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Graphical Abstract Angew. Chem. Int. Ed. 242003

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Contents
News
S. Mann Elected Fellow of the Royal
Society
2703
W. Lubitz Receives Bruker Prize
D. Seebach Receives Prize during Liebig
Memorial Colloquium
Books
Aqueous Organometallic Catalysis
2704
Ferenc Joó
reviewed by Boy Cornils
Enzyme Kinetics
2705
Alejandro G. Marangoni
reviewed by Thorsten Friedrich
Highlights
Hydroamination
P. W. Roesky,* T. E. M.ller*
2708 – 2710
Enantioselective Catalytic Hydroamination of Alkenes
Macrolide Syntheses
L. O. Haustedt, I. V. Hartung,
H. M. R. Hoffmann*
2711 – 2716
The Total Syntheses of Phorboxazoles—
New Classics in Natural Product
Synthesis
Catalytically to chirality: Enantioselective
catalytic hydroamination (see scheme) is
one of the major challenges in synthetic
organic and organometallic chemistry and
offers a very attractive synthetic pathway
to chiral amines. Recent progress made
with this reaction is presented.
The marine sponge metabolites phorboxazoles A (see structural formula) and B
were the targets of several clever total
syntheses, whose special features are
described in this Highlight. Now that the
synthetic entry to these compounds has
been cleared, their cytostatic activity can
be studied thoroughly in vitro and in vivo.
Reviews
Structure-Based Drug Design
A. M. Davis,* S. J. Teague,
G. J. Kleywegt
2718 – 2736
Application and Limitations of X-ray
Crystallographic Data in Structure-Based
Ligand and Drug Design
2696
A main source of information on protein–
ligand complexes is X-ray crystallography.
In the structure shown oleic acid (orange)
is complexed to an IFABP mutant (green);
the experimentally determined electron
density is represented by a blue mesh.
Uncertainties in the atomic model can
have far-reaching consequences when this
model is subsequently used in manual
design, docking, scoring, and virtual
screening.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 2696 – 2702
Angewandte
Chemie
Communications
pH-Induced Changes in Conformation
C. Dolain, V. Maurizot,
I. Huc*
Extensions and compressions on the
molecular scale: A synthetic oligomer
unfolds from a helical to a linear conformation upon partial and selective pro-
tonation and refolds into another helical
conformation upon further protonation
(see scheme).
J. G. Moore, E. J. Lochner, C. Ramsey,
N. S. Dalal, A. E. Stiegman* 2741 – 2743
Transparent, Superparamagnetic
KIx CoIIy [FeIII(CN)6]–Silica Nanocomposites
with Tunable Photomagnetism
Stereoselective Oxygenation
Impressions of enzymes: A stable naphthoxyl radical was formed in the cavity of
an iron porphyrin by peroxy acid oxidation.
The intermediate was characterized by
spectroscopic methods. This reaction was
applied to the catalytic oxygenation of Z,Z1,4-diene regio- and stereoselectively to
give the corresponding alcohol under an
O2 atmosphere (see picture). This is the
first example of a mimic of the active site
of the prostaglandin H synthases.
Angew. Chem. Int. Ed. 2003, 42, 2696 – 2702
Protonation-Induced Transition between
Two Distinct Helical Conformations of a
Synthetic Oligomer via a Linear
intermediate
Photomagnetic Nanocomposites
Moldable magnetism: Tunable photomagnetism is exhibited by homogeneous,
optically transparent, moldable silica
xerogel nanocomposites containing the
ferromagnetic Prussian blue analogue
KxCoIIy [FeIII(CN)6]z. These materials also
show a blue-shifted intervalence chargetransfer band and superparamagnetic
behavior. The picture shows the temperature dependence of the field-cooled (FC)
and zero-field-cooled (ZFC) dc magnetization m of a xerogel sample (inset).
For the USA and Canada:
ANGEWANDTE CHEMIE International
Edition (ISSN 1433-7851) is published weekly
by Wiley-VCH PO Box 191161, D 69451 Weinheim, Germany. Air freight and mailing in the
USA by Publications Expediting Inc. 200 Meacham Ave., Elmont, NY 11003. Periodicals
2738 – 2740
E. Matsui, Y. Naruta,* F. Tani,
Y. Shimazaki
2744 – 2747
An Active-Site Model of Prostaglandin H
Synthase: An Iron “Twin-Coronet” Porphyrin with an Aryloxyl Radical Overhang
and Its Catalytic Oxygenation of 1,4-Diene
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
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price for institutions: Europe E 2998.00/
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delivery); for individuals who are personal
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are retired or self-employed consultants, print
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Europe E 248.00/Outside Europe US$ 348.00.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2697
Contents
Fullerenes in Calixarenes
G.-B. Pan, J.-M. Liu, H.-M. Zhang,
L.-J. Wan,* Q.-Y. Zheng,
C.-L. Bai*
2747 – 2751
Configurations of a Calix[8]arene
and a C60/Calix[8]arene Complex on a
Au(111) Surface
Having a ball: Molecules of a calix[8]arene
derivative, and the inclusion complex it
forms with C60 (see schematic), can be
adsorbed onto a Au(111) surface in
solution to yield self-organized highly
ordered arrays. The structures of the two
Polymer-Coated Gold Nanoparticles
K. Ohno, K. Koh, Y. Tsujii,
T. Fukuda*
A brush with gold: Gold nanoparticles
with a narrow size distribution have been
coated with well-defined, high-density
polymer brushes (see AFM image) by
means of surface-initiated living radical
polymerization. The gold nanoparticles
have formed a 2D array with a high degree
of structural order and exceptional controllability of the interparticle distance.
2751 – 2754
Fabrication of Ordered Arrays of Gold
Nanoparticles Coated with High-Density
Polymer Brushes
meso–meso-Linked ZnII Diporphyrin
H. Shinmori, T. K. Ahn, H. S. Cho, D. Kim,*
N. Yoshida, A. Osuka*
2754 – 2758
Dihedral-Angle Modulation of meso–mesoLinked ZnII Diporphyrin through Diamine
Coordination and Its Application to
Reversible Switching of Excitation Energy
Transfer
Small-Molecule Inhibitors
H. Razavi, S. K. Palaninathan, E. T. Powers,
R. L. Wiseman, H. E. Purkey,
N. N. Mohamedmohaideen,
S. Deechongkit, K. P. Chiang,
M. T. A. Dendle, J. C. Sacchettini,
J. W. Kelly*
2758 – 2761
Benzoxazoles as Transthyretin Amyloid
Fibril Inhibitors: Synthesis, Evaluation,
and Mechanism of Action
2698
arrays have been investigated by scanning
tunnelling microscopy, which gives clear
evidence of the inclusion of the fullerene
molecules. The stable configuration and
well-defined arrays should be useful for
the construction of nanostructures.
The dihedral angle between the two
porphyrins in meso–meso-linked ZnII
diporphyrin can be modulated effectively
by adding 1,7-diaminoheptane, which
coordinates at the both ZnII centers (see
picture). This mechanical torsion gives
rise to a decrease in the energy of the S1
state in the meso–meso-linked ZnII-diporphyrin subunit, and results in the change
in direction of the energy transfer in the
excited state. This process can be reversed
by adding acetic acid.
Benzoxazoles pevent misfolding: Benzoxazole-based inhibitors of transthyretin
(TTR) amyloid fibril formation are among
the most effective found to date. They
stabilize TTR against both acid-mediated
misfolding and urea denaturation by raising the activation barrier to tetramer
dissociation, the rate-limiting step for
amyloid formation. The figure depicts the
cocrystal structure of one of the better
benzoxazole inhibitors bound to TTR.
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 2696 – 2702
Angewandte
Chemie
Potassium slips a disk: A novel slipped h2coordination mode with differing K N
separations is found in the complexes
(3,5-diisopropyltriazolato)([18]crown-6)potassium and (phenyltetrazolato)
([18]crown-6)potassium (see diagram),
which are thus extremely rare examples of
terminal h2 coordination of nitrogen-rich
azolato ligands.
Azolato Coordination Modes
W. Zheng, M. J. Heeg,
C. H. Winter*
2761 – 2764
Coordination of 3,5-Diisopropyl-1,2,4-triazolato and 5-Phenyltetrazolato Ligands
to the [K([18]crown-6)]+ Fragment: Structural Insight into the Coordination of
Nitrogen-Rich Azolato Ligands to Single
Metal Centers
Organosulfur Conducting Bridges
N. Gautier, F. Dumur, V. Lloveras,
J. Vidal-Gancedo, J. Veciana, C. Rovira,*
P. Hudhomme*
2765 – 2768
Radical bridge design: The diquinonetetrathiafulvalene (TTF) species shown
exhibits effective electron coupling
between the quinone centers which is
mediated by the TTF bridge. Stepwise
one-electron reduction of the molecule
occurs, and the observed potential difference between reduction events is an
indication that reduction of the second
quinone unit is affected by the radical
species already formed on the other side
of the bridge.
Intramolecular Electron Transfer
Mediated by a Tetrathiafulvalene Bridge
in a Purely Organic Mixed-Valence System
Pd and B in 1,4-Additions
T. Nishikata, Y. Yamamoto,
N. Miyaura*
A cationic palladium complex was found
to be an efficient catalyst for the 1,4addition of aryl boronic acids to enones at
room temperature (see scheme; X = ClO4,
OTf, BF4, PF6, or SbF6); Tf = trifluoromethanesulfonyl).
Conjugate Addition of Aryl Boronic Acids
to Enones Catalyzed by Cationic
Palladium(ii)–Phosphane Complexes
Gold(i)/Gold(iii) Perovskites
Chemistry with a golden touch: The first
examples of organic-based mixed-valent
AuI/AuIII layered perovskites are reported
(see picture). The crystal structures of
the new hybrid compounds feature
[AuI2] /[AuI4] layers pillared by I3 ions
and appropriate organic dications. The
measured optical band gaps of the new
organic–inorganic semiconductors are
smaller than the value for Cs2Au2I6.
Angew. Chem. Int. Ed. 2003, 42, 2696 – 2702
2768 – 2770
L. M. Castro-Castro,
A. M. Guloy*
2771 – 2774
Organic-Based Layered Perovskites of
Mixed-Valent Gold(i)/Gold(iii) Iodides
www.angewandte.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2699
Contents
Alkane Adsorption on Zeolites
Picking on the short one: Molecular
arrangement of long-chain hydrocarbon
mixtures in the 2D pore system of ZSM-5
(depicted) causes strong and unexpected
selectivity effects to occur. The formation
of azeotropes and selective uptake of the
shortest molecule from mixtures is
observed for a range of hydrocarbon
mixtures, and has significant implications
for separative applications.
J. F. M. Denayer,* K. De Meyer,
J. A. Martens, G. V. Baron
2774 – 2777
Molecular Competition Effects in LiquidPhase Adsorption of Long-Chain n-Alkane
Mixtures in ZSM-5 Zeolite Pores
Phosphorus–Carbon Compounds
J. M. Lynam, M. C. Copsey, M. Green,*
J. C. Jeffery, J. E. McGrady, C. A. Russell,*
J. M. Slattery, A. C. Swain
2778 – 2782
Selective Preparation of the
[3,5-tBu2-1,2,4-C2P3] Ion and Synthesis
and Structure of the Cationic Species
nido-[3,5-tBu2-1,2,4-C2P3]+, Isoelectronic
with [C5R5]+
Zeolites from Plant Leaves
V. Valtchev,* M. Smaihi, A.-C. Faust,
L. Vidal
2782 – 2785
Biomineral-Silica-Induced Zeolitization of
Equisetum Arvense
Building pyramids: The first P–C cluster,
namely, the novel nido species 2, is readily
prepared from 1 (* = CtBu), which is also
an excellent precursor for the selective
synthesis of the anion 3. DFT calculations
show that there is a switch in the global
minimum, on the introduction of three P
atoms (MCH) into the [C5H5]+ ion, from
cyclic-unsaturated to saturated cage species, such as 2.
Turning over a new leaf: Leaves of Equisetum Arvense can be successfully treated
to yield zeolite-type structures which, after
calcination, are transformed into a
micro-/mesoporous material which keeps
all of the morphological features of the
vegetal template (see SEM image). Faithful zeolitization of the plant structure is
induced by the highly reactive biomorphic
silica deposited in the epidermal surface
of the plant.
Enolexo Aldol Reactions
C. Pidathala, L. Hoang, N. Vignola,
B. List*
2785 – 2788
Direct Catalytic Asymmetric Enolexo
Aldolizations
32 years after the first, and still the only,
catalytic asymmetric intramolecular aldol
reaction was published in this journal, the
proline-catalyzed Hajos–Parrish–Eder–
Sauer–Wiechert reaction is extended for
the first time to catalytic asymmetric
2700
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
enolexo aldolizations. The process provides substituted cyclohexanes in excellent diastereo- and enantioselectivities.
For example, heptanedial is converted into
the corresponding cyclic anti-configured
aldol in 99 % ee (see scheme).
Angew. Chem. Int. Ed. 2003, 42, 2696 – 2702
Angewandte
Chemie
Peroxo-Bridged Heme–Copper Complex
A stable bridge: A peroxo-bridged Fe–O2–
Cu complex (see picture) was synthesized
and isolated as crystals. The X-ray structure analysis revealed that the Fe–O2–Cu
moiety has a m-h2 :h1 coordination mode; a
peroxo ligand is bound to Fe in a side-on
fashion with only one oxygen atom of the
peroxide bound to Cu. The two metal ions
(high-spin FeIII and CuII) were strongly
coupled in an antiferromagnetic fashion,
thus resulting in a total spin of S = 2.
T. Chishiro, Y. Shimazaki, F. Tani, Y. Tachi,
Y. Naruta,* S. Karasawa, S. Hayami,
Y. Maeda
2788 – 2791
Isolation and Crystal Structure of a
Peroxo-Bridged Heme – Copper Complex
Mononitrobenzene derivatives and 1chloro-1-arylsulfonyl-methyl anions react
with formation of stable sH adducts (see
scheme; Ts = tosyl) which are observed by
UV/Vis and NMR spectroscopy. The
generally accepted energy profiles for
vicarious nucleophilic substitutions
with sH adducts as high-energy
intermediates have to be revised.
Vicarious Substitutions
T. Lemek,* M. Ma˛kosza, D. S. Stephenson,
H. Mayr*
2793 – 2795
Direct Observation of the Intermediate in
Vicarious Nucleophilic Substitutions of
Hydrogen
Catalytic Diels–Alder Reactions
G. Hilt,* K. I. Smolko
Versatile building blocks with a dihydroaromatic vinylic boron substructure
can be generated efficiently by cobaltcatalyzed Diels–Alder reactions and used
in Suzuki coupling reactions for the synthesis of functionalized polycyclic compounds (see scheme).
2795 – 2797
Alkynylboronic Esters as Efficient Dienophiles in Cobalt-Catalyzed Diels–Alder
Reactions
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
The publication of Communications labeled with this symbol has been accelerated because of their topical or highly competitive
nature.
Service
Keywords
2798
Authors
2799
Vacancies
Preview
Angew. Chem. Int. Ed. 2003, 42, 2696 – 2702
www.angewandte.org
2707, 2802
2803
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2701
Contents
Corrigenda
*
In the Communication “A Zeolite Structure (ITQ-13) with Three Sets of MediumPore Crossing Channels Formed by 9- and
10-Rings” by A. Corma et al. in Angew.
Chem. 2003, 115, 1188–1191; Angew.
Chem. Int. Ed. 2003, 42, 1156–1159, it
should have been made clear early on in
the manuscript that the synthesis of the
ITQ-13 material was first reported in a
patent published in 2002 (T. Boix, M.
Puche, M. A. Camblor, A. Corma, US
Patent 6 471 941 B1, 2002; reference [12] in
the manuscript). Furthermore, owing to
an editorial error the reference to this
patent was wrongly introduced into
the Experimental Section, where reference
[13] should read reference [12] and vice
versa.
We apologize to our readers and to the
authors of the above mentioned patent
if this mistake has resulted in any misunderstanding.
In the Communication by S. Shimada,
M. Tanaka et al. published in Angew.
Chem. Int. Ed. 2003, 42, 1845–1848, the
incorrect formula was printed on p. 1845.
The correct formula is that shown below.
Furthermore, the e-mail address for Pro-
fessor Tanaka should be
m.tanaka@res.titech.ac.jp.
tBu
N
Bi
R
3a – 3g
2702
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3a:
3b:
3c:
3d:
3e:
3f:
3g:
R = Ph
R = 3,5-(CF3)2C6H3R = 3,4-(CH2O2)C6H3R = 2,4,6-(MeO)3C6H2R = CH2=C(Me)R = Br
R = Cl
www.angewandte.org
Avelino Corma
Corresponding Author
Peter GSlitz
Editor
Me
N
Bi
R
4
Angew. Chem. Int. Ed. 2003, 42, 2696 – 2702
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