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Graphical Abstract Angew. Chem. Int. Ed. 242005

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Contents
The following Communications have been judged by at least two referees to be ?very
important papers? and will be published online at www.angewandte.org soon:
C.-J. Wang, X. Sun, X. Zhang*
Enantioselective Hydrogenation of Allylphthalimides: An
Efficient Method For Synthesis of b-Methyl Chiral Amines
T. Matsuda, M. Makino, M. Murakami*
Synthesis of Seven-Membered-Ring Ketones by Arylative Ring
Expansion of Alkyne-Substituted Cyclobutanones
G. Gopalakrishnan, J.-M. Segura, D. Stamou, C. Gaillard, M. Gjoni,
R. Hovius, K. J. Schenk, P. A. Stadelmann, H. Vogel*
Synthesis of Nanoscopic Optical Fibers using Lipid Membranes
as Templates
K. Ohmori, M. Tamiya, M. Kitamura, H. Kato, M. Oorui, K. Suzuki*
Regio- and Stereocontrolled Total Synthesis of Benanomicin B
Y. Ding, A. Mathur, M. Chen, J. Erlebacher*
Epitaxial Casting of Nanotubular Mesoporous Platinum
N. Shibata,* J. Kohno, K. Takai, T. Ishimaru, S. Nakamura, T. Toru,*
S. Kanemasa
Highly Enantioselective Catalytic Fluorination and Chlorination
Reactions of Carbonyl Compounds Capable of Two-Point Binding
Web Sites
Chemical Genealogy: Lessons from
History
P. Cintas
3648
Evolutionary Methods in Biotechnology
Susanne Brakmann,
Andreas Schwienhorst
reviewed by N. Budisa
3649
Chemistry and Technology of Flavors and
Fragrances
David J. Rowe
reviewed by A. Herrmann
3650
http://www.scs.uiuc.edu/~mainzv/
Web_Genealogy/
Books
Highlights
Supramolecular Chemistry
K. Rissanen*
Welcome to the superbowl! The coupling
of five resorcinarene-based compounds
affords the covalent bowl-shaped analogues of hydrogen-bonded hexameric
capsular assemblies (see picture). Such
molecules offer stability, solubility, and
functionality beyond those of their noncovalent cousins, and provide interesting
insight into intracavity reactions,
molecular transport, and complexation
processes.
3652 ? 3654
Very Large Container Molecules
Minireviews
IIII and IV Reagents
T. Wirth*
3656 ? 3665
Hypervalent Iodine Chemistry in
Synthesis: Scope and New Directions
3638
New reagents and reactions show the
potential of hypervalent iodine compounds in organic synthesis: The understanding of the structures and reactivities
of iodine(iii) and iodine(v) compounds
forms the basis for novel synthetic
strategies and their application in the
synthesis of complex natural products.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3638 ? 3646
Angewandte
Chemie
Reviews
Enzyme Mechanisms
L. Poppe, J. Rtey*
In the enzymatic superelectrophile
5-methylene-3,4-dihydroimidazol-4-one
(MIO), delocalization of the lone pair of
electrons on the nitrogen atom into the
Michael system is prohibited for stereoelectronic reasons, and nucleophilic
attack at the exocyclic double bond makes
the ring aromatic. The MIO group in
histidine and phenylalanine ammonialyases activates a b hydrogen atom of the
corresponding amino acid and facilitates
the elimination of ammonia (see
scheme).
3668 ? 3688
Friedel?Crafts-Type Mechanism for the
Enzymatic Elimination of Ammonia from
Histidine and Phenylalanine
Communications
Oxoiron(iv) Complexes
Stabilizing the oxoiron(iv) unit: From a
combination of X-ray crystallography,
NMR spectroscopy, and DFT calculations,
the relative thermal stabilities of two
oxoiron(iv) complexes with pentaaza
ligands, such as that shown in the picture,
can be ascribed to the number of pyridine
rings that are oriented parallel to the Fe=
O bond. (Fe pink, N blue, O red, C black.)
E. J. Klinker, J. Kaizer, W. W. Brennessel,
N. L. Woodrum, C. J. Cramer,*
L. Que, Jr.*
3690 ? 3694
Structures of Nonheme Oxoiron(iv)
Complexes from X-ray Crystallography,
NMR Spectroscopy, and DFT Calculations
All aglow: A new class of highly luminescent dyes is built by the attachment of a
pyrene fragment to the boron center of a
boradiazaindacene moiety through an
ethynyl unit (see scheme). Very efficient
energy transfer from the pyrene to the
indacene center produces virtual large
Stokes shifts, which are maintained, along
with strong luminescence (F = 32?45 %)
when the dyes are attached to proteins
such as bovine serum albumin.
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Angew. Chem. Int. Ed. 2005, 44, 3638 ? 3646
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
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individuals who are personal members of a
www.angewandte.org
Fluorescence Imaging
G. Ulrich,* C. Goze, M. Guardigli, A. Roda,
R. Ziessel*
3694 ? 3698
Pyrromethene Dialkynyl Borane
Complexes for ?Cascatelle? Energy
Transfer and Protein Labeling
national chemical society, or whose institution
already subscribes, or who are retired or selfemployed consultants, print only: US$ 394.00.
Postage and handling charges included. All
Wiley-VCH prices are exclusive VAT.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3639
Angewandte
Chemie
Crystal Growth
The critical length and density of the
steps, rather than step morphology and
velocity of deposition, are useful for
understanding the effectiveness of the
additive molecules in modifying the crystallization kinetics in biomineralization.
This biological control stems from a
change in solid?solution interfacial energies, which delays the formation of active
steps on the growing crystal face (see
picture).
R. Tang, M. Darragh, C. A. Orme, X. Guan,
J. R. Hoyer,
G. H. Nancollas*
3698 ? 3702
Control of Biomineralization Dynamics by
Interfacial Energies
Enantioselective Fluorination
M. Marigo, D. Fielenbach, A. Braunton,
A. Kj鎟sgaard,
K. A. J鴕gensen*
3703 ? 3706
An easy protocol has been developed for
the formation of stereogenic carbon?
fluorine centers by the organocatalytic
asymmetric a-fluorination of aldehydes 1.
The 2-fluoroaldehydes 4 are formed with 2
as the fluorinating agent and only 1 mol %
of a sterically demanding silylated prolinol
3 as catalyst. The 2-fluoroaldehydes are
subsequently reduced to the corresponding alcohols 5 without loss of enantiomeric excess.
Enantioselective Formation of
Stereogenic Carbon?Fluorine Centers by a
Simple Catalytic Method
Enantioselective Fluorination
D. D. Steiner, N. Mase,
C. F. Barbas, III*
Linear and branched aldehydes are asymmetrically a-fluorinated with l-prolineand pyrrolidine-based organocatalysts
(see scheme; NFSi: N-fluorobenzenesulfonamide). In the first case, yields and
enantioselectivities were high; in the
second, the yields remained high and
the enantioselectivities were moderate.
Significantly, linear aldehydes were only
monofluorinated.
3706 ? 3710
Direct Asymmetric a-Fluorination of
Aldehydes
Bioorganic Chemistry
G. Bansal, J. E. I. Wright, C. Kucharski,
H. Uludag?*
3710 ? 3714
A Dendritic Tetra(bisphosphonic acid) for
Improved Targeting of Proteins to Bone
Close to the bone: A dendritic molecule
that contains four bone-seeking bisphosphonic acid groups (see picture) has been
prepared for targeting proteins to bone
tissue. The tetra(bisphosphonic acid)
Angew. Chem. Int. Ed. 2005, 44, 3638 ? 3646
molecule provides a high density of
bisphosphonic acid groups per attachment site at the protein and will aid the
design of bone-seeking proteins with
minimal modification.
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3641
Contents
Natural Product Synthesis
P. S. Baran,* R. A. Shenvi,
C. A. Mitsos
One-of-a-kind. A bromine-induced rearrangement has been designed for the
formation of the spiro-b-lactam ring present in the structurally unique chartelline
alkaloids (see picture of chartelline A).
This method is used in combination with
others to provide rapid access to the
carbocyclic skeletons of the chartelline,
securine, and securamine alkaloids.
3714 ? 3717
A Remarkable Ring Contraction En Route
to the Chartelline Alkaloids
Metal triangles: The first stable telluradistibirane and telluradibismirane derivatives (see structure) have been successfully synthesized by the reaction of an
overcrowded distibene (BbtSb=SbBbt)
and dibismuthene (BbtBi=BiBbt) with
nBu3P=Te, respectively. (C cyan, Si red).
Main Group Chemistry
T. Sasamori, E. Mieda, N. Takeda,
N. Tokitoh*
3717 ? 3720
Telluradistibirane and Telluradibismirane:
Three-Membered Heterocycles of Heavier
Main Group Elements
Nanoparticles
P. Ionita, B. C. Gilbert,
V. Chechik*
3720 ? 3722
Radical Mechanism of a Place-Exchange
Reaction of Au Nanoparticles
Spin-trapping experiments show the formation of sulfur-centered radicals during
Aqueous Foams
B. P. Binks,* T. S. Horozov
Foamability and foam stability: By using a
novel dispersion method, suitably hydrophobic silica particles can be dispersed in
water to form very stable foams through
adsorption of particle aggregates at the
surfaces of micrometer-sized bubbles.
The optical microscope image shows air
bubbles in pure water stabilized solely by
partially hydrophobic silica nanoparticles
(scale bar: 50 mm).
3722 ? 3725
Aqueous Foams Stabilized Solely by Silica
Nanoparticles
3642
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
a ligand-exchange reaction between Ph3Pprotected Au nanoparticles and alkanethiols in air (see picture). Oxidation of the
alkanethiols by molecular O2 adsorbed on
the nanoparticles is proposed as the key
step. The feasibility of such a process is
demonstrated by the Au-nanoparticle-catalyzed oxidation of BH4 and tBuOOH
with air.
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Angew. Chem. Int. Ed. 2005, 44, 3638 ? 3646
Angewandte
Chemie
Metallooctaphyrin complexes: Dimetalation of perfluorinated [36]octaphyrin with
copper(ii) results in the hydrolytic ring
opening of one of the pyrrole rings (see
structure), whereas with silver ions perfluorinated [36]octaphyrin and meso-pentafluorophenyl-substituted [36]octaphyrin
gave disilver(i) complexes of [34]octaphyrin.
Metalloporphyrinoids
S. Shimizu, Y. Tanaka, K. Youfu,
A. Osuka*
3726 ? 3729
Dicopper and Disilver Complexes of
Octaphyrin(1.1.1.1.1.1.1.1): Reversible
Hydrolytic Cleavage of the Pyrrolic Ring to
a Keto?Imine
Chemical Traps
N. MacLeod, F. J. Williams, M. S. Tikhov,
R. M. Lambert*
3730 ? 3732
An Electrochemically Driven and
Electrochemically Regenerated NOx Trap
Fort NOx: The principle of an NOx trap
based on the use of solid alkali-metal-ion
conductors is demonstrated. The trap
efficiently stores NOx and subsequently
releases mainly NO2 under isothermal
conditions (see scheme); this is relevant
to the abatement of nitrogen oxides in the
exhaust gases of fuel-efficient automotive
engines.
Strained Polycycles
An unprecedented skeletal reorganization
initially hindered a concise route based on
a tandem [4�/[3� nitroalkene
cycloaddition for the synthesis of the
strained title compound. Conditions to
suppress the observed dyotropic rearrangement were developed, and X-ray crystallographic analysis of the BF3 derivative
(see picture) of the azafenestrane
revealed significant planarization around
the central carbon atom.
S. E. Denmark,*
J. I. Montgomery
3732 ? 3736
Synthesis of cis,cis,cis,cis-[5.5.5.4]-1Azafenestrane with Discovery of an
Unexpected Dyotropic Rearrangement
Indole Synthesis
K. C. Nicolaou,* S. H. Lee, A. A. Estrada,
M. Zak
3736 ? 3740
Generation (1!2) and trapping (2!3) of
the fleeting a,b-unsaturated nitrone
system 2 leads to the rare, biologically
important N-hydroxyindole 3 in syntheti-
Angew. Chem. Int. Ed. 2005, 44, 3638 ? 3646
cally useful yields. This structural motif is
found within the molecule of the antibiotic
nocathiacin I.
www.angewandte.org
Construction of Substituted
N-Hydroxyindoles: Synthesis of a
Nocathiacin I Model System
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3643
Contents
DNA Structures
D. Miyoshi, H. Karimata,
N. Sugimoto*
3740 ? 3744
Drastic Effect of a Single Base Difference
between Human and Tetrahymena
Telomere Sequences on Their Structures
under Molecular Crowding Conditions
Making a difference: Tetrahymena telomere sequences form well-ordered
G-wires in the presence of cosolutes,
whereas human telomere sequences
remain as compact G-quadruplexes (see
Host?Guest Systems
picture). A single base difference in telomere sequences therefore can affect telomere function under cell-like conditions.
The G-wire structure may be useful in the
design of DNA nanomaterials.
An accommodating host: A new capsuleshaped host molecule, the cavitand?porphyrin shown, reversibly encapsulates
single hydrocarbon molecules smaller
than propane (see picture). With the
exception of acetylene, the binding affinities are inversely correlated with the size
of the guest hydrocarbons.
J. Nakazawa, J. Hagiwara, M. Mizuki,
Y. Shimazaki, F. Tani,
Y. Naruta*
3744 ? 3746
Size-Selective and Reversible
Encapsulation of Single Small
Hydrocarbon Molecules by a
Cavitand?Porphyrin Species
Protein Trapping
R. W. Clarke, S. S. White, D. Zhou,
L. Ying,* D. Klenerman*
3747 ? 3750
Trapping of Proteins under Physiological
Conditions in a Nanopipette
Caught in a trap and on camera: A
nanopipette is used for electrodeless
dielectrophoresis and clear evidence is
shown, by using wide-field fluorescence
imaging (see image), for the reversible
trapping of Alexa-488-labeled proteins
Inclusion Complexes
J. Mohanty, W. M. Nau*
Exceptionally stable aqueous dye solutions, resistant towards aggregation as
well as unspecific adsorption to material
surfaces, and with improved photostability, in particular at high levels of irradiation, are obtained when the supramolecular host cucurbit[7]uril (CB7) is added to
a rhodamine 6G solution. Complexation
by CB7 (see picture) increases the fluorescence lifetime because of the low
polarizability inside the cucurbituril cavity.
3750 ? 3754
Ultrastable Rhodamine with Cucurbituril
3644
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
(protein G and immunoglobulin G) and
also of the fluorophore alone. The
dielectrophoretic concentration is
enhanced by at least a factor of 300 for
these fluorophore-labeled proteins.
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Angew. Chem. Int. Ed. 2005, 44, 3638 ? 3646
Angewandte
Chemie
Polyphosphorus Ligands
M. Scheer,* S. Deng, O. J. Scherer,
M. Sierka
3755 ? 3758
Different faces of phosphorus chemistry:
The reaction of the bicyclotetraphosphine
complex 1 with tBuCP leads to the first
1,2,3,4-tetraphosphaferrocene complex 2
and an allylic P3-bridged complex 3.
Cp??? = h5-C5H2tBu3.
Tetraphosphacyclopentadienyl and
Triphosphaallyl Ligands in Iron Complexes
Carbene Complexes
F. E. Hahn,* V. Langenhahn, T. Lgger,
T. Pape, D. Le Van
3759 ? 3763
Template Synthesis of a Coordinated
Tetracarbene Ligand with Crown Ether
Topology
A template-controlled reaction cascade
starting from [Pt(PMe3)4](CF3SO3)2 and 2azidophenyl isocyanide yields the tetracarbene complex [1](CF3SO3)2. The four
NH,NH-stabilized carbene ligands in [1]2+
can be bridged at the metal template by
reaction with N,N-dimethylformamide
(DMF) and diphosgene to give the coordinated cyclic tetracarbene ligand with
crown ether topology in complex [2](Cl)2.
The heat is on: In the first instance of
thermal reactivity of the terminal borylenes [(OC)5M=B=N(SiMe3)2] (M = Cr,
W), the new heterodinuclear complexes
[(OC)4M(m-CO){m-BN(SiMe3)2}Pd(PCy3)]
(see structure; M = Cr) are synthesized.
The compounds feature a semibridging
borylene ligand and, by virtue of the dative
PdB bonding interaction, represent the
only examples of terminal borylene species stabilized by a transition-metal base.
The unusual [5.3.2]bicyclic structure of the
insecticidal Amaryllidaceae alkaloids cri-
Angew. Chem. Int. Ed. 2005, 44, 3638 ? 3646
powellins A and B has been synthesized
for the first time by a sequence of Sharpless dihydroxylation, ring-closing metathesis (RCM), and intramolecular Heck
reaction (see scheme). The asymmetric
synthesis of the 1-epi aglycon proceeds
with virtually complete diastereo- and
enantioselectivity ( 98 % de, 98 % ee)
in 13 steps and an overall yield of 5.6 %.
www.angewandte.org
Borylene Complexes
H. Braunschweig,* D. Rais,
K. Uttinger
3763 ? 3766
Terminal Borylene Complexes Stabilized
by a Transition-Metal Base
Natural Product Synthesis
D. Enders,* A. Lenzen,
G. Raabe
3766 ? 3769
Asymmetric Synthesis of the 1-epi Aglycon
of the Cripowellins A and B
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3645
Contents
Theoretical Chemistry
P. Raiteri,* R. Marton?k,
M. Parrinello*
Gazing into the crystal ball: The prediction
of crystal structures is one of the most
challenging problems in theoretical
chemistry. In the metadynamics approach
described, the search for stable polymorphs is guided by the Gibbs free energy
and takes the role of temperature and
pressure fully into account. This method
was used to predict the polymorphs of
benzene (see picture) and solve many
contradictions and uncertainties about its
phase diagram.
3769 ? 3773
Exploring Polymorphism: The Case of
Benzene
Polyoxometalates
U. Kortz,* F. Hussain,
M. Reicke
Great balls of tungsten: Two polyoxotungstates with spectacular size (almost
1000 atoms), molar mass (approximately
33 000 g mol1), and spherical symmetry
have been synthesized. The dimethyltinsubstituted [{Sn(CH3)2(H2O)}24{Sn(CH3)2}12(A-XW9O34)12]36 ions (see polyhedral representation; X = P, As; red
octahedra WO6, yellow tetrahedra XO4)
consist of 12 (A-XW9O34) Keggin moieties
linked by 36 dimethyltin groups resulting
in a spherical structure with a cavity 8 in
diameter.
3773 ? 3777
The Ball-Shaped Heteropolytungstates
[{Sn(CH3)2(H2O)}24{Sn(CH3)2}12(A-XW9O34)12]36
Polyoxometalates
S. S. Mal, U. Kortz*
Anions get wheely big: A Cu20-containing
polyoxotungstate of large size and high
symmetry was synthesized by making use
of the template effect. The wheel-shaped
[Cu20Cl(OH)24(H2O)12(P8W48O184)]25 ion
(see picture; black W, turquoise Cu, yellow P, violet Cl, red O) is the first transition-metal-substituted derivative of
[H7P8W48O184]33 and incorporates more
paramagnetic 3d metal ions than any
other polyoxotungstate to date.
3777 ? 3780
The Wheel-Shaped Cu20
Tungstophosphate
[Cu20Cl(OH)24(H2O)12(P8W48O184)]25 Ion
Service
3646
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Keywords
3782
Authors
3783
Preview
3785
Angew. Chem. Int. Ed. 2005, 44, 3638 ? 3646
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