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Graphical Abstract Angew. Chem. Int. Ed. 412003

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Contents
The following articles are available online (in Wiley InterScience). You can find them at
www.angewandte.org, under Full Text, Early View.
X. Wang, L. Andrews*:
Gold Is Noble but Gold Hydride Anions
Are Stable
DOI: 10.1002/anie.200351780
Published online: October 14, 2003
F. Dumestre, B. Chaudret,* C. Amiens,
M. Respaud, P. Fejes, P. Renaud, P. Zurcher:
Unprecedented Crystalline Super-Lattices
of Monodisperse Cobalt Nanorods
DOI: 10.1002/anie.200352090
Published online: October 14, 2003
J. P. Camden, H. A. Bechtel, R. N. Zare*:
Dynamics of the Simplest Reaction of a
Carbon Atom in a Tetrahedral Environment
DOI: 10.1002/anie.200352642
Published online: October 14, 2003
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 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.
News
Awards for John M. Thomas and
Tobin J. Marks
4992
Books
Structural Bioinformatics
4993
Philip E. Bourne, Helge Weissig
reviewed by Lars-Oliver Essen
DNA and RNA Binders
4994
Martine Demeunynck, Christian Bailly,
W. David Wilson
reviewed by Oliver Seitz
From unexpected side products to new
catalytic cyclizations: Numerous ruthenium-catalyzed cyclization reactions that
probably proceed via five-membered
ruthenium metallacycles and do not
involve olefin metathesis have been
described recently. The border between
metathesis and nonmetathesis cyclization
pathways is not always clearly defined.
This phenomenon can lead to the discovery of new ruthenium-catalyzed reactions
(see scheme; X = CR2, NR).
In October, 1953 an experiment was
carried out in the Max Planck Institut fDr
Kohlenforschung in MDlheim an der Ruhr,
that even today has a huge influence on
the chemical industry: the catalytic polymerization of ethylene under normal
pressure carried out with what at the time
was known as the MDlheim mixed catalyst. The story of what is know known as
the Ziegler catalyst reveals its discovery to
be the result of the meticulous analysis of
apparently failed experiments.
Highlights
Cyclizations
B. Schmidt*
4996 – 4999
Ruthenium-Catalyzed Cyclizations: More
than Just Olefin Metathesis!
Essays
Fifty Years of Ziegler Catalysts
G. Wilke*
5000 – 5008
Fifty Years of Ziegler Catalysts:
Consequences and Development of
an Invention
4982
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 4982 – 4988
Angewandte
Chemie
Reviews
Happy birthday! 50 years after the discovery of the catalytic polymerization of
ethylene with Ziegler catalysts (see
scheme) this process is still a vital,
modern, industrial process. Based on
high-performance catalysts and a broad
process knowledge, products with excellent combinations of properties for a widerange of applications can be produced in
an economical environmentally friendly
and resources saving way.
Fifty Years of Ziegler Catalysts
L. L. BGhm*
5010 – 5030
The Ethylene Polymerization with Ziegler
Catalysts: Fifty Years after the Discovery
Communications
Electronic Transitions in Silicon
M. Chiesa, G. Amato, L. Boarino,
E. Garrone, F. Geobaldo,
E. Giamello*
5032 – 5035
Gas works wonders! Conduction-band
electrons can be generated in p+-type
mesoporous crystalline silicon through
the adsorption of ammonia (see scheme).
Free-carrier concentration increases with
increasing NH3 adsorption to a critical
value, where a reversible insulator-tometal transition occurs.
Reversible Insulator-to-Metal Transition in
p+-Type Mesoporous Silicon Induced by
the Adsorption of Ammonia
CdSe Quantum Shells and Wells
D. Battaglia, J. J. Li, Y. Wang,
X. Peng*
5035 – 5039
Thin CdSe layers (“quantum shells”) were
epitaxially grown onto CdS nanocrystal
templates. Their optical properties are
dominated by the shell thickness despite
the different bandgap and size of the
templates. The emission of the CdSe
quantum shells, which can be tuned by
varying the shell thickness, ranges from
520 to 650 nm (see Figure), and the
emission quantum yield can be increased
to over 40 % by coating the quantum
shells with epitaxially grown CdS thin
layers (CdSe colloidal “quantum wells”).
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Angew. Chem. Int. Ed. 2003, 42, 4982 – 4988
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Colloidal Two-Dimensional Systems:
CdSe Quantum Shells and Wells
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4983
Contents
“Nano-ion Chromatograph”
A decision-making capsule! Where cation
trafficking comes to a halt is predetermined, with the process corresponding to
a “nano-ion chromatograph” in action:
starting from pores the route may end in a
finely sculpturable interior of a stable,
soluble spherical capsule but in many
cases it ends in between in channels that
exhibit a variety of cation-capturing functionalities at different positions (one of
the twenty channels is shown with the
residing cations).
A. MDller,* S. K. Das, S. Talismanov,
S. Roy, E. Beckmann, H. BGgge,
M. Schmidtmann, A. Merca, A. Berkle,
L. Allouche, Y. Zhou,
L. Zhang
5039 – 5044
Trapping Cations in Specific Positions in
Tuneable “Artificial Cell” Channels: New
Nanochemistry Perspectives
Oxy-Cope Reaction Mechanism
P. Maurin, S.-H. Kim, S. Y. Cho,
J. K. Cha*
5044 – 5047
On the Mechanism of the Anionic OxyCope Rearrangement of trans-1,2-Dialkenylcyclobutanols
A concerted mechanism involving a
chairlike transition state (see scheme)
and no appreciable loss of enantiopurity
was concluded for the anionic oxy-Cope
rearrangement of sterically unencum-
bered trans-1,2-dialkenylcyclobutanols
from a study employing nonracemic substrates containing vinyl and propenyl
groups with evaluation of the enantio- and
diastereofacial selectivity.
CO2 in, CH4 out! From NMR spectroscopic measurements of composition and
kinetics, it can be shown that the recovery
of methane from methane hydrate is
possible through its reaction with CO2
(see diagram), even though the yield is
less than that expected from kinetic and
thermodynamic arguments.
The long-standing challenge of developing
a general method for the title methodology is met for a broad range of aryl
chlorides through the use of bicyclic
P(iBuNCH2CH2)3N (1) as a bulky electronrich ligand for palladium (see scheme,
dba = dibenzylideneacetone).
CH4 from Methane Hydrate
H. Lee, Y. Seo, Y.-T. Seo,
I. L. Moudrakovski,
J. A. Ripmeester*
5048 – 5051
Recovering Methane from Solid Methane
Hydrate with Carbon Dioxide
Arylation of Nitriles
J. You, J. G. Verkade*
5051 – 5053
A General Method for the Direct aArylation of Nitriles with Aryl Chlorides
4984
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 4982 – 4988
Angewandte
Chemie
Baylis–Hillman Reaction
J. You, J. Xu, J. G. Verkade*
5054 – 5056
A Highly Active and Selective Catalyst
System for the Baylis–Hillman Reaction
A key role for sulfur and the potential for
Nax !P intrabridgehead interactions are
invoked to explain the impressive effect of
the cocatalyst (shown in color) in the
TiCl4-mediated Baylis–Hillman reaction
[Eq. (1)]. Even sterically hindered and
electronically deactivated aldehydes such
as o-anisaldehyde can be coupled under
these conditions. EWG = electron-withdrawing group, RT = room temperature.
Enantioselective Alkynylation
G. Lu, X. Li, X. Jia, W. L. Chan,
A. S. C. Chan*
5057 – 5058
The smooth addition of phenylacetylene to
aromatic ketones in the presence of
catalytic amounts of Cu(OTf)2 and camphorsulfonamide provides the corresponding tertiary propargylic alcohols in
A general route to oxoindolizino quinolines, such as nothapodytine A, mappi-
high yields and with up to 97 % ee. This
reaction represents a highly enantioselective catalytic addition of dialkynyl zinc
reagents to simple ketones.
cine, camptothecin, and several chemotherapeutic derivatives, is illustrated by
the synthesis of the antiviral natural
product from Nothapodytes foetida, mappicine ketone (R1 = R4 = H, R2 = CH3,
R3 = COC2H5). A wide range of new
camptothecinoids should now be readily
available for biological testing.
Enantioselective Alkynylation of Aromatic
Ketones Catalyzed by Chiral Camphorsulfonamide Ligands
Synthesis of Quinoline Alkaloids
G. B. Raolji, S. GarPon, A. E. Greene,*
A. Kanazawa*
5059 – 5061
A Modular Approach to Oxoindolizino
Quinolines: Efficient Synthesis of
Mappicine Ketone (Nothapodytine B)
Radical Additions to C = N Bonds
G. K. Friestad,* Y. Shen,
E. L. Ruggles
A radical concept: In the presence of
chiral CuII–bisoxazoline complexes, the
addition of alkyl radicals to achiral N-acyl
hydrazones, which have a two-pointbinding motif, proceeded with high enan-
Angew. Chem. Int. Ed. 2003, 42, 4982 – 4988
tioselectivity. Evidence of catalyst turnover
was demonstrated, providing the first
example of asymmetric catalysis in radical
additions to C¼N bonds.
www.angewandte.org
5061 – 5063
Enantioselective Radical Addition to
N-Acyl Hydrazones Mediated by Chiral
Lewis Acids
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4985
Contents
Green Chemistry
C. Li,* P. Zheng, J. Li, H. Zhang, Y. Cui,
Q. Shao, X. Ji, J. Zhang, P. Zhao,
Y. Xu
5063 – 5066
The Dual Roles of Oxodiperoxovanadate
Both as a Nucleophile and an Oxidant in
the Green Oxidation of Benzyl Alcohols or
Benzyl Halides to Aldehydes and Ketones
Regioselective Allylic Substitution
M. D. Mbaye, B. Demerseman,*
J.-L. Renaud, L. Toupet,
C. Bruneau*
5066 – 5068
[Cp*(h2-bipy)(MeCN)RuII][PF6] Catalysts
for Regioselective Allylic Substitution and
Characterization of Dicationic [Cp*(h2-bipy)(h3-allyl)RuIV][PF6]2 Intermediates
One catalyst, two roles: VO(O2)2 reacts
as a nucleophilic oxidant under acidic
conditions towards benzyl alcohols. Alto-
gether 15 alcohols have been oxidized, in
the absence of organic solvent, in excellent yields. Benzyl halides are also oxidized by H2O2 in water catalyzed by
oxodiperoxovanadate and a phase transfer
catalyst into aromatic aldehydes and
ketones (see scheme). This reaction is the
first green oxidation of benzyl halides.
The coordination of a 2,2’-bipyridyl derivative to a (C5Me5)RuII fragment provides
both a facile route to unprecedented
dicationic (allyl)RuIV complexes (see picture) and new highly efficient catalysts for
the regioselective allylic substitution from
unsymmetrical allylic carbonates.
Dipyranose Ethers
H. Takahashi, T. Fukuda, H. Mitsuzuka,
R. Namme, H. Miyamoto, Y. Ohkura,
S. Ikegami*
5069 – 5071
Development of a Novel Sugar Linkage:
6,6’-Ether-Connected Sugars
Catalytic Methanol Oxidation
H. Liu, N. Bayat, E. Iglesia* 5072 – 5075
Site Titration with Organic Bases During
Catalysis: Selectivity Modifier and Structural Probe in Methanol Oxidation on
Keggin Clusters
4986
Unusual sugar dimers: The synthesis of
6,6’-ether-connected pyranoses by an
acetalization–reduction procedure is
described (see scheme). Structure–activity-relationship studies of these novel
carbohydrate dimers suggested that the
natural product coyolosa, which has been
shown to have a significant effect on
fasting blood-glucose levels, may have a
different structure from the one previously
reported.
The selective and permanent titration of
protons with organic bases (2,6-di-tertbutylpyridine or pyridine) provides an
accurate measure of the dispersion of
Keggin structures during catalytic oxidation of methanol. Titration allows the
systematic control of the redox and acid
properties of H3+nPVnMo12nO40 (n = 0–4)
Keggin clusters and leads to unprecedented selectivity in the formation of
dimethoxymethane (> 80 %) and high
yields.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 4982 – 4988
Angewandte
Chemie
Easily accessible, the tris(alkyl) complexes
of rare-earth elements [Ln(CH2SiMe3)3(thf)2] are activated by [NMe2HPh]
[B(C6F5)4] in the presence of AliBu3 to
catalyze homogeneous ethylene polymerization. Model reactions show that the
bis(alkyl) yttrium monocation is converted into the mono(alkyl) dication (see
picture), which appears to be the active
species in ethylene polymerization.
Efficient Ethylene Polymerization
S. Arndt, T. P. Spaniol,
J. Okuda*
5075 – 5079
Homogeneous Ethylene-Polymerization
Catalysts Based on Alkyl Cations of the
Rare-Earth Metals: Are Dicationic Mono(alkyl) Complexes the Active Species?
Expanding the Stille Coupling
H. Tang, K. Menzel,
G. C. Fu*
Alkyldiaminophosphanes (PR(NR’2)2) are
a new class of ligands for palladiumcatalyzed cross-couplings of alkyl halides
(see scheme). In comparison with trialkylphosphanes, alkyldiaminophosphanes
furnish more versatile catalysts for Stille
Masses of evidence: Mass spectrometry
combined with 18O labeling reveals that
the imidazole and pyridine complexes
Angew. Chem. Int. Ed. 2003, 42, 4982 – 4988
5079 – 5082
reactions of alkyl bromides and achieve
efficient couplings with both vinyl and aryl
stannanes. Furthermore, Pd/PR(NR’2)2
provides the first method for accomplishing Stille cross-couplings of simple
alkyl iodides that bear b-hydrogen atoms.
Ligands for Palladium-Catalyzed CrossCouplings of Alkyl Halides: Use of an
Alkyldiaminophosphane Expands the
Scope of the Stille Reaction
Mild reduction with metals: Elemental
gallium is used as mild reducing agent for
transition-metal halides to generate subvalent GaCl ligands in novel clusters. In
the reaction of Ga with [{Cp’’RhCl2}]
(Cp’’ = h5-1,3-C5H3tBu2), clusters with
GaCl ligands and with unprecedented
two-coordinate Ga centers in a multicenter–multiple-bonding interaction between
two rhodium centers are formed (see
picture).
Cluster Chemistry
[LnZnOH]+ (n = 1, 2) are capable of activating carbon dioxide, under thermal
conditions. These gas-phase reactions
thus provide a simple mimic for the
function of the active site in carbonic
anhydrase.
Carbon Dioxide Activation
www.angewandte.org
M. Scheer,* M. Kaupp,* A. V. Virovets,
S. N. Konchenko*
5083 – 5086
Elemental Gallium as a Source of Subvalent Gallium Units in Gallium–Rhodium
Clusters
D. SchrGder,* H. Schwarz, S. Schenk,
E. Anders
5087 – 5090
A Gas-Phase Reaction as a Functional
Model for the Activation of Carbon
Dioxide by Carbonic Anhydrase
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4987
Contents
Kinetics of Olefin Polymerization
Picture this: The simultaneous growth of
many single grains of catalyst culminating
in polymer particles can be observed by
videomicroscopy, and single-grain kinetics can be studied. The gas-phase polymerization of ethylene on 40 particles was
examined in an autoclave equipped with a
glass window by automatic image processing. The picture shows the overlap of
three different stages of the polymerization after 0 (blue), 60 (red), and 180
(yellow) minutes.
S. Knoke, D. Ferrari, B. Tesche,
G. Fink*
5090 – 5093
Microkinetic Videomicroscopic Analysis
of Olefin Polymerization with a Supported
Metallocene Catalyst
Blocked Isocyanate Equivalents
S. Maier, T. Loontjens, B. Scholtens,
R. MDlhaupt*
5094 – 5097
Carbonylbiscaprolactam: A Versatile
Reagent for Organic Synthesis and Isocyanate-Free Urethane Chemistry
The power of the rings: The reactions of
carbonylbiscaprolactam (CBC, 1) with
amines and alcohols proceed either by
ring elimination (RE) or by ring opening
(RO). The conversion and selectivity of
these reactions were optimized in studies
with various hydroxy and amino compounds, catalysts, reaction temperatures,
and ratios of 1/nucleophile.
Service
Keywords
5098
Authors
5099
Sources
A59
Vacancies
A61
Preview
4988
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5101
Angew. Chem. Int. Ed. 2003, 42, 4982 – 4988
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