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Graphical Abstract Angew. Chem. Int. Ed. 82003

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Contents
Obituary
Harry Georg Drickamer
(1918 ? 2002)
Electronic Phenomena in Condensed
Matter at High Pressure
F. Hensel
850
851
T. Fukuyama and P. Wipf Recognized for
Heterocyclic Chemistry
851
H. Wiezer New Member of the Editiorial
Board
851
News
H. Kessler Receives Philip Morris
Award
Books
Titanium and Zirconium in Organic
Synthesis
852
Peptides: Chemistry and Biology
853
edited by R. Mahrwald
Ilan Mark
edited by B. Merrifield
Norbert Sewald, Hans-Dieter Jakubke
Highlights
E
Aromatic Substitution
D. Lenoir*
E
E-
?
+
854 ? 857
The Electrophilic Substitution of Arenes:
Is the p Complex a Key Intermediate and
What is Its Nature?
-H+
E
H
Aromatic substitution in detail: How does
one prove that the intermediate chargetransfer (CT) complex (see scheme, where
E = electrophile) is a key intermediate in
the electrophilic substitution of arenes,
and what is the structure, nature, and
significance of this intermediate? On the
basis of recent experimental findings
these questions and others will be examined.
Keywords:
ab initio calculations и arenes и aromatic
substitutions и electrophilic additions и
reaction mechanisms
O
Cross-Aldol Reactions of Aldehydes
H
B. Alcaide,* P. Almendros*
donor
858 ? 860
842
+
O
metal-free amino acid
R2
H
acceptor
asymmetric catalyst
OH
R2
H
R1
R1 = Me, nBu, Bn
R2 = iPr, c-C6H11, Ph
The Direct Catalytic Asymmetric CrossAldol Reaction of Aldehydes
Keywords:
aldol reactions и asymmetric catalysis и
asymmetric synthesis и C C coupling и
enantioselectivity
O
R1
Although the more elegant and most
economically attractive way to introduce
chirality into a molecule is by using a
catalytic amount of chiral controller to
induce chiral transformation without the
need for any other activation of the
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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starting materials, the first report of
chemical catalysis for the direct catalytic
asymmetric cross-aldol reaction of aldehydes has only recently appeared (see
scheme).
Angew. Chem. Int. Ed. 2003, 42, No. 8
Angewandte
Chemie
Reviews
NMR Spectroscopy of Proteins
B. Meyer,* T. Peters*
864 ? 890
NMR Spectroscopy Techniques for
Screening and Identifying Ligand Binding
to Protein Receptors
Picking the locks of protein binding: NMR
spectroscopic techniques for the characterization of binding processes have
recently gained much attention. Binding
epitopes on the ligands and on the protein
can be identified easily without the aid of
crystal structures (see scheme). Hereby,
rational design of new drugs has become
more accessible.
Keywords:
drug design и ligand?protein interactions и
NMR spectroscopy и proteins и screening
Communications
Methanol-to-Olefin Catalyst
W. Song, J. F. Haw*
892 ? 894
Improved Methanol-to-Olefin Catalyst
with Nanocages Functionalized through
Ship-in-a-Bottle Synthesis from PH3
Active phosphate flotsam: Tetramethylphosphonium cations can be prepared in
the cages of HSAPO-34 catalysts from
PH3 and methanol by using a ship-in-abottle approach (see picture). Calcination
of this material leaves phosphate debris in
some of the cages, which produces an
active methanol-to-olefin catalyst with
improved ethylene selectivity.
Surface Effects from Nanostructure
Dry and bright: To mimic the wings of the
displayed Morpho butterfly, a new decorative material that exhibits both structural color and superhydrophobicity (the
?lotus effect?) was developed by taking
advantage of the unique structural properties of an inverse opal film, which was
fabricated by the self-assembly of polystyrene spheres and silica nanoparticles.
For the USA and Canada:
ANGEWANDTE CHEMIE International
Edition (ISSN 1433-7851) is published weekly
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USA by Publications Expediting Inc. 200 Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2003, 42, 842 ? 849
Keywords:
heterogeneous catalysis и hydrocarbons и
microporous materials и nanostructures и
NMR spectroscopy
Z.-Z. Gu, H. Uetsuka, K. Takahashi,
R. Nakajima, H. Onishi, A. Fujishima,
O. Sato*
894 ? 897
Structural Color and the Lotus Effect
Keywords:
colloids и nanostructures и self-assembly и
structural color и wettability
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
delivery); for individuals who are personal
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Europe E 248.00/Outside Europe US$ 348.00.
1433-7851/03/4208-0843 $ 20.00+.50/0
843
Contents
Liquid-Crystal Molecular Design
S.-W. Tam-Chang,* W. Seo, I. K. Iverson,
S. M. Casey
897 ? 900
Ionic Quaterrylenebis(dicarboximide): A
Novel Mesogen and Long-Wavelength
Polarizing Material
Keywords:
aggregation и liquid crystals и polarization и
supramolecular chemistry и thin films
An absorbing study: The displayed quaterrylenebis(dicarboximide) was imparted
with lyotropic liquid-crystalline properties
by molecular design. The ability of the
molecule to self-organize in solution
allows for the subsequent control of its
orientation in thin solid films. Induced
orientation of the liquid-crystalline
domains of the molecule under a shearing
force results in highly anisotropically
ordered films that serve as dichroic
polarizers of light at wavelengths greater
than 600 nm.
Breaking the rule: The structure of
Sc3N@C68и[NiII(OEP)]и2 C6H6 has been
determined by single-crystal X-ray diffraction. The fullerene cage exists as an
isomer with D3 symmetry (see picture), as
initially predicted by density functional
calculations. The scandium atoms are
located over the centers of three pentalene
units within the three-cornered carbon
cage, which cannot obey the isolated
pentagon rule. OEP = Octaethylporphyrinate.
Pentalene Bonding in Fullerenes
M. M. Olmstead, H. M. Lee,
J. C. Duchamp, S. Stevenson, D. Marciu,
H. C. Dorn,* A. L. Balch*
900 ? 903
Sc3N@C68 : Folded Pentalene Coordination in an Endohedral Fullerene that Does
Not Obey the Isolated Pentagon Rule
Keywords:
fullerenes и isomers и nitrogen и scandium и
structure elucidation
Multiparallel Organic Synthesis
S. A. Kozmin,* Y. Wang
903 ? 905
A Three-Dimensional Array for Multiparallel Synthesis
Keywords:
combinatorial chemistry и multiparallel
synthesis и peptides и synthetic methods
844
An operationally simple and general
technique for multiparallel organic synthesis is based on the three-dimensional
delivery of reactants to an array of interconnected reaction wells. This technology
can be readily adapted to the design of
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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substantially large arrays, or multiple
copies of interconnected arrays, thus
allowing the necessary flexibility for the
synthesis and screening of a wide range of
chemical libraries.
Angew. Chem. Int. Ed. 2003, 42, No. 8
Angewandte
Chemie
Detection and characterization of unstable and complex DNA species, including
hyperstranded DNA species such as the
forklike structure of replicating DNA (see
picture), is made possible by cold-spray
ionization mass spectrometry.
DNA Structure
S. Sakamoto,
K. Yamaguchi*
905 ? 908
Hyperstranded DNA Architectures
Observed by Cold-Spray Ionization Mass
Spectrometry
Keywords:
DNA structures и hydrogen bonds и mass
spectrometry и supramolecular chemistry
More rapidly to the target: Screening
experiments in a miniautoclave demonstrate the different effects of catalytically
active additives such as Raney nickel and
basic alkali-metal compounds on the
reaction of methane in supercritical water.
Accordingly, this opens up the possibility
to convert methane into hydrogen and
carbon dioxide with water in a single
process step without the need to pass
through the intermediate carbon monoxide stage which is currently necessary in
industrial set ups (see scheme).
Starting from germanium(i) bromide,
which can be obtained by preparative cocondensation, the first polyhedral Ge
cluster [Ge8{N(SiMe3)2}6] (see picture)
has been synthesized in which the average
oxidation state of all the Ge atoms in the
cluster core lies between 0 and + 1.
Reactions in Supercritical Water
A. Kruse,* E. Dinjus
909 ? 911
Hydrogen from Methane and Supercritical
Water
Keywords:
high-pressure chemistry и hydrogen и
methane и reforming и supercritical fluids
Clusters with Ge0 Atoms
A. Schnepf,* R. KQppe
911 ? 913
[Ge8{N(SiMe3)2}6]: A Ligand-Stabilized Ge
Cluster Compound with Formally ZeroValent Ge Atoms
Keywords:
bond theory и cluster compounds и density
functional calculations и
disproportionation и germanium
The Rh-catalyzed asymmetric hydrogenation of b-aryl-substituted (E)-b-acylaminoacrylates, which were isolated for the
first time, with, for example [Rh{(R,R)(Et-FerroTANE)}(nbd)]+ as catalyst (see
picture) proceeds under very mild conditions (25 8C, normal pressure) and high
substrate/catalyst ratios with very good
enantioselectivity (Et-FerroTANE = (+)1,1?-bis(2,4-diethylphosphyltane)ferrocene, nbd = 3,5-norbornadiene).
Angew. Chem. Int. Ed. 2003, 42, 842 ? 849
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Asymmetric Hydrogenation
J. You, H.-J. Drexler, S. Zhang, C. Fischer,
D. Heller*
913 ? 916
Preparation and Asymmetric Hydrogenation of b-Aryl-Substituted b-Acylaminoacrylates
Keywords:
amino acids и asymmetric catalysis и
hydrogenation и P ligands и rhodium
1433-7851/03/4208-0845 $ 20.00+.50/0
845
Contents
Synthesis of Lipoteichoic Acids
A. Stadelmaier, S. Morath, T. Hartung,
R. R. Schmidt*
916 ? 920
Synthesis of the First Fully Active
Lipoteichoic Acid
Keywords:
biological activity и glycolipids и
lipoteichoic acid и natural products и
synthetic methods
Stable Spirobis(radical cation)
A. Ito, M. Urabe, K. Tanaka*
921 ? 924
Keywords:
EPR spectroscopy и magnetic properties и
radical ions и spiro compounds
Redox-Switchable Lithium Trap
M. Scheibitz, R. F. Winter, M. Bolte,
H.-W. Lerner, M. Wagner*
924 ? 927
[1.1]Diborataferrocenophane: A Highly
Efficient Li+ Scavenger
Keywords:
boron и electrochemistry и lithium и metal?
metal interactions и sandwich complexes
Novel spirobis(radical cation) 12+ was
prepared to examine the magnetic interaction between the two radical centers.
The dication 12+ was found to be a robust
triplet diradical on the basis of the ESR
spectrum, magnetic susceptibility measurements, which indicated ferromagnetic
interaction between the radical centers
(i.e., J > 0), and quantum chemical calculations.
d-alanine residues in the required ratio
with other substituents, resulted in the
same activity as exhibited by the natural
product obtained by a new isolation
procedure. Thus, the biological activity of
LTA could be ascertained for the first time.
J>0?
OMe
+
A Spiro-Fused Triarylaminium Radical
Cation with a Triplet Ground State
Nature outfoxed! Owing to the sensitivity
of lipoteichoic acids (LTAs) to hydrolysis
their biological activity could not be
ascertained thus far. The chemical synthesis of LTA of Staphylococcus aureus 1,
which contains hydrolytically labile
MeO
N
Me
O
Si
N
+
OMe
O
Me
OMe
12+
A naked lithium cation is efficiently
trapped within the [1.1]diborataferrocenophane dianion [1]2 , but released upon
electrochemical oxidation of the ferrocene
moieties. The complex [1-Li]Li([12]crown4)2 provides the first experimental evidence for a theoretically predicted ferroceneиииLi+ complex in which the Li+ ion is
laterally bound to the Fe atom.
Li-Intercalated Oxometallocubanes
J. Gracia, A. MartTn, M. Mena,*
M. d. C. Morales-Varela, J.-M. Poblet,
C. SantamarTa
927 ? 930
Intercalation of Alkali Metal Cations into
Layered Organotitanium Oxides
Keywords:
alkali metals и cyclopentadienyl ligands и
density functional calculations и oxo
ligands и titanium
846
Deprotonation of the complex [{Ti(h5C5Me5)(m-O)}3(m3-CH)] with different
alkali metal alkyl and amide reagents
provides a method for the intercalation of
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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alkali-metal ions into layered organometallic titanium oxides (see picture). The
process and the structures were analyzed
by DFT calculations.
Angew. Chem. Int. Ed. 2003, 42, No. 8
Angewandte
Chemie
H3CO
H3C
CH3 OCH3
OH
CO2CH3
H3CO
1
CH3
O
O H3CO
O
O
Unselectivity as an Advantage
CH3 OCH3
CH3 OCH3
2
H3CO
O
O
OCH3
H3CO
O
O
2
kotanin
One monomeric orsellinate (1) suffices for
a highly efficient total synthesis of the
dimeric coumarins kotanin, isokotanin A,
and desertorin C. The reason is the unse-
isokotanin A
D. Drochner, W. HUttel, M. Nieger,
M. MUller*
931 ? 933
desertorin C
lective course of its oxidative phenolic
coupling, which leads to three regioisomeric biaryls as precursors of the dimers.
Large pores comprising 48-membered
rings characterize the isostructural lanthanide?transition-metal coordination
polymers [{[Ln(dipic)3Mn1.5(H2O)3]и
n H2O}Ц], H2dipic = pyridine-2,6-dicarboxylic acid; Ln = Pr, n = 2 (shown here);
Ln = Gd, n = 3.5; Ln = Er, n = 3. Many
water molecules are trapped in the nanotubular structure, and the framework
remains intact on removal of the uncoordinated water molecules.
Unselective Phenolic Coupling of Methyl
2-Hydroxy-4-methoxy-6-methylbenzoate?A Valuable Tool for the Total Synthesis of Natural Product Families
Keywords:
atropisomerism и biaryls и biomimetic
synthesis и molecular diversity и total
synthesis
3d-4f Metal Coordination Polymers
B. Zhao, P. Cheng,* Y. Dai, C. Cheng,
D.-Z. Liao,* S.-P. Yan, Z.-H. Jiang,
G.-L. Wang
934 ? 936
A Nanotubular 3D Coordination Polymer
Based on a 3d?4f Heterometallic Assembly
Keywords:
coordination polymers и lanthanides и selfassembly и transition metals и zeolite
analogues
Capped Metal Polyhydride Clusters
M. Ohashi, K. Matsubara, T. Iizuka,
H. Suzuki*
937 ? 940
The cluster's clever cap: Treatment of 1
with an equimolar amount of diethylzinc
yields the cluster 2 together with the
elimination of ethane (see scheme). The
pentahydride 1 also reacts with metal
alkyls, such as MgiPr2, MeLi, AlEt3, and
Angew. Chem. Int. Ed. 2003, 42, 842 ? 849
GaMe3, to yield complexes 3?6 analogous
to 2 that contain a triply bridged metal
ligand. The effect of these ligands on
reactivity is evaluated by means of cyclic
voltammetry.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Trinuclear Ruthenium Polyhydride Complexes with a Triply Bridging Ligand: [{(h5C5Me5)Ru}3(m3-M)(m-H)3(m3-H)] (M = Li,
MgiPr, and ZnEt) and [{(h5-C5Me5)Ru}3(m3-M)(m-H)3] (M = AlEt and GaMe)
Keywords:
cluster compounds и cyclic voltammetry и
hydride ligands и ruthenium и trinuclear
complexes
1433-7851/03/4208-0847 $ 20.00+.50/0
847
Contents
Epoxidation
N. Makita, Y. Hoshino,
H. Yamamoto*
O
2 mol % VO(OiPr)3
6 mol % 1
R1
Asymmetric Epoxidation of Homoallylic
Alcohols and Application in a Concise
Total Synthesis of ( )-a-Bisabolol and
( )-8-epi-a-Bisabolol
Keywords:
bisabolol и epoxidation и homoallylic
alcohols и hydroxamic acids и vanadium
OH
cumene hydroperoxide
toluene, 0 ░C, 10 h
2
941 ? 943
O
O
R1 *
N
OH
O
3
tBu
Ph
N
OH
Ph
1
84?91% ee
42?89% yield
Vanadium triisopropoxide oxide and an aamino acid-based hydroxamic acid (e.g. 1)
form the catalyst for the asymmetric
epoxidation of homoallylic alcohols presented here. 3-Substituted alcohols 2 were
epoxidized to the corresponding epoxy
alcohols 3 with good ee values. In addition, a concise total synthesis of ( )-aand ( )-8-epi-a-bisabolol was achieved.
A new class of chiral phospholane?oxazoline ligands P* was developed for Ircatalyzed asymmetric hydrogenation (see
scheme, e.g. R = Ph; Ar = m-CH3C6H4).
High enantioselectivities (up to 99 % ee)
were obtained for the hydrogenation of
methylstilbene derivatives and (E)-bmethylcinnamic esters.
Catalytic Asymmetric Hydrogenation
W. Tang, W. Wang,
X. Zhang*
943 ? 946
Phospholane?Oxazoline Ligands for IrCatalyzed Asymmetric Hydrogenation
Keywords:
asymmetric catalysis и hydrogenation и
iridium и ligand design и N,P ligands
p-BrC6H4
Allylation of Aldehydes
N
K. Kubota, J. L. Leighton*
O
Si
946 ? 948
Cl
N
R
1
A Highly Practical and Enantioselective
Reagent for the Allylation of Aldehydes
Keywords:
aldehydes и allylation и asymmetric
synthesis и chiral auxiliaries и homoallylic
alcohols
848
BnO
OBn
Me3NO (4 equiv)
O
CSA (6 equiv)
H
H
HO
OH
CH2Cl2
84%
Dihydroxylation of 1,5-dienes under acidic
conditions is sufficient to induce an
efficient oxidative cyclization that produces stereochemically defined tetrahydrofurans in one step [Eq. (1)]. This method
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
61-93 % yield
95-98% ee
enantioselective allylation of aldehydes is
easily prepared as an air-stable solid and
may be stored without significant
decomposition.
OsO4 (5%)
OBn
Keywords:
cyclization и heterocycles и osmium и
oxidation и synthetic methods
R
1.0 equiv
OBn
948 ? 951
A General Oxidative Cyclization of 1,5Dienes Using Catalytic Osmium Tetroxide
-10 ░C
H
Strain at silicon is the key to success of
reagent 1 since this strain, which is
induced by the diazasilacyclopentane ring,
determines its reactivity. This practical
and general new reagent for the highly
One-Step Route to Tetrahydrofurans
T. J. Donohoe,*
S. Butterworth
p-BrC6H4
1.0 equiv
OH
CH2Cl2
+
1433-7851/03/4208-0848 $ 20.00+.50/0
(1)
is very general and efficient for a range of
dienes and shows complete stereoselectivity for formation of the 2,5-cis diastereoisomers. Bn = benzyl, CSA = camphorsulfonic acid.
Angew. Chem. Int. Ed. 2003, 42, No. 8
Angewandte
Chemie
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Keywords
952
Authors
953
Preview
955
Corrigendum
*
In the Meeting Reviews ?The 50th Birthday of the Organocuprates? by Norbert Krause in Issue 4, 2003, the lecture by Gernot Boche
was wrongly cited. Instead of ?...and it could be shown that Michael additions of organocuprates proceed via solvent-separated ion
pairs? it should say ?...that Michael additions of organocuprates proceed via contact ion pairs? (see also Boche et al., Chem. Eur. J.
2002, 6, 3060?3068). The author apologises for this error.
Angew. Chem. Int. Ed. 2003, 42, 842 ? 849
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