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Graphical Abstract Angew. Chem. Int. Ed. 342004

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Contents
The following Communications are available online (in Wiley InterScience). You can find them, as
well as forthcoming Reviews, Highlights, and Essays, at www.angewandte.org, under Early View.
F. E. Hahn,* C. Schulze Isfort, T. Pape:
A Dinuclear, Triple-Stranded Helicate with a Diamide-Bridged
Catechol/Benzenedithiol Ligand
DOI: 10.1002/anie.200460188
Published online: August 9, 2004
M. B. Steffensen, E. E. Simanek*:
Synthesis and Manipulation of Orthogonally Protected
Dendrimers: Building Blocks for Library Synthesis
DOI: 10.1002/anie.200460031
Published online: August 12, 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.
Obituary
Cyril A. Grob (1917–2003): Fragmentation and Inductivity
4392
P. Schiess
Books
Microsystem Engineering for
Lab-on-a-Chip Devices
4393
Oliver Geschke, Henning Klank,
Pieter Tellemann
reviewed by J. Moorthy, D. T. Eddington,
D. J. Beebe
Industrial Organic Pigments
4393
Willy Herbst, Klaus Hunger
reviewed by P. Erk
Metal–Ligand Bonding
4394
Bob Janes, Elaine Moore
reviewed by S. Schindler
Twisting a belt-shaped loop of p orbitals
results in a M7bius structure (see
scheme). Only recently have synthetic
chemists realized this idea first proposed
by Heilbronner 40 years ago. The interac-
tion of theory and synthesis, which has
distinguished the concept of aromaticity
since its inception, has opened a new
chapter in this field.
Highlights
Aromaticity
T. Kawase,* M. Oda*
4396 – 4398
M7bius Aromatic Hydrocarbons:
Challenges for Theory and Synthesis
Topochemistry
C. A. Schalley*
4399 – 4401
Borromean Rings: A One-Pot Synthesis
4382
Elegance and precision are shown in the
self-assembly strategy developed by
Stoddart, Atwood, and co-workers for the
synthesis of molecular Borromean rings.
Metal-ion template effects direct the
dynamic formation of covalent bonds,
which result in the energetically favorable
product having the highly symbolic ring
motif (see picture).
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
Angewandte
Chemie
Minireviews
Cubosomes, cubic liquid-crystalline
nanoparticles (see cryo-TEM image), can
be prepared from aqueous dispersions of
cubic lipid–water phases and are stabilized in the presence of dispersing agents
and through polymerization of reactive
lipids in cubic lipid assemblies. These
nanoparticles can incorporate and release
lipophilic, amphiphilic, and water-soluble
molecules in a controlled manner.
Nanostructures
D. Yang, B. Armitage,
S. R. Marder*
4402 – 4409
Cubic Liquid-Crystalline Nanoparticles
A golden age for theoretical chemistry:
From studies of small molecules to
molecular dynamics simulations, including the aurophilic attraction and predictions for new species such as the those for
the [WAu12] cluster depicted, theoretical
chemistry of gold has come of age. Certain
aspects of the softness and the electronic
plasmon oscillations may provide further
challenges.
Reviews
Theoretical Chemistry
P. Pyykk7*
4412 – 4456
Theoretical chemistry of gold
Communications
Coordination Polymers
J. M. J. Paulusse,
R. P. Sijbesma*
Breaking up and making up: The ultrasonic cleavage of high-molecular-weight
linear coordination polymers of phosphane telechelic polytetrahydrofuran and
palladium dichloride in dilute solution is a
reversible process (see picture).
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Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
Sonication for 1 h led to a decrease in the
weight-averaged molecular weight of the
polymer from 1.7 K 105 to 1.0 K 105 g mol 1.
Upon leaving the sample to stand for 24 h,
the original molecular weight was
completely restored.
4460 – 4462
Reversible Mechanochemistry of a PdII
Coordination Polymer
Green degradation: Organic contaminants such as volatile organic compounds
and dyes (e.g. acetaldehyde and methylene blue (MB)) can be photocatalytically
degraded over a novel CaBi2O4 catalyst.
The reaction is environmentally friendly
(O2 oxidant) and proceeds at room temperature under visible-light irradiation of
wide-ranging wavelength (see picture:
x = conversion of CH3CHO into CO2,
A = absorbance).
Photocatalysis
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J. Tang, Z. Zou, J. Ye*
4463 – 4466
Efficient Photocatalytic Decomposition of
Organic Contaminants over CaBi2O4
under Visible-Light Irradiation
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4383
Contents
Nanostructures
Lithium ion trafficking: Surprisingly stable
and soluble spherical molybdenum oxide
based porous nanocontainers/artificial
cells (see graphic) interact specifically
with their environment, for example, with
cations abundant in solution, to incorporate them at well-defined internal cell
positions. In the present case, the traffic
of Li+ ions between the “outside and
inside” is in equilibrium (homeostasis) as
measured by NMR spectroscopy. (Li
purple, Mo blue, O red)
A. MLller,* D. Rehder,* E. T. K. Haupt,
A. Merca, H. B7gge, M. Schmidtmann,
G. Heinze-BrLckner
4466 – 4470
Artificial Cells: Temperature-Dependent,
Reversible Li+-Ion Uptake/Release
Equilibrium at Metal Oxide
Nanocontainer Pores
Molecular Electronics
P. Jiang, G. M. Morales, W. You,
L. Yu*
4471 – 4475
Synthesis of Diode Molecules and Their
Sequential Assembly to Control Electron
Transport
A sequential deprotection and immobilization procedure was enabled by the
synthesis of two thiophene–thiazole
diblock oligomers with two different thiol
protection groups. Investigation of the
I/V behaviors of these diblock molecules
between two gold electrodes (see picture)
showed that the rectifying direction was
controlled by their orientation between
the electrodes.
Asymmetric Organocatalysis
W. Zhuang, S. Saaby,
K. A. Jørgensen*
4476 – 4478
Direct Organocatalytic Enantioselective
Mannich Reactions of Ketimines: An
Approach to Optically Active Quaternary
a-Amino Acid Derivatives
Biomimetic Catalysis
C. Dro, S. Bellemin-Laponnaz,* R. Welter,
L. H. Gade*
4479 – 4482
A C3-Symmetrical Chiral Trisoxazoline
Zinc Complex as a Functional Model for
Zinc Hydrolases: Kinetic Resolution of
Racemic Chiral Esters by
Transesterification
4384
You’re in control of which diastereomer of
a quaternary a-amino acid derivative is
formed in a direct organocatalytic
diastereoselective and enantioselective
Mannich reaction of ketimines with
aldehydes (see scheme). The reactions are
high yielding and can be controlled
through the choice of the catalyst to give
either diastereomer of the product with
diastereomeric ratios as high as > 20:1
and with 83–98 % ee. Pg = protecting
group.
Mimicking the activity of tris(histidine)zinc-based enzymes, chiral dinuclear trisoxazolinezinc complexes such as the triflato cation (see picture) are the first nonenzymatic catalysts for the asymmetric
transesterification of activated esters.
First results of the kinetic resolution of
amino acid phenolates establish the stereoselectivity for this reaction. (F pink,
N blue, O red, S yellow, Zn cyan)
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
Angewandte
Chemie
Tying nice neat knots is demonstrated on
a molecular level with the stereoselective
synthesis of a trefoil knot. The key reaction
was the completely stereoselective formation of a double-stranded helical precursor from two pinene–bipyridine
threads around two CuI centers (the
pinene moieties contain stereogenic centers). The helix was then transformed
through several steps into 1; demetallation of the complex 1 yielded the configurationally predetermined free trefoil knot.
A method for the calculation of NMR
shieldings is presented, which allows for
the first time the study of molecular
systems with one thousand and more
atoms at the ab initio level (see picture),
by reducing the computational scaling
from cubic to linear. This opens new
possibilities for the often difficult assignment of experimental NMR spectra.
Supramolecular Chemistry
L.-E. Perret-Aebi, A. von Zelewsky,*
C. Dietrich-Buchecker,
J.-P. Sauvage
4482 – 4485
Stereoselective Synthesis of a
Topologically Chiral Molecule:
The Trefoil Knot
Quantum Chemistry
C. Ochsenfeld,* J. Kussmann,
F. Koziol
4485 – 4489
Ab Initio NMR Spectra for Molecular
Systems with a Thousand and More
Atoms: A Linear-Scaling Method
Enantioselective Synthesis
I. Sato, R. Sugie, Y. Matsueda, Y. Furumura,
K. Soai*
4490 – 4492
The light touch: Asymmetric photoequilibrium and autocatalysis act as sources of
homochirality in a highly enantioselective
preparation of chiral alcohols (see
scheme). This process is initiated by left-
and right-circularly polarized light (CPL)
and exploits the resulting photoequilibrium between chiral olefin substrates to
yield 2-alkynyl-5-pyrimidyl alkanols.
Asymmetric Synthesis Utilizing Circularly
Polarized Light Mediated by the Photoequilibrium of Chiral Olefins in Conjunction with Asymmetric Autocatalysis
Reaction Mechanisms
N. Yamagiwa, S. Matsunaga,
M. Shibasaki*
4493 – 4497
The power of three: Mechanistic studies
based on the kinetic profiles of the
catalytic asymmetric 1,4-addition of an
amine to chalcone revealed that all three
Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
binol ligands of the [YLi3{tris(binaphthoxide)}] complex 1 are involved in the active
species of the Y–Li heterobimetallic
catalyst.
www.angewandte.org
Mechanistic Studies of a Reaction Promoted by the [YLi3{tris(binaphthoxide)}]
Complex: Are Three 1,1’-Bi-2-naphthol
Units in a Rare-Earth–Alkali-Metal
Heterobimetallic Complex Necessary?
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4385
Contents
Buckybowls
P. A. Vecchi, C. M. Alvarez, A. Ellern,
R. J. Angelici,* A. Sygula, R. Sygula,
P. W. Rabideau
4497 – 4500
Synthesis and Structure of a Dimetallated
Buckybowl: Coordination of One
{Cp*Ru}+ Unit to Each Side of
Corannulene
Main-Group Chemistry
H. Cox,* P. B. Hitchcock, M. F. Lappert,*
L. J.-M. Pierssens
4500 – 4504
A 1,3-Diaza-2,4-distannacyclobutanediide: Synthesis, Structure, and Bonding
A significantly flattened corannulene,
which is h6-coordinated on each side by a
{Cp*Ru}+ moiety, is revealed in the X-ray
structure analysis of [(Cp*Ru)2(m2-h6,h6C20H10)][PF6]2. The reaction of [{Cp*Ru(m3Cl)}4] with Ag+ ions and the curved-surface buckybowl corannulene (C20H10) in
CD3NO2 solvent affords this dimetallated
corannulene complex (see picture).
A combined experimental and computational study throws light on the structure
and bonding of the diamagnetic {(SnN)2}
compound [{Sn{N(SiMe3)}Cl}2] (see picture), obtained from the reaction of
[Sn{N(SiMe3)2}(m-Cl)]2 with AgOCN.
Bioinorganic Chemistry
I. Mulyani, A. Levina,
P. A. Lay*
4504 – 4507
Biomimetic Oxidation of Chromium(iii):
Does the Antidiabetic Activity of
Chromium(iii) Involve Carcinogenic
Chromium(vi)?
The insulin-enhancing activities of some
CrIII complexes, such as [Cr3O(OCOEt)6(OH2)3]+ (1), previously attributed to
specific interactions of CrIII ions with
cellular insulin receptors, are more likely
to be caused by the formation of [CrO4]2
Coordination Modes
Two transition-metal rhodizonate complexes, [M(C6O6)(bpym)(H2O)]·n H2O
(M = Cd, n = 1; M = Mn, n = 2;
bpym = 2,2’-bipyrimidine), are reported.
Both the rhodizonate and bpym ligands
are bis-bidentate ligands (see the Cd
example depicted) which chelate the
metal ions, thus forming a novel 2D
chairlike M6 metal–organic framework.
C.-C. Wang,* C.-T. Kuo, P.-T. Chou,
G.-H. Lee
4507 – 4510
Rhodizonate Metal Complexes with a 2D
Chairlike M6 Metal–Organic Framework:
[M(C6O6)(bpym)(H2O)]·n H2O
4386
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
(2). Oxidation of 1 to 2 by biologically
relevant oxidants, including enzymes (see
scheme), and inhibition of an isolated
protein tyrosine phosphatase by a CrVI
complex are reported.
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
Angewandte
Chemie
Silylenes
M. Kira,* S. Ishida, T. Iwamoto,
A. de Meijere, M. Fujitsuka,
O. Ito
4510 – 4512
The singlet 1,1-diradical (1B1) state of a
silylene plays a key role in its photoreactions with benzenes and alkenes, even
though similar 1B1 states are rarely
encountered in carbene chemistry. The
photochemical addition to alkenes should
be stepwise and the ring closure of the
intermediate singlet 1,3-diradicals was
very facile with rates (kc) of more than
109 s 1 (see scheme).
The Singlet Excited State of a Stable
Dialkylsilylene Is Responsible for Its
Photoreactions
Selenium Compounds
S. S. Zade, H. B. Singh,*
R. J. Butcher
Enzyme mimicry: Halogenation of diselenide 1 affords the cyclic selenenate ester 2
(see scheme) through a highly unstable
selenenic acid intermediate. Compound 2
exhibits a strong intramolecular nonbonding Se···O interaction. Both 1 and 2
show excellent glutathione peroxidase-like
catalytic activity.
A potentially tetradentate pyridyl–thiazole
ligand chain and an additional “external”
crown ether binding site connect the two
halves of a new ditopic ligand. The pyridylthiazole binding sites can be changed or
“reprogrammed” by the addition of Ba2+:
In the presence of Hg2+ and Na+ the
ligand L1 forms a dinuclear double helicate ([Hg2(L1)2Na2]6+), whereas in the
presence of Hg2+ and Ba2+ a mononuclear
species is formed ([Hg(L1)Ba]4+).
Gold-plated gold: NAD(P)H cofactors
mediate the catalytic growth of Au nanoparticles in the presence of AuCl4 and
CTAB (cetyltrimethylammonium bromide;
see picture). The process allows for the
optical detection of the cofactors and the
analysis of NAD(P)+-dependent biocatalyzed transformations in solutions and on
surfaces.
Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
www.angewandte.org
4513 – 4515
The Isolation and Crystal Structure of a
Cyclic Selenenate Ester Derived from
Bis(2,6-diformyl-4-tert-butylphenyl)diselenide and its Glutathione Peroxidase-Like
Activity
Reprogrammable Ligands
C. J. Baylies, L. P. Harding, J. C. Jeffery,
T. Riis-Johannessen,
C. R. Rice*
4515 – 4518
Allosteric and Electrostatic
Reprogramming of a Ditopic Ligand
Nanotechnology
Y. Xiao, V. Pavlov, S. Levine, T. Niazov,
G. Markovitch, I. Willner*
4519 – 4522
Catalytic Growth of Au Nanoparticles by
NAD(P)H Cofactors: Optical Sensors for
NAD(P)+-Dependent Biocatalyzed
Transformations
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4387
Contents
Natural Products Synthesis
A. Sorg, R. BrLckner*
4523 – 4526
Total Synthesis of Xerulinic Acid
An inhibitor of the biosynthesis of cholesterol, xerulinic acid, has been synthesized for the first time. The convergent
approach applied involves the palladiumcatalyzed coupling of an enediynoic ester
building block, a conjunctive C6 bisstannane, and a bromine-containing methylenebutenolide (see scheme;
R = Me3SiCH2CH2).
The “ringmaster” [Pd(tBu3P)2] serves as
the catalyst in the direct synthesis of
indoles by annulation of ortho-chloroanilines with ketones (see picture). This
versatile method can be used to synthesize a variety of functionalized indoles and
azaindoles. DMA = dimethylacetamide.
Indole Synthesis
M. NazarW,* C. Schneider,
A. Lindenschmidt,
D. W. Will
4526 – 4528
A Flexible, Palladium-Catalyzed Indole
and Azaindole Synthesis by Direct
Annulation of Chloroanilines and
Chloroaminopyridines with Ketones
Bioengineering
H. Pfruender,* M. Amidjojo, U. Kragl,
D. Weuster-Botz*
4529 – 4531
Efficient Whole-Cell Biotransformation in
a Biphasic Ionic Liquid/Water System
Biocompatible ionic liquids act as a substrate reservoir and an in situ extracting
agent in biotransformations with whole
cells (see scheme). In the reduction of 4chloroacetophenone to (R)-1-(4-chlorophenyl)ethanol, high product concentration (82 g L 1) and purity (99.6 % ee) were
achieved without the addition of cofactors
and without damaging the biocatalyst.
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
Service
Keywords
4532
Authors
4533
Vacancies
Preview
4388
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
A55
4535
Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
Corrigenda
*
Angewandte
Chemie
It was reported that 1,N6-etheno-2’-deoxyadenosine-3’-monophosphate (etheno-dAMP)
elutes before 2’-deoxyadenosine-3’-monophosphate (dAMP). The authors have now
found that etheno-dAMP elutes immediately after 2’-deoxythymidine-3’-monophosphate (dTMP). The assignment of the signals in the Communication relied on a
commercially modified oligonucleotide standard thought to contain etheno-dAMP. As
the synthesized 1,N6-etheno-2’-deoxyadenosine-3’-monophosphates are now characterized unambiguously, the mistake must have been because of an improperly defined
oligonucleotide standard or decomposition of the modified oligonucleotide. The
authors apologize for the error.
Capillary Electrophoresis Analysis of DNA
Adducts as Biomarkers for Carcinogenesis
The reported physical data in reference [25] are from a by-product. The physical data for
compound 3 are the following:
TLC (petroleum ether/ethyl acetate 1:1): Rf = 0.20; [a]D = 13.8 (c = 1.1, chloroform);
1
H NMR (250 MHz, CDCl3): d = 0.12 (s, 3 H), 0.15 (s, 3 H), 0.83 (s, 6 H), 0.85 (s, 3 H),
0.88 (s, 3 H), 1.61 (sept, 6.8 Hz, 1 H), 1.96 (s, 3 H), 3.21 (dt, J = 10.3, 7.8 Hz, 1 H), 3.53
(m, 1 H), 3.60 (dd, J = 9.5, 8.3 Hz, 1 H), 3.70 (m, 2 H), 3.81 (s, 3 H), 3.90 (dd, J = 10.3,
8.3 Hz, 1 H), 4.17 (dd, J = 12.8, 5.8 Hz, 1 H), 4.27 (dd, J = 12.8, 9.5 Hz, 1 H), 4.51 (s,
2 H), 5.06 (d, J = 8.0 Hz, 1 H), 5.19 (m, 2 H), 5.65 (d, J = 7.8 Hz, 1 H), 5.90 (m, 1 H), 6.88
(d, J = 8.5 Hz, 2 H), 7.26 ppm (d, J = 8.5 Hz, 2 H); 13C NMR (62.5 MHz, CDCl3):
d = 3.53, 1.82, 18.52, 20.04, 23.61, 24.77, 34.03, 55.26, 59.19, 70.61, 72.96, 73.19,
73.34, 73.62, 80.28, 94.89, 113.84, 116.94, 129.29, 129.95, 135.16, 159.28, 170.10 ppm.
Furthermore, the desilylation step c in the transformation of compound 7 to 6 requires
addition of acetic acid to be successful.
Stereoselective Synthesis of b-dMannopyranosides with Reactive
Mannopyranosyl Donors Possessing a
Neighboring Electron-Withdrawing Group
In this Communication C. R. D. Correia is also a correspondence author.
In addition, the structure for compound 18 is incorrectly depicted in Scheme 5; the
correct structure for 18 is the one shown in Scheme 4, which corresponds to 2-(4methoxyphenyl)-2,5-dihydrofuran. The first sentence of the third paragraph on
page 2515 should read as follows: “Interestingly, the composition of the cationic
intermediates changes drastically with time, as observed by continuous monitoring of
these intermediates by ESIMS.”
Probing the Mechanism of the Heck
Reaction with Arene Diazonium Salts by
Electrospray Mass and Tandem Mass
Spectrometry
O. J. Schmitz,* C. C. T. W7rth, D. Stach,
M. Wießler
Angew. Chem. Int. Ed. 2002, 41, 445–448
DOI 10.1002/15213773(20020201)41:3 < 445::AIDANIE445 > 3.0.CO;2-7
A. A.-H. Abdel-Rahman, S. Jonke,
E. S. H. El Ashry,* R. R. Schmidt*
Angew. Chem. Int. Ed. 2002, 41, 2972–2974
DOI 10.1002/15213773(20020816)41:16 < 2972::AIDANIE2972 > 3.0.CO;2-4
A. A. Sabino, A. H. L. Machado,
C. R. D. Correia,* M. N. Eberlin*
Angew. Chem. Int. Ed. 2004, 43, 2514–2518
DOI 10.1002/anie.200353076
In this Communication, Figure 4 b was incorrect. The correct graph is shown.
Enzyme Microarrays: On-Chip
Determination of Inhibition Constants
Based on Affinity-Label Detection of
Enzymatic Activity
J. Eppinger,* D. P. Funeriu,* M. Miyake,
L. Denizot, J. Miyake
Angew. Chem. Int. Ed. 2004, 43, 3806–3810
DOI 10.1002/anie.200353623
Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4389
Apology
Contents
*
A Dodecameric Water Cluster Built
Around a Cyclic Quasiplanar Hexameric
Core in an Organic Supramolecular
Complex of a Cryptand
A relevant paper by O. Ermer and J. Neudoerfl in Chem. Eur. J. 2001, 7, 4961–4980 was
not cited. The authors apologize for the omission.
S. K. Ghosh, P. K. Bharadwaj*
Angew. Chem. Int. Ed. 2004, 43, 3577–3580
DOI 10.1002/anie.200454002
4390
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 4382 – 4390
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