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Graphical Abstract Angew. Chem. Int. Ed. 232006

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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. Burke, Y. Shi*
Regio- and Enantioselective Epoxidation of Dienes by a Chiral
Dioxirane: Synthesis of Optically Active Vinyl cis-Epoxides
C.-W. So, H. Roesky,* J. Magull, R. Oswald
Synthesis and Characterization of [{PhC(NtBu)2}SiCl]: A Stable
Monomeric Chlorosilylene
H. Yu, S. Huang, H. Chokhawala, M. Sun, H. Zheng, X. Chen*
Highly Efficient Chemoenzymatic Synthesis of Naturally
Occurring and Non-Natural a2,6-Linked Sialosides: A
P. damsela a2,6-Sialyltransferase with Extremely Flexible Donor
Substrate Specificity
D. Rohde, C.-J. Yan, H.-J. Yan, L.-J. Wan*
From Lamellar to Hexagonal Self-Assembly of Bis(dioxaborin)
Molecules
Meeting Reviews
J. Krger, F. Grinberg
3732
Lixin Zhang, Arnold L. Demain
reviewed by F. von Nussbaum
3735
Metathesis reactions are among the most
important processes in organic synthesis.
The decisive breakthrough in making
these reactions practical for industrial
purposes, which range from the synthesis
of polymers to pharmaceuticals, came
with the discovery of the reaction
mechanism by Yves Chauvin and the
targeted development of transition-metalbased metathesis catalysts by Richard
Schrock and Robert Grubbs. The winners
of the Chemistry Nobel Prize in 2005
present first-hand accounts of these
developments.
A Closer Look at Nanoporous Materials
Books
Natural Products
Reviews
Metathesis Reactions
Y. Chauvin*
3740 – 3747
Olefin Metathesis: The Early Days (Nobel
Lecture)
R. R. Schrock*
3748 – 3759
Multiple Metal–Carbon Bonds for
Catalytic Metathesis Reactions (Nobel
Lecture)
R. H. Grubbs*
3760 – 3765
Olefin-Metathesis Catalysts for the
Preparation of Molecules and Materials
(Nobel Lecture)
3720
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
Angewandte
Chemie
Communications
Nickel Thiolates
A tale of two toroids: New cyclic nickel(ii)
thiolate complexes (see structures;
Ni green, S red, C purple) were synthesized by stepwise introduction of two
kinds of thiolates to a nickel(ii) center.
The flexible {Ni10S20} core configuration
crystallizes in different forms, either circular or ellipsoidal, depending on the
presence or absence of an encapsulated
guest molecule.
C. Zhang, S. Takada, M. K6lzer,
T. Matsumoto, K. Tatsumi* 3768 – 3772
Nickel(ii) Thiolate Complexes with a
Flexible cyclo-{Ni10S20} Framework
Drug Design
High-throughput screening of a library of
compounds has led to the identification of
a new structural class of human methionine aminopeptidases inhibitors. They
inhibited the processing of 14-3-3g in cells
and blocked proliferation of both endothelial cells and transformed cancer cell
lines. The picture shows the crystal
structure of the complex of one inhibitor
(yellow) with the type 1 human methionine aminopeptidase (blue CoII, red H2O).
X. Hu, A. Addlagatta, B. W. Matthews,*
3772 – 3775
J. O. Liu*
Identification of Pyridinylpyrimidines as
Inhibitors of Human Methionine
Aminopeptidases
Move over directed ortho-metalation, here
comes directed meta-metalation. The
unprecedented meta-zincation of two
anilides by a synergic mixed sodium/zinc
dialkyl–amide base is presented. The
orientation of the deprotonation of the
anilides is remarkably switched to the
meta site using this heterometallic mixedmetal system.
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
D. R. Armstrong, W. Clegg, S. H. Dale,
E. Hevia, L. M. Hogg, G. W. Honeyman,
R. E. Mulvey*
3775 – 3778
Directed meta-Metalation Using AlkaliMetal-Mediated Zincation
Molecular Devices
Spinning around: By insertion of a
bifunctional ligand that acts as an axle—
one end tethered to a silver surface, the
other bonded to the metal center of a
metalloporphyrin—an entire population
of porphyrin molecules can be induced to
spin. Removal of the axle quenches the
motion. The switching process may be
repeated an indefinite number of times.
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
Aromatic Substitution
O. P. H. Vaughan, F. J. Williams,
N. Bampos, R. M. Lambert* 3779 – 3781
A Chemically Switchable Molecular
Pinwheel
Meacham Ave., Elmont, NY 11003. Periodicals
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
Chemie, Wiley-VCH, 111 River Street, Hoboken,
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included. All prices are subject to local VAT/
sales tax.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3721
Angewandte
Chemie
Carbonaceous Materials
V. Budarin, J. H. Clark,* J. J. E. Hardy,
R. Luque, K. Milkowski, S. J. Tavener,
A. J. Wilson
3782 – 3786
Starbons: New Starch-Derived
Mesoporous Carbonaceous Materials
with Tunable Properties
A star is born: The complex molecular
architecture found in plants is used in the
design of new nanostructured materials.
Carbon-based mesoporous materials with
tunable surfaces and bulk properties can
be synthesized by the low-temperature
carbonization of expanded natural starches that are in turn prepared by a simple
gelatinization–retrogradation process.
The dynamic dual chirality of D2-symmetric saddle-shaped porphyrin 1 decreases
the stereochemical complexity of cocrystallization with racemic mandelic acid
derivatives, such as BrMA, and allows
spontaneous optical resolution (see picture). Each resulting cocrystal is porous
and consists of one-handed double-helical
porphyrin arrays in which chiral guests are
enantioselectively included.
In the groove: The “drugability” of protein–protein interaction domains is still a
matter of debate. The 3D structure of a
complex of a small organic ligand and the
AF6 PDZ domain revealed the creation of
a binding pocket by the ligand (see
picture). The derived compound is able to
compete with a natural peptide ligand of
the domain and represents a basic building block for the generation of selective
PDZ inhibitors.
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
Optical Resolution
Y. Mizuno, Md. A. Alam, A. Tsuda,
K. Kinbara, K. Yamaguchi,
T. Aida*
3786 – 3790
Hermaphroditic Chirality of a D2Symmetric Saddle-Shaped Porphyrin in
Multicomponent Spontaneous Optical
Resolution: Inclusion Cocrystals with
Double-Helical Porphyrin Arrays
Protein–Protein Interactions
M. Joshi, C. Vargas, P. Boisguerin, A. Diehl,
G. Krause, P. Schmieder, K. Moelling,
V. Hagen, M. Schade,*
H. Oschkinat*
3790 – 3795
Discovery of Low-Molecular-Weight
Ligands for the AF6 PDZ Domain
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3723
Contents
Water Chemistry
N. J. Singh, M. Park, S. K. Min, S. B. Suh,
K. S. Kim*
3795 – 3800
Magic and Antimagic Protonated Water
Clusters: Exotic Structures with Unusual
Dynamic Effects
It’s a kinda magic! Contrary to conventional wisdom that O H bonds associated with dangling hydrogen atoms and
those in the H3O+ ion in molecular
clusters display characteristic peaks in IR
spectra, a dynamic effect makes such
peaks disappear, even in the gas phase at
low temperatures. This finding helps solve
the long-standing problems of magic and
antimagic protonated water clusters with
21 (top structures) and 22 (bottom
structures) water molecules.
Chemosensors
D. Filippini, A. Alimelli, C. Di Natale,
R. Paolesse, A. D’Amico,
I. Lundstr6m*
3800 – 3803
Chemical Sensing with Familiar Devices
Multiple Bonds
M. Brynda,* L. Gagliardi,* P.-O. Widmark,
P. P. Power, B. O. Roos
3804 – 3807
A Quantum Chemical Study of the
Quintuple Bond between Two Chromium
Centers in [PhCrCrPh]: trans-Bent versus
Linear Geometry
Water Clusters
P. S. Lakshminarayanan, E. Suresh,
P. Ghosh*
3807 – 3811
A Hybrid Water–Chloride Structure with
Discrete Undecameric Water Moieties
Self-Assembled in a Heptaprotonated
Octaamino Cryptand
3724
www.angewandte.org
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Seeing sense: The detection of detailed
absorption and emission responses
caused by amines, CO, and NOx is
possible using an inexpensive array of
porphyrins as sensors combined with a
computer screen and web camera. The
computer-screen image shows the array in
the presence of triethylamine. [Zn] = [Zn(tpp)], [Fe] = [Fe(tppCl)] (tpp =
5,10,15,20-tetraphenylporphyrin),
BD = 2,3,17,18-tetraethyl-7,8,12,13-tetramethyl-a,c-biladiene dihydrobromide.
High five: Multiconfigurational quantum
chemical methods show that a quintuple
bond is present between the two CrI units
in the model complex [PhCrCrPh]. The Cr
Cr (1.75 S) and Cr Ph (2.02 S) bonds are
shorter than those in the recently reported
compound [Ar’CrCrAr’] (Ar’ = 2,6-(2,6iPr2C6H3)2C6H3 ; 1.83 and 2.15 S, respectively). This difference is attributed to the
additional Cr Ar’ interactions.
Odd water clusters: An unprecedented
propeller-shaped undecameric water
motif is stabilized within the lattice of the
heptahydrochloride of a homoditopic
octaamino cryptand with C3 symmetry.
The discrete water clusters are oriented
symmetrically around the cryptand moiety
and interact with encapsulated chloride
inside the cavity (see structure; Cl green,
O red, N blue).
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
Angewandte
Chemie
Synthetic Methods
N. Z. Burns, B. M. Hackman, P. Y. Ng,
I. A. Powelson,
J. L. Leighton*
3811 – 3813
A strained allylsilane reagent is highly
effective in the enantioselective allylation
of hydroxyphenylketones. The method is
uniquely tolerant both of sterically hindered aliphatic ketones and highly func-
tionalized diaryl ketones and has been
extended to include the first examples of
highly diastereo- and enantioselective
ketone crotylation, which provides access
to both diastereomers.
The Enantioselective Allylation and
Crotylation of Sterically Hindered and
Functionalized Aryl Ketones: Convenient
Access to Unusual Tertiary Carbinol
Structures
Asymmetric Catalysis
R. Matsubara, N. Kawai,
S. Kobayashi*
Added benefits: Catalytic enantio- and
diastereoselective addition of aldehydederived enecarbamates to aldehydes is
reported (see scheme). A copper(I)–diimine complex works well as the catalyst
and the catalyst loading is not more than
1 mol % in most cases. By taking advantage of this reaction, the total synthesis of
(2S,3S,4S)-3-hydroxy-4-methylproline has
been accomplished.
3814 – 3816
Catalytic Enantioselective and
Diastereoselective Addition of AldehydeDerived Enecarbamates to a-Oxo
Aldehydes
Transition-Metal Catalysis
Y. Yamashita, M. M. Salter, K. Aoyama,
S. Kobayashi*
3816 – 3819
Easy activation: A Lewis acid catalyst
based on molybdenum relies on activation by molecular oxygen for its high
catalytic activity. The novel complex catalyzes the aza-Diels–Alder reaction of acyl
hydrazones with Danishefsky dienes (see
scheme) and other Lewis acid mediated
reactions, such as the Mukaiyama aldol
addition, Mannich-type reactions, and the
addition of trimethylsilylcyanide to
imines.
With Molecular-Oxygen-Activated Lewis
Acids: Dinuclear Molybdenum Complexes
for Aza-Diels–Alder Reactions of Acyl
Hydrazones
Alkylation
G. Onodera, Y. Nishibayashi,*
S. Uemura
3819 – 3822
The compatibility between [{IrCl(cod)}2]
and ruthenium complex 1 to achieve
asymmetric a-alkylative reduction of prochiral ketones with primary alcohols is an
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
essential factor in obtaining optically
active alcohols with elongation of the
carbon skeleton in good yields with a high
enantioselectivity.
Ir- and Ru-Catalyzed Sequential
Reactions: Asymmetric a-Alkylative
Reduction of Ketones with Alcohols
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3725
Contents
Tandem Annulation
Multitasking catalyst: 1,2-Dihydroisoquinoline derivatives are prepared in good
yields by an In(OTf)3-catalyzed tandem
annulation reaction. The catalyst activates
both the imine and alkyne to the addition
of various nucleophiles and the subsequent intramolecular cyclization (see picture; OTf = trifluoromethanesulfonate).
R. Yanada, S. Obika, H. Kono,
Y. Takemoto*
3822 – 3825
In(OTf)3-Catalyzed Tandem Nucleophilic
Addition and Cyclization of
ortho-Alkynylarylaldimines to
1,2-Dihydroisoquinolines
Nanostructures
X. W. Lou, C. Yuan, Q. Zhang,
L. A. Archer*
3825 – 3829
Platinum-Functionalized Octahedral
Silica Nanocages: Synthesis and
Characterization
Hole in one! Octahedral silica nanocages
are prepared by a facile one-step
approach, which also enables controlled
functionalization with Pt in the cavities.
The strategy is based on mediated
deposition of silica on simultaneously
generated salt quasi-templates, which are
simply removed by washing with water.
Nanotechnology
D. B. Cordes, S. Gamsey,
B. Singaram*
3829 – 3832
Fluorescent Quantum Dots with Boronic
Acid Substituted Viologens To Sense
Glucose in Aqueous Solution
A quantum leap in glucose sensing:
Commercially available fluorescent quantum dots are used in combination with
boronic acid modified viologens to sense
glucose in aqueous solution. The signal
response is optimized by adjusting the
ratio of quantum dots to viologen
quencher.
A catalyst system composed of Pd(OCOCF3)2 complexed with the electrondonating, rigid chiral diphosphane TangPhos gives excellent enantioselectivities
(up to 99 % ee) and conversions (up to
> 99 %) in the hydrogenation of N-tosylimines 1 (see scheme). A variety of
aromatic, aliphatic, and cyclic chiral
amines 2 can be prepared by this methodology.
Palladium-Catalyzed Hydrogenation
Q. Yang, G. Shang, W. Gao, J. Deng,
X. Zhang*
3832 – 3835
A Highly Enantioselective, Pd–TangPhosCatalyzed Hydrogenation of
N-Tosylimines
3726
www.angewandte.org
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
Angewandte
Chemie
Thermoelectric Materials
Worthy of merit: The new class of nanostructured p-type thermoelectrics
Na1 xPbmSbyTem+2 is reported. The exceptionally high thermoelectric figures of
merit ZT of these materials (see graph),
which exceed those of the state-of-the-art
materials PbTe and (GeTe)1 x((Ag2Te)1 y(Sb2Te3)y)x (TAGS), derive from their very
low lattice thermal conductivities.
P. F. P. Poudeu, J. D’Angelo, A. D. Downey,
J. L. Short, T. P. Hogan,
M. G. Kanatzidis*
3835 – 3839
High Thermoelectric Figure of Merit and
Nanostructuring in Bulk p-type
Na1 xPbmSbyTem+2
Asymmetric Synthesis
T. Ooi, K. Fukumoto,
K. Maruoka*
3839 – 3842
Construction of Enantiomerically
Enriched Tertiary a-Hydroxycarboxylic
Acid Derivatives by Phase-TransferCatalyzed Asymmetric Alkylation of
Diaryloxazolidin-2,4-diones
Center of attention: The chiral ammonium
bromide 1 has been used as a catalyst for
the highly enantioselective alkylation of
diaryloxazolidindiones 2 under mild
phase-transfer conditions (TBME = tert-
butyl methyl ether). This method provides
practical access to a variety of optically
active tertiary a-hydroxycarboxylic acid
derivatives.
Nonlinear Optics
Two merocyanine dyes are assembled by
multiple hydrogen bonds with summation
of their dipole moments (see formula;
R = 2-ethylhexyl). It exhibits a strongly
increased degree of dye alignment in an
electric field according to electrooptical
absorption spectroscopy.
F. WUrthner,* J. Schmidt, M. Stolte,
R. Wortmann*
3842 – 3846
Hydrogen-Bond-Directed Head-to-Tail
Orientation of Dipolar Merocyanine Dyes:
A Strategy for the Design of Electrooptical
Materials
Light switch: Noncovalently connected
micelles are formed by the photoisomerization of azobenzene groups in copolymer building blocks and the hydrogenbonding interaction within the polymer
pair. The UV-induced micellar structure
can be fixed through core cross-linking,
which allows the reversible optical
switching of a micelle–hollow-sphere
transition (see picture).
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
Photoisomerization
X. Liu, M. Jiang*
3846 – 3850
Optical Switching of Self-Assembly:
Micellization and Micelle–Hollow-Sphere
Transition of Hydrogen-Bonded Polymers
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3727
Contents
Oligosaccharide Synthesis
O. Kanie,* I. Ohtsuka, T. Ako, S. Daikoku,
Y. Kanie, R. Kato
3851 – 3854
Orthogonal Glycosylation Reactions on
Solid Phase and Synthesis of a Library
Consisting of a Complete Set of Fucosyl
Galactose Isomers
A dream team: Orthogonal glycosylation
and solid-phase synthesis were shown to
be an excellent combination for polysaccharide synthesis (see scheme). The
method was applied to generate a complete library of structural isomers with an
l-fucosyl-d-galactose sequence.
Quinone Complexes
J. Moussa, D. A. Lev, K. Boubekeur,
M. N. Rager, H. Amouri*
3854 – 3858
A h4-Dithio-para-benzoquinone Metal
Complex
Overcoming a long-standing challenge: A
rational synthetic procedure allows the
isolation of the first stable h4-dithio-parabenzoquinone complex (2; Cp* = C5Me5).
The X-ray molecular structure of 2 con-
Carbocyclic Carbenes
W. A. Herrmann,* K. Vfele,
S. K. Schneider, E. Herdtweck,
S. D. Hoffmann
3859 – 3862
A Carbocyclic Carbene as an Efficient
Catalyst Ligand for C C Coupling
Reactions
Structure Elucidation
M. Nett, V. Erol, S. Kehraus, M. K6ck,
A. Krick, E. Eguereva, E. Neu,
G. M. K6nig*
3863 – 3867
Siphonazole, an Unusual Metabolite from
Herpetosiphon sp.
3728
www.angewandte.org
firms the coordination of the elusive
intermediate 1 in an h4 manner. Computational analyses of 2 support the role of
the {Cp*Ir} fragment in stabilizing this
reactive intermediate.
A new player on the field: Carbocyclic
carbenes are potentially better control
ligands than N-heterocyclic carbenes
(NHCs) in catalyzed C C coupling reactions. PdII complexes of cycloheptatrienylidene (see picture), which are readily
prepared, thermally stable, and highly
stable towards acid, are as effective as the
familiar NHC complexes in Suzuki and
Heck reactions or perform even better.
Deep and complex: The first representative (see picture) of a new structural class
has been isolated from a deep-rooted
filamentous bacterium of the genus Herpetosiphon. Feeding with 13C and 15Nlabeled precursors showed the complex
biosynthesis to involve shikimate, the
polyketide, and the amino acid metabolism.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
Angewandte
Chemie
Copper Dioxygen Compounds
No doubt: The high-quality crystal structure of [Cu(TMG3tren)(O2)]SbF6 (see picture) presents the first unambiguous
characterization of a bioinorganic compound in which a dioxygen molecule
coordinates end-on to a CuI ion. This
species, which is best described as a
superoxo copper(II) complex, serves as a
model complex for initially formed Cu–O2
adducts present in a variety of active sites
of copper enzymes.
C. WUrtele, E. Gaoutchenova, K. Harms,
M. C. Holthausen,* J. Sundermeyer,*
S. Schindler*
3867 – 3869
Crystallographic Characterization of a
Synthetic 1:1 End-On Copper Dioxygen
Adduct Complex
One for all? The nucleophilicity parameters N, which have been derived from the
rate constants k of reactions of nucleophiles with carbocations, also hold for
SN2-type reactions (see scheme). A general equation is suggested which includes
established correlations (Swain–Scott,
Ritchie) as special cases.
Spin doctoring: Site-directed spin labeling
was used to determine the structure of T4
lysozyme adsorbed on quartz. At high
ionic strength significant changes of the
backbone fold are limited to the region
around the enzymatic cleft. In contrast, at
low ionic strength the previously unperturbed parts of the protein interact with
the surface. Hydrophobic interactions are
thought to play an important role in the
partial unfolding at high ionic strength.
B0
wrt
qM=54.7°
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
Slim peaks: Using a perdeuterated protein
recrystallized from a 10:90 H2O:D2O
mixture in magic-angle spinning (MAS)
solid-state NMR spectroscopy experiments gives small 1H line widths at
moderate spinning frequencies without
application of homonuclear decoupling.
This labeling strategy opens new perspectives for assignment of large protein
spin systems.
Nucleophilicity Scales
T. B. Phan, M. Breugst,
H. Mayr*
3869 – 3874
Towards a General Scale of
Nucleophilicity?
Protein Folding
K. Jacobsen, W. L. Hubbell, O. P. Ernst,
T. Risse*
3874 – 3877
Details of the Partial Unfolding of T4
Lysozyme on Quartz Using Site-Directed
Spin Labeling
Protein NMR Spectroscopy
V. Chevelkov, K. Rehbein, A. Diehl,
B. Reif*
3878 – 3881
Ultrahigh Resolution in Proton Solid-State
NMR Spectroscopy at High Levels of
Deuteration
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3729
Angewandte
Chemie
Service
Keywords
3882
Authors
3883
Vacancies
Preview
Angew. Chem. Int. Ed. 2006, 45, 3720 – 3731
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
A33
3885
www.angewandte.org
3731
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