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Graphical Abstract Angew. Chem. Int. Ed. 92004

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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.
N. D. Clement, K. J. Cavell,* C. Jones, C. J. Elsevier:
Oxidative Addition of Imidazolium Salts to Ni0 and Pd0 : Synthesis and Structural Characterization of Unusually Stable
Metal–Hydride Complexes
DOI: 10.1002/anie.200353409
Published online: February 11, 2004
N. Halland, P. S. Aburel, K. A. Jørgensen*:
Highly Enantio- and Diastereoselective Organocatalytic Asymmetric Domino Michael–Aldol Reaction of b-Ketoesters and a,bUnsaturated Ketones
DOI: 10.1002/anie.200353364
Published online: February 11, 2004
S. E. McLain, C. J. Benmore, J. E. Siewenie, J. Urquidi,
J. F. C. Turner*:
On the Structure of Liquid Hydrogen Fluoride
DOI: 10.1002/anie.200353289
Published online: February 11, 2004
J. M. Ready, S. E. Reisman, M. Hirata, M. M. Weiss, K. Tamaki,
T. V. Ovaska, J. L. Wood*:
A Mild and Efficient Synthesis of Oxindoles: Progress Towards
the Synthesis of Welwitindolinone A Isonitrile.
DOI: 10.1002/anie.200353282
Published online: February 11, 2004
E. Hittinger, A. Kokil, C. Weder*:
Synthesis and Characterization of Cross-Linked Conjugated
Polymer Milli-, Micro-, and Nanoparticles
DOI: 10.1002/anie.200352863
Published online: February 29, 2004
J. K. Cammack, H. Amouri, P. W. Leonard, R. L. Myrabo,
K. P. C. Vollhardt*:
Electron Exchange Along the Tercyclopentadienyltrimetallic
Scaffold: Kinetics, Equilibria, and Bond Strengths
DOI: 10.1002/anie.200352479
Published online: February 9, 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 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
Cotton Award to J. Ellis
1044
Research Prizes to P. Schwille and
P. Fromherz
1044
F. Diederich: New Editorial Board
Chairman
David E. Metzler
reviewed by B. Schwenzer, K.-H. van Pe
Judit E. Puskas, Timothy E. Long,
Robson F. Storey
reviewed by B. Abel
Highly functionalized carbo- and heterocycles can be prepared enantioselectively
from simple enynes in transition-metalcatalyzed reactions. This versatile, atomeconomic, and environmentally friendly
approach has become a mainstay in
natural product synthesis. The concise
synthesis of (+ )-pilocarpine is one
example (see scheme). binap = 2,2’-bis(diphenylphosphanyl)-1,1’-binaphthyl),
cod = cyclooctadiene, RT = room temperature.
1044
Books
Biochemistry
1045
In Situ Spectroscopy of Monomer and
Polymer Synthesis
1045
Highlights
Synthetic Methods
I. J. S. Fairlamb*
1048 – 1052
Asymmetric Cycloisomerization of 1,6and 1,7-Enynes by Transition-Metal
Catalysts
1036
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 1036 – 1043
Angewandte
Chemie
Essays
Staudinger’s visions paved the way for the
development of modern polymeric materials with very versatile properties and new
opportunities at the interface of materials
and life sciences. This is confirmed in this
Essay, written to mark the 50th anniversary of the award of the Nobel Prize for
Chemistry to Hermann Staudinger. His
revolutionary concept, which initially
attracted heavy opposition, marked the
beginning of the new era of rational
molecular design of structural and functional polymeric materials, whose property profiles are tailored by varying their
molecular architectures.
History of Science
Chemistry was his life, but Hermann
Staudinger’s dreams belonged to biology
and to the unity of chemistry and biology.
That is the central theme of this Essay,
which, on the occasion of the fiftieth
anniversary of the award of the Nobel
Prize to Hermann Staudinger, discusses
the significance of Staudinger’s discoveries for the biosciences, not only retrospectively, but deliberately also prospectively. General questions of science ethics
and the interplay of research, politics, and
responsibility are also considered.
History of Science
R. M<lhaupt*
1054 – 1063
Hermann Staudinger and the Origin of
Macromolecular Chemistry
H. Ringsdorf*
1064 – 1076
Hermann Staudinger and the Future of
Polymer Research: Jubilees—Beloved
Occasions for Cultural Piety
Minireviews
Plastics
Biodegradable plastics based on renewable raw materials are interesting alternatives considering the limited availability
of fossil fuel feedstocks and the emission
of greenhouse gases. Biological degradability has been defined in Germany since
1998 by an industrial standard, the logo of
which is depicted.
S. Mecking*
1078 – 1085
Nature or Petrochemistry?—Biologically
Degradable Materials
Communications
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Angew. Chem. Int. Ed. 2004, 43, 1036 – 1043
Complex anionic partial structures of the
general formula [BeN ] occur in nitridoberyllates Ae[Be2N2] (Ae = Mg, Ca, Sr, Ba).
Planar 4.82 nets are present in Ca[Be2N2]
and Sr[Be2N2] (see structure; Ca, Sr: gray;
Be: purple; N: green), whereas Mg[Be2N2]
displays puckered 63 nets connected to
form double layers and a peculiar bonding
situation for nitrogen.
Layered Compounds
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M. Somer, A. Yarasik, L. Akselrud, S. Leoni,
H. Rosner, W. Schnelle,
R. Kniep*
1088 – 1092
Ae[Be2N2]: Nitridoberyllates of the Heavier
Alkaline-Earth Metals
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1037
Contents
NMR Spectroscopic Methods
B. Luy, K. Kobzar,
H. Kessler*
Stretched polystyrene gel (see picture)
induces partial alignment of small
molecules in an organic solvent for the
measurement of residual dipolar couplings in high-resolution NMR spectroscopy. The degree of orientation can be
varied over a wide range by the amount of
cross-linking of the polymer. An important
NMR parameter can thus be measured
routinely.
1092 – 1094
An Easy and Scalable Method for the
Partial Alignment of Organic Molecules
for Measuring Residual Dipolar Couplings
Pd-Catalyzed Couplings
L. J. Gooßen,* J. Paetzold
1095 – 1098
Decarbonylative Heck Olefination of Enol
Esters: Salt-Free and Environmentally
Friendly Access to Vinyl Arenes
Biosynthesis
B. Irlinger, H.-J. KrMmer, P. Mayser,*
W. Steglich*
1098 – 1100
Pityriarubins, Biologically Active
Bis(indolyl)spirans from Cultures of the
Lipophilic Yeast Malassezia furfur
Thank you, no salt on the side. In this
variant of the Heck olefination, enol esters
serve as environmentally friendly synthetic
equivalents of aryl halides. These reactants, in turn, are available from a wastefree synthesis from carboxylic acids and
propyne. Thus, a salt-free overall process
has been devised for preparing vinyl
arenes from a variety of aromatic
carboxylic acids.
Indole alkaloids, such as pityriarubin A
(1), may be of importance for the pathogenesis of the common skin disease
pityriasis versicolor. The metabolite 1 is
produced in cultures of the lipophilic yeast
Malassezia furfur with tryptophan present
as the sole source of nitrogen. The
structures of the pityriarubins were
derived from spectroscopic investigations, and insight into their biosynthesis
was gained by feeding experiments with
[1’-13C]tryptophan.
Structures of Macromolecules
C. Li, N. Gunari, K. Fischer, A. Janshoff,
M. Schmidt*
1101 – 1104
New Perspectives for the Design of
Molecular Actuators: Thermally Induced
Collapse of Single Macromolecules from
Cylindrical Brushes to Spheres
1038
Polymethacrylates with densely grafted
poly-N-isopropylacrylamide side chains
change their shape at the lower critical
solution temperature from cylindrical
brushes (left) to spherical structures
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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(right). This is an interesting example of a
temperature-induced cylinder-to-sphere
transition observed for single macromolecules.
Angew. Chem. Int. Ed. 2004, 43, 1036 – 1043
Angewandte
Chemie
Solid-Phase Synthesis
U. H<nger, J. Ohnsmann,
H. Kunz*
Irrespective of the sequence, the carbohydrate scaffold 1 as a molecular platform
for combinatorial diversification can be
selectively deprotected and equipped with
side chains, for example amino acids or
peptides, in every position (see picture).
This allows the flexible arrangement of
functional groups and structural elements. PG = protective group.
1104 – 1107
Carbohydrate Scaffolds for Combinatorial
Syntheses That Allow Selective
Deprotection of All Four Positions
Independent of the Sequence
Asymmetric Catalysis
A. Bøgevig, H. SundOn,
A. CPrdova*
Proline-catalyzed reactions between
unmodified ketones and nitrosobenzene
proceed with excellent diastereo- and
enantioselectivities to provide protected
1109 – 1112
Direct Catalytic Enantioselective
a-Aminoxylation of Ketones: A Stereoselective Synthesis of a-Hydroxy and
a,a’-Dihydroxy Ketones
a-hydroxy and a,a’-dihydroxy ketones
[Eq. (1)]. Such compounds with chiral
a-hydroxy carbonyl units are crucial in
natural product synthesis.
Asymmetric Catalysis
Nitrosobenzene is the oxygen source in
the direct catalytic enantioselective
a-aminoxylation of ketones catalyzed by
l-proline [Eq. (1)]. Versatile a-aminoxylated ketones are obtained in high yield
and with excellent enantioselectivities.
Y. Hayashi,* J. Yamaguchi, T. Sumiya,
M. Shoji
1112 – 1115
Direct Proline-Catalyzed Asymmetric
a-Aminoxylation of Ketones
Magnetic Nanoparticles
W. S. Seo, H. H. Jo, K. Lee, B. Kim, S. J. Oh,
J. T. Park*
1115 – 1117
Highly crystalline and monodisperse
MnO and Mn3O4 nanoparticles are prepared by thermal decomposition of
[Mn(acac)2] in oleylamine under an inert
atmosphere in the presence and absence
of a small amount of water, respectively
(see picture). The particle size of both
manganese oxide systems can be easily
manipulated by changing the employed
reaction temperature, and it has been
demonstrated that the magnetic behavior
depends on the size of the particles.
Size-Dependent Magnetic Properties of
Colloidal Mn3O4 and MnO Nanoparticles
Lipid Amphiphiles
K. By, M. H. Nantz*
Making and breaking lipids: A general
synthesis of a new class of ortho ester
lipids from a dioxazocinium ketene acetal
is disclosed. Both single- and dual-chain
Angew. Chem. Int. Ed. 2004, 43, 1036 – 1043
analogues were prepared, and the most
sensitive of these (see structure) was
shown to disassemble at 38 8C within 6 h
at pH 5.0.
www.angewandte.org
1117 – 1120
Dioxazocinium Ortho Esters: A Class of
Highly pH-Vulnerable Amphiphiles
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1039
Contents
Synthesis Techniques
T. Hirabayashi, S. Sakaguchi,
Y. Ishii*
1120 – 1123
A New Route to Lactam Precursors from
Cycloalkanes: Direct Production of
Nitrosocycloalkanes or Cycloalkanone
Oximes by Using tert-Butyl Nitrite and
N-Hydroxyphthalimide
Clean and selective: Nitrosation and
oximation of cycloalkanes was achieved by
treating them with tBuONO under Ar in
the presence of a catalytic amount of
N-hydroxyphthalimide (see scheme). The
novel, clean nitrosation procedure uses
halogen-free, relatively mild reaction
conditions and results in good product
Silicon squares up: The silylene Si[1,2(NR)2C6H4] (R = CH2tBu) is thermally
stable owing to its bulky substituent.
What effect will a reduction of the size of R
have on the stability of a two-coordinate
SiII species? Results show that a silylene
with R = Et cannot be isolated but will
yield a stable radical anion (see picture)
and dianion of a cyclotetrasilane.
Silanes
B. Gehrhus,* P. B. Hitchcock,
L. Zhang
1124 – 1126
An Isolable Radical Anion and Dianion of
a Cyclotetrasilane: Synthesis and
Structure of [Si{1,2-(NEt)2C6H4}]4 C and
[Si{1,2-(NEt)2C6H4}]42
Conjugate Addition–Alkylations
F. F. Fleming,* Z. Zhang, Q. Wang,
O. W. Steward
1126 – 1129
Oxonitriles: Multicomponent Grignard
Addition–Alkylations
Three at a time: Sequential carbonyl
addition, chelation-controlled conjugate
addition, and alkylation triggers the
Heme Degradation
Concerted or stepwise? A homolytic
stepwise pathway is taken by the enzyme
heme-oxygenase (HO) to degrade the
porphyrin ring in heme species. The
porphyrin ring assists the enzyme by
trapping the hydroxyl radical during the
degradation (see scheme). HO is
compared to cytochrome P450.
P. K. Sharma, R. Kevorkiants,
S. P. de Visser, D. Kumar,
S. Shaik*
1129 – 1132
Porphyrin Traps Its Terminator! Concerted
and Stepwise Porphyrin Degradation
Mechanisms Induced by HemeOxygenase and Cytochrome P450
Stille Coupling
S. P. H. Mee, V. Lee,
J. E. Baldwin*
1132 – 1136
Stille Coupling Made Easier—The
Synergic Effect of Copper(i) Salts and
the Fluoride Ion
1040
selectivity (almost no organic byproducts)
and high recovery of the catalyst.
CsF and CuI do the trick: Stille coupling
reactions of aryl/vinyl iodides, triflates,
and bromides with aryl/vinyl stannanes
are greatly enhanced by the inclusion of
CsF and CuI in the reaction mixture (see
scheme; Conditions A: [Pd(PPh3)4]/CsF/
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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multicomponent assembly of diverse
nitriles. The chelation-controlled conjugate addition–alkylation installs three new
stereocenters (see scheme), thereby generating substituted nitriles that are ideal
terpenoid precursors as illustrated in the
synthesis of epi-dehydroabietic acid.
CuI/DMF/45 8C; Conditions B: PdCl2/
PtBu3/CsF/CuI/DMF/45 8C).
Angew. Chem. Int. Ed. 2004, 43, 1036 – 1043
Angewandte
Chemie
Magnetic Properties
A relaxing time: A dramatic increase of the
energy barrier (Ueff ) in tetrairon(iii)
single-molecule magnets can be achieved
by simple chemical modification. Sitespecific replacement of the six methoxide
bridges in [Fe4(OMe)6(dpm)6]
(Hdpm = dipivaloylmethane; Ueff/
kB = 3.5 K) with two tripodal 1,1,1-tris(hydroxymethyl)ethane (H3thme) ligands
affords the compound [Fe4(thme)2(dpm)6]
(see figure) with Ueff/kB = 15.6(2) K and a
magnetic relaxation time exceeding
1000 s below 0.2 K.
A. Cornia,* A. C. Fabretti, P. Garrisi,
C. MortalW, D. Bonacchi, D. Gatteschi,
R. Sessoli, L. Sorace, W. Wernsdorfer,
A.-L. Barra
1136 – 1139
Energy-Barrier Enhancement by Ligand
Substitution in Tetrairon(iii) SingleMolecule Magnets
Membranes of gold nanotubes in polycarbonate films are used to study catalytic
reactions at gas–liquid interfaces. The
catalytic properties of gold for CO oxidation with O2 can be enhanced by liquid
water and promoted by increasing the
pH value of the solution. The membrane
is sandwiched between other membranes
that contain thiol-functionalized gold
nanotubes, which control mass transport
to the central reaction zone (see picture).
Nanotubes as Catalysts
M. A. Sanchez-Castillo, C. Couto,
W. B. Kim, J. A. Dumesic*
1140 – 1142
Gold-Nanotube Membranes for the
Oxidation of CO at Gas–Water
Interfaces
DNA Recognition
A. M. Whitney, S. Ladame,
S. Balasubramanian*
1143 – 1146
Templated Ligand Assembly by Using
G-Quadruplex DNA and Dynamic
Covalent Chemistry
Reversible disulfide chemistry is used to
identify ligands that bind G-quadruplex
DNA from a small dynamic combinatorial
library (DCL) (see scheme). The biological
macromolecular target is shown to induce
an equilibrium shift. Surface plasmon
resonance demonstrates that the two
amplified species bind the quadruplex
DNA.
Long-range forces (capillary force) are
used in the self-assembly of three-dimensional (3D) micropatterns of aligned
carbon nanotubes films. This method
involves the spreading of a droplet of
water after the growth of the carbon
nanotube film. Controlling the density of
the carbon nanotube film is crucial to the
formation of 3D patterned structures (see
picture).
Angew. Chem. Int. Ed. 2004, 43, 1036 – 1043
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Carbon Nanotubes
H. Liu, S. Li, J. Zhai, H. Li, Q. Zheng,
L. Jiang,* D. Zhu
1146 – 1149
Self-Assembly of Large-Scale
Micropatterns on Aligned Carbon
Nanotube Films
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1041
Contents
Crystal Growth
P. K. Thallapally, R. K. R. Jetti, A. K. Katz,
H. L. Carrell, K. Singh, K. Lahiri, S. Kotha,
R. Boese,* G. R. Desiraju* 1149 – 1155
Polymorphism of 1,3,5-Trinitrobenzene
Induced by a Trisindane Additive
The most stable is not necessarily the
most easy to obtain! Two new stable
crystal forms of the 120 year old compound sym-trinitrobenzene are reported.
Analyzing Zeolites
S. Chenevarin,
F. Thibault-Starzyk*
Probing pores: Adsorbed species on a
zeolite are perturbed by pressure jumps
(see picture; top), relaxation by means of
diffusion and adsorption follows and is
monitored by fast IR (middle). 2D maps
are obtained by a second Fourier transform (bottom): the spectrum of each
adsorbate/site pair is distinguished.
1155 – 1158
Two-Dimensional IR Pressure-Jump
Spectroscopy of Adsorbed Species for
Zeolites
Antimicrobial Agents
D. Liu, S. Choi, B. Chen, R. J. Doerksen,
D. J. Clements, J. D. Winkler, M. L. Klein,
W. F. DeGrado*
1158 – 1162
Nontoxic Membrane-Active Antimicrobial
Arylamide Oligomers
These elusive forms have been obtained
by the use of an additive, trisindane, that
can act as a mimic in the crystallization
experiment (see scheme).
Cracking the case: Aryl amide oligomers
with amphiphilic secondary structure
were designed that attack bacteria by
lysing their membranes. A variety of
groups were appended to the lead compound to adjust its overall charge, hydrophobicity, and hydrophobic moment. An
Arg-containing oligomer (see figure) was
found to have good antimicrobial activity
and low toxicity towards human
erythrocytes.
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
The issues for February 2004 appeared online on the following dates
Issue 5: January 21 · Issue 6: January 27 · Issue 7: February 2 · Issue 8: February 11
1042
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 1036 – 1043
Angewandte
Chemie
Service
Keywords
1164
Authors
1165
Sources
A17
Vacancies
A19
Preview
1167
Corrigendum
*
In the Review “Modern Synthetic Methods
for Copper-Mediated C(aryl) O, C(aryl)
N, and C(aryl) S Bond Formation” by
S. V. Ley and A. W. Thomas (Angew. Chem.
Int. Ed. 2003, 42, 5400–5449), the “Avendano-Modified Ullmann Condensation
Reaction” (Section 1.1, Equation 11)
should be correctly termed the “Barton
Plumbane-Modified Ullmann Condensation Reaction”.
Furthermore, the following important references are missing: D. H. R. Barton, N.
Yadav-Bhatnagar, J.-P. Finet, J. Khamsi,
Tetrahedron Lett. 1987, 28, 3111–3114;
D. H. R. Barton, D. M. X. Donnely, J.-P.
Finet, P. J. Guiry, Tetrahedron Lett. 1989,
30, 1377–1380; D. H. R. Barton, D. M. X.
Donnely, J.-P. Finet, P. J. Guiry, J. Chem.
Soc. Perkin Trans. 1 1991, 2095–2102.
Apology
*
In the Communication “Chiral, Porous,
Hybrid Solids for Highly Enantioselective
Heterogeneous Asymmetric Hydrogenation of b-Keto Esters” by A. Hu, H. L. Ngo,
and W. Lin (Angew. Chem. Int. Ed. 2003,
Angew. Chem. Int. Ed. 2004, 43, 1036 – 1043
42, 6000–6003), the authors neglected to
cross-reference their thematically related
communication in J. Am. Chem. Soc. 2003,
125, 11 490–11 491. The latter publication
reported the hydrogenation of aromatic
www.angewandte.org
ketones with up to 99.2% ee by a different
mechanism in the presence of a different
[Ru(4,4’-binap)(diamine)Cl2]–derived
solid catalyst. The authors apologize for
this accidental oversight.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1043
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