrando,
P. Rigo
3584 – 3588
Cyclometalated Ruthenium(ii) Complexes
as Highly Active Transfer Hydrogenation
Quantitative conversion: Reaction of the
14-electron complex [RuCl2{(2,6Me2C6H3)PPh2}2] with CH2O in the
presence of NEt3 gave a five-coordinate
cyclometalated complex with a d-agostic
interaction of one ortho-methyl group
(see X-ray crystal structure). Displacement
of one phosphane group with 2-(aminomethyl)pyridine gave a highly active
catalyst for the quantitative conversion of
ketones into alcohols.
Gas-Phase Reactions
T. Giroldo, L. A. Xavier,
J. M. Riveros*
reactants), mild (room temperature), and
simple (no additional ligand), and a range
of functional groups are tolerated (e.g.,
CC double bonds, heteroatoms, and
hydroxy groups).
Quick reactions: The gas-phase nucleophilic displacement reaction of fluoride
ions with nitrobenzene proceeds with a
rate constant close to the collision limit.
The calculated energy profile indicates
that the reaction proceeds by an out-ofplane attack, with the Meisenheimer
complex being the local transition state
for the reaction (see picture).
3588 – 3590
An Unusually Fast Nucleophilic Aromatic
Displacement Reaction: The Gas-Phase
Reaction of Fluoride Ions with
DNA Bisintercalators
E. J. Fechter, B. Olenyuk,
P. B. Dervan*
3591 – 3594
Design of a Sequence-Specific DNA
Programmable bisintercalators: Symmetric synthetic DNA bisintercalators (see
picture) based on the H-pin polyamide
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
motif afford high affinity and
programmable sequence specificity.
Angew. Chem. Int. Ed. 2004, 43, 3500 – 3506
H. Tohma,* A. Maruyama, A. Maeda,
T. Maegawa, T. Dohi, M. Shiro, T. Morita,
Y. Kita*
3595 – 3598
A wide range of oxidative reactions are
mediated by novel, nonpolymeric, and
recyclable hypervalent IIII reagents (e.g. 2).
In all cases, tetraiodide 1 was recovered
nearly quantitatively in pure form after a
simple workup. Reoxidation of 1 to 2 with
m-chloroperbenzoic acid also proceeded
quantitatively, without loss of oxidative
Preparation and Reactivity of
1,3,5,7-Tetrakis[4-(diacetoxyiodo)phenyl]adamantane, a Recyclable Hypervalent
Iodine(iii) Reagent
Radical Reactions
Desulfuration as a source of alkyl radicals:
The addition of alkylsulfanyl radicals to
isocyanides gives the corresponding alkyl
radicals. This methodology can replace
the usual tin-mediated radical procedures
and allows for the generation of tertiary,
secondary, and even nonstabilized primary radicals that can be used efficiently
in reductive defunctionalizations and
intermolecular additions to electron-rich
olefins (see scheme).
L. Benati, R. Leardini, M. Minozzi,*
D. Nanni,* R. Scialpi, P. Spagnolo,
S. Strazzari, G. Zanardi
3598 – 3601
A Novel Tin-Free Procedure for Alkyl
Radical Reactions
Natural Product Synthesis
X. Wang, E. J. Bowman, B. J. Bowman,
J. A. Porco, Jr.*
3601 – 3605
Total Synthesis of the Salicylate Enamide
Macrolide Oximidine III: Application of
Relay Ring-Closing Metathesis
The vacuolar-type (Hþ)-adenosine triphosphatase inhibitor oximidine III and
its enamide and epoxide stereoisomers
have been synthesized enantioselectively.
A relay ring-closing metathesis (RCM)
strategy was employed to facilitate the
macrocyclization of a well-defined
substrate possessing two differentially
functionalized RCM alkene partners
(see scheme).
Heterocycle Synthesis
J. E. Ney, J. P. Wolfe*
The formation of a CC and a CN bond
in a reaction between g-(N-arylamino)
alkenes and aryl bromides results in the
stereoselective synthesis of substituted
pyrrolidine derivatives (see scheme).
Preliminary studies suggest these
reactions proceed by intramolecular
alkene insertion into the PdN bond of
intermediate [Pd(Ar)(amido)] complexes.
dba = dibenzylideneacetone, dppb = 1,3bis(diphenylphosphanyl)butane.
3605 – 3608
Palladium-Catalyzed Synthesis of N-Aryl
Pyrrolidines from g-(N-Arylamino)
Alkenes: Evidence for Chemoselective
Alkene Insertion into PdN Bonds
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
Angew. Chem. Int. Ed. 2004, 43, 3500 – 3506
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 3500 – 3506
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abstract, int, 272004, angel, chem, graphical
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