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Graphical Abstract Angew. Chem. Int. Ed. 252005

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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:
F. Studt, F. Tuczek*
Energetics and Mechanism of a Room Temperature Catalytic
Synthesis of Ammonia (Schrock Cycle): Comparison with
Biological Nitrogen Fixation
C. Schaefer, G. C. Fu*
Catalytic Asymmetric Couplings of Ketenes with Aldehydes To
Generate Enol Esters
M. Capdevila,* J. Domnech, A. Pagani, L. To, L. Villarreal,
S. Atrian
Zn and Cd Metallothionein Recombinant Species from the Most
Diverse Phyla May Contain Sulfide (S2) Ligands
H. Zhu, J. Chai, H. Fan, H. W. Roesky,* C. He, V. Jancik,
H.-G. Schmidt, M. Noltemeyer, W. A. Merrill, P. P. Power
A Stable Aluminacyclopropene LAl(h2-C2H2) and Its End-On
Azide Insertion to an Aluminaazacyclobutene
D. Loffreda,* F. Delbecq, F. Vign, P. Sautet
Catalytic Hydrogenation of Unsaturated Aldehydes on Pt (111):
Understanding the Selectivity from First-Principles Calculations
R. Shintani, W.-L. Duan, T. Nagano, A. Okada, T. Hayashi*
Chiral Phosphine?Olefin Bidentate Ligands in Asymmetric
Catalysis: Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl
Boronic Acids to Maleimides
Obituary
Hans Bethe (1906?2005) and Ligand Field Theory
W. Kutzelnigg
3800
Books
Modern Rhodium-Catalyzed Organic
Reactions
P. Andrew Evans
reviewed by B. Schmidt
3802
Acetylene Chemistry
Franois Diederich, Peter J. Stang,
Rik R. Tykwinski
reviewed by A. Hirsch
3803
Reversibility makes the difference:
30 years after Staab reported the synthesis
of the phenylene-acetylene macrocycle 1
in 4.6 % yield starting from a simple
precursor (see scheme), these structures
are now available in nearly 80 % yield, also
from simple precursors.
Highlights
Macrocycle Synthesis
S. Hger*
3806 ? 3808
Shape-Persistent Phenylene-Acetylene
Macrocycles: Large Rings?Low Yield?
3790
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
Angewandte
Chemie
Go with the flow: Liquid inorganic salts
formed by a combination of inorganic
substances (for example, nanoparticles
such as SiO2 and Fe2O3 or polyoxometalates) with organic liquid salts (see picture: A is poly(ethylene glycol) sulfonate
ion, cN+ is C3H6N+(CH3)(C10H21)2)
combine the characteristics of both components in a homogenous material that
can be used in batteries and solar cells.
Ionic Liquids
B. Smarsly,* H. Kaper
3809 ? 3811
Liquid Inorganic?Organic
Nanocomposites: Novel Electrolytes and
Ferrofluids
Reviews
Medicinal Chemistry
L. Bialy, H. Waldmann*
Tyrosine phosphatases and kinases
govern the phosphorylation states of
numerous proteins (see scheme) and
modulate many cellular processes. Similar
to the rise of tyrosine kinase inhibitors as
established drug targets, inhibitors of
tyrosine phosphatases also show promise
in this regard, and only recently have
moved into the spotlight.
3814 ? 3839
Inhibitors of Protein Tyrosine
Phosphatases: Next-Generation Drugs?
Communications
Molecular Complexes
A preferred conformation of the internally
highly dynamic fluoromethane?trifluoromethane molecular complex results from
the stabilization of the two subunits by
three weak CH贩稦 hydrogen bonds and
electrostatic dipole?dipole interactions
(see picture). The two subunits are not
rigidly locked, but exhibit large amplitude
motions by almost freely spinning around
their symmetry axes as shown.
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Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
W. Caminati,* J. C. Lpez, J. L. Alonso,
J.-U. Grabow
3840 ? 3844
Weak CH贩稦 Bridges and Internal
Dynamics in the CH3F稢HF3 Molecular
Complex
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3791
Angewandte
Chemie
If you look for holes, you will find them in
a novel 3D metal?organic framework
complex with zeolite MTN topology. The
framework of [{Cd(H2O)3}34(N4C6H12)17]Cl68� H2O� DMF greatly
expands the original structure of MTN
and contains large cages with a volume of
about 2522 3 (see structure).
MTN = zeolite socony mobil ? thirty-nine,
DMF = N,N-dimethylformamide.
Q.-R. Fang, G.-S. Zhu,* M. Xue, J.-Y. Sun,
Y. Wei, S.-L. Qiu,* R.-R. Xu
3845 ? 3848
A Metal?Organic Framework with the
Zeolite MTN Topology Containing Large
Cages of Volume 2.5 nm3
Water Transport
Burrowing water: The apohost phase of a
substituted hydrophobic calixarene,
grown by sublimation, forms lattice voids
but not channels. Exposure of the crystals
to liquid water results in a single-crystalto-single-crystal phase transformation
during which water molecules become
embedded in the lattice voids (see picture); thus the classical view of diffusion
might not be appropriate at the atomic
scale.
P. K. Thallapally, G. O. Lloyd,
J. L. Atwood,* L. J. Barbour* 3848 ? 3851
Diffusion of Water in a Nonporous
Hydrophobic Crystal
Striking similarity: An efficient synthetic
route to native ubiquitin and its diastereomer [d-Gln 35]ubiquitin was realized by
combining a one-pot native chemical
ligation process with protein desulfurization. High-resolution X-ray crystallographic studies of the protein diastereomer (see picture) revealed a striking
conservation of molecular structure.
Protein Structures
D. Bang, G. I. Makhatadze, V. Tereshko,
A. A. Kossiakoff, S. B. Kent* 3852 ? 3856
Total Chemical Synthesis and X-ray Crystal
Structure of a Protein Diastereomer:
[d-Gln 35]Ubiquitin
Polyoxometalates
Sphere we go: A spherical capsule is
prepared simply by the interaction of
linkers to pentagonal structural units. The
metal centers (M) of the {(MoVI)MoVI5}12M30 type Keplerates formed (M = VIV, FeIII)
describe an icosidodecahedron (see picture). For M = FeIII the magnetic configuration of the 30 spin centers (colored
spheres) can be pictured geometrically in
terms of three sets, each of 10 spins, with
different angular orientations (arrows).
With M = VIV the compound behaves
according to the demands of quantum
mechanics and a clear geometrical picture
of the magnetism is not possible.
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
Coordination Polymers
A. Mller,* A. M. Todea, J. van Slageren,
M. Dressel, H. Bgge, M. Schmidtmann,
M. Luban, L. Engelhardt,
M. Rusu
3857 ? 3861
Triangular Geometrical and Magnetic
Motifs Uniquely Linked on a Spherical
Capsule Surface
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3793
Contents
Bioorganic Chemistry
H. Kurosaki,* Y. Yamaguchi, T. Higashi,
K. Soga, S. Matsueda, H. Yumoto,
S. Misumi, Y. Yamagata, Y. Arakawa,
M. Goto
3861 ? 3864
Irreversible Inhibition of Metallo-blactamase (IMP-1) by 3-(3-Mercaptopropionylsulfanyl)propionic Acid
Pentafluorophenyl Ester
Resistance is futile: Pathogenic bacteria
that produce metallo-b-lactamases are
recognized as a serious threat because of
their resistance to antibiotics. The title
compound has now been shown to be an
irreversible inhibitor for a metallo-b-lactamase (IMP-1). The X-ray crystallographic structure (see picture) has
revealed that the inhibitor binds to IMP-1
with formation of a covalent amide bond
with the amino group (Nz) of Lys 224.
Coordination Polymers
X.-J. Luan, Y.-Y. Wang,* D.-S. Li, P. Liu,
H.-M. Hu, Q.-Z. Shi,
S.-M. Peng
3864 ? 3867
Self-Assembly of an Interlaced
Triple-Stranded Molecular Braid with
an Unprecedented Topology through
Hydrogen-Bonding Interactions
Molecular weaving: Mixing a CuII complex
having a paddle-wheel structure with a
highly flexible neutral 1,3-bis(4-pyridyl)propane ligand (1:2 ratio) gives an inter-
laced braid which looks just like a hair
plait (see X-ray crystallographic structure).
The three strands are held together
through hydrogen-bonding interactions.
No metal required: Double-helical
assemblies can be constructed through
hydrogen bonds upon formation of
amidinium?carboxylate salt bridges (see
schematic representation). The doublehelical structures formed including the
helix sense are predictable by this
approach.
Fully controlled total synthesis of benanomicin B was achieved by exploiting two
key steps: a stereocontrolled ring-opening
of a lactone (see scheme, step A), and a
semipinacol cyclization of an acetal-aldehyde derivative discriminating the two
hydroxy groups of the pseudo-C2-symmetric 1,2-diol moiety (step B).
Helical Structures
Y. Tanaka, H. Katagiri, Y. Furusho,*
E. Yashima*
3867 ? 3870
A Modular Strategy to Artificial
Double Helices
Total Synthesis
K. Ohmori, M. Tamiya, M. Kitamura,
H. Kato, M. Oorui,
K. Suzuki*
3871 ? 3874
Regio- and Stereocontrolled Total
Synthesis of Benanomicin B
3794
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
Angewandte
Chemie
Multicomponent Reactions
K. C. Nicolaou,* W. Tang, P. Dagneau,
R. Faraoni
3874 ? 3879
Three?s not always a crowd: A threecomponent reaction involving a,b-unsaturated enones 1, aldehydes 2, and alkenyl
zirconium species 3 in the presence of a
Rh?binap catalyst leads, sequentially, to
aldols 4, enones 5, and 2,3-disubstituted
cycloalkanones 6 in good yields and with
high ee values.
A Catalytic Asymmetric Three-Component
1,4-Addition/Aldol Reaction:
Enantioselective Synthesis of the
Spirocyclic System of Vannusal A
Natural Product Synthesis
R. E. Looper, M. T. C. Runnegar,
R. M. Williams*
3879 ? 3881
Naturally occurring! The cyanobacterial
metabolite 7-deoxycylindrospermopsin
has been synthesized and its natural
occurrence confirmed by HPLC. Structural
analysis and protein-inhibition studies
show that the uracil unit does not appear
to adopt the unconventional tautomeric
structure (see scheme), as previously
thought, and that oxygenation at C7 is
not required for the inhibition of protein
biosynthesis.
Synthesis of the Putative Structure of
7-Deoxycylindrospermopsin:
C7 Oxygenation Is Not Required for
the Inhibition of Protein Synthesis
Henry Reaction
C. Palomo,* M. Oiarbide,
A. Laso
A simple assembly of commercially available materials, namely, zinc triflate (Zn(OTf)2), a tertiary amine base (iPr2EtN),
and reusable (�)-N-methylephedrine,
effectively activates the Henry reaction
between aldehydes and nitromethane (see
scheme). The catalytic system can be used
in substoichiometric quantities and leads
to good yields and enantioselectivities.
Enantioselective Henry Reactions under
Dual Lewis Acid/Amine Catalysis Using
Chiral Amino Alcohol Ligands
Asymmetric Catalysis
An efficient and facile method is used to
develop new (salen)ruthenium(ii) catalysts for the asymmetric cyclopropanation
of olefins, in which a chiral additive
induces asymmetry in inexpensive and
readily synthesized achiral (salen)ruthenium(ii) catalysts (see scheme; EDA =
ethyl diazoacetate). This approach is
amenable to parallel-screening optimization and has great potential advantages
over traditional catalyst development and
synthetic methods.
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
3881 ? 3884
J. A. Miller, B. A. Gross, M. A. Zhuravel,
W. Jin, S. T. Nguyen*
3885 ? 3889
Axial Ligand Effects: Utilization of Chiral
Sulfoxide Additives for the Induction of
Asymmetry in (Salen)ruthenium(ii) Olefin
Cyclopropanation Catalysts
www.angewandte.org
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3795
Contents
Synthetic Methods
M. D. Helm, J. E. Moore, A. Plant,
J. P. A. Harrity*
3889 ? 3892
Synthesis of Highly Substituted
Pyridazines through Alkynyl Boronic Ester
Cycloaddition Reactions
Natural Products Synthesis
P. S. Baran,* C. A. Guerrero,
B. D. Hafensteiner,
N. B. Ambhaikar
3892 ? 3895
Total Synthesis of Avrainvillamide
(CJ-17,665) and Stephacidin B
A highly regioselective transformation of
tetrazines through a cycloaddition reaction with alkynyl boronic esters provides
highly substituted pyridazine boronic
esters as intermediates for CO and CC
bond-forming reactions (see scheme).
Functionalization reactions of the CB
bond, such as oxidation and the Suzuki
cross-coupling, show the versatility of
these species.
Enantioselective total syntheses of the
naturally occurring forms of the highly
oxidized indole alkaloids avrainvillamide
(CJ-17,665) and stephacidin B (see formula) are reported, facilitated by a
remarkable oxidation of stephacidin A.
A streamlined route to stephacidin A is
also reported along with the absolute
configuration determination of this
family of natural products.
Ring Systems
K. C. Nicolaou,* G. E. A. Carenzi,
V. Jeso
3895 ? 3899
Construction of Highly Functionalized
Medium-Sized Rings: Synthesis of
Hyperforin and Perforatumone Model
Systems
Bridging the gap: A sequence of reactions
(1!2!3!4) leads to bridged, polyfunctional, medium-sized rings in synthetically
Natural Product Synthesis
A transannular ring contraction induced
by the addition of an aryl radical intermediate to a proximal arene facilitated the
construction of the highly strained macrocyclic core of cavicularin (1). The precursor, an iodinated derivative of another
natural product, riccardin C, was prepared
from four commercially available arenes
in a highly convergent sequence.
D. C. Harrowven,* T. Woodcock,
P. D. Howes
3899 ? 3901
Total Synthesis of Cavicularin and
Riccardin C: Addressing the Synthesis of
an Arene That Adopts a Boat
Configuration
3796
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
useful yields. These rings are reminiscent
of the molecular architectures of hyperforin and perforatumone.
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
Angewandte
Chemie
Cheers! Specificity for riboflavin in waterrich media with an affinity on the order
found for the corresponding biological
receptor, riboflavin binding protein, is
shown by a receptor containing a complementary hydrogen bonding array (see
picture). Microcalorimetry performed at
low receptor concentrations in a solution
mimicking an alcoholic beverage indicated the presence of a small but uniform
population of high-affinity sites
(K > 106 m1).
Bioorganic Chemistry
P. Manesiotis, A. J. Hall,* J. Courtois,
K. Irgum, B. Sellergren*
3902 ? 3906
An Artificial Riboflavin Receptor Prepared
by a Template Analogue Imprinting
Strategy
Platinum?Gallium Compounds
Formal substitution of two terminal trans
chlorine substituents in a Ga2Cl6 molecule
by platinum groups leads to the platinum(0)?chrysene compound shown. The
complex has been structurally characterized.
M. Gorlov, A. Fischer,
L. Kloo*
3906 ? 3909
One-Step Synthesis of a Platinum(0)?
Gallium(iii) Chrysene Complex
Asymmetric Catalysis
R. Shintani, A. Tsurusaki, K. Okamoto,
T. Hayashi*
3909 ? 3912
A rhodium catalyst promotes the arylative
cyclization of alkyne-tethered electrondeficient olefins in the presence of aryl
boronic acids. High chemoselectivity was
attained uniquely by the use of diene
Highly Chemo- and Enantioselective
Arylative Cyclization of Alkyne-Tethered
Electron-Deficient Olefins Catalyzed by
Rhodium Complexes with Chiral Dienes
ligands, and high enantioselectivity was
successfully realized by employing a C2symmetric chiral bicyclo[2.2.2]octadiene
ligand (see scheme).
Arene Functionalization
I. Iovel, K. Mertins, J. Kischel, A. Zapf,
M. Beller*
3913 ? 3917
Green grow the diarylmethanes: Substituted arenes and heteroarenes can be
easily benzylated in the presence of
inexpensive and relatively nontoxic metal
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
salts such as FeCl3 (see scheme). This
arylation method with benzyl alcohols is a
state-of-the-art green route to diarylmethanes as water is the only by-product.
www.angewandte.org
An Efficient and General Iron-Catalyzed
Arylation of Benzyl Alcohols and Benzyl
Carboxylates
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3797
Contents
What appears to be ?LaI? with a NaCl-type
structure is in fact an Al-stabilized cluster
compound consisting of disordered
La6AlI12 clusters that share I atoms (see
picture). Quantitative analysis of diffuse
diffraction data revealed both the constitution of this compound and the fact that
this disorder is not statistical, but as
uniform as possible for the composition
La0.7I1xAlx (x 0.14) given the observed
lattice.
Analysis of X-ray Data
O. Oeckler, T. Weber, L. Kienle,
H. Mattausch, A. Simon*
3917 ? 3921
Cluster Disorder and Ordering Principles
in Al-Stabilized ?LaI?
DNA?Peptide Complexes
Peptide?DNA recognition: The specific
binding of peptides to DNA representing
a section of the binding sequence of a
transcription activator has been demonstrated for the first time at the singlemolecule level with AFM (experimental
principle, see picture). The results underscore the importance of peptide length
and cooperative effects as well as the
contribution of single-point mutations on
specific binding.
R. Eckel, S. D. Wilking, A. Becker,
N. Sewald,* R. Ros,
D. Anselmetti*
3921 ? 3924
Single-Molecule Experiments in Synthetic
Biology: An Approach to the Affinity
Ranking of DNA-Binding Peptides
Propellanes
M. Messerschmidt, S. Scheins, L. Grubert,
M. Ptzel, G. Szeimies, C. Paulmann,
P. Luger*
3925 ? 3928
Electron Density and Bonding at Inverted
Carbon Atoms: An Experimental Study of
a [1.1.1]Propellane Derivative
Stable Methanides
H. Brand, P. Mayer, A. Schulz,*
J. J. Weigand
3929 ? 3932
Nitro(nitroso)cyanomethanides
3798
Synchrotron radiation was required for
high-resolution diffraction experiments to
determine the electron density and analyze the topology of a new [1.1.1]propellane derivative. A bond path with a bond
critical point of significant electron density was found between the ?inverted?
bridgehead atoms C4贩稢4a (see picture),
which is characteristic for a covalent
bond; however, no charge accumulation
at the bond critical point was seen.
More bangs for the buck. Explosive
nitro(nitroso)cyanomethanides
M?[C(NO2)(NO)(CN)] (M? = alkali metal,
NMe4) were prepared in a simple, twostep, high-yielding procedure, fully characterized, and shown to be stable at
ambient temperature. The thermal properties were studied, and the structures of
several nitro(nitroso)cyanomethanide
salts were determined by X-ray diffraction.
The structure and bonding in these
compounds are discussed on the basis
of calculations.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
Angewandte
Chemie
Cluster Compounds
Molecular alloys: The composition and
properties of the title compounds suggests that they can be regarded as molecular alloys. The single-crystal structures
of these phosphine-stabilized compounds
are determined (see picture for structure
of [Cu45Sb16(PEt2Me)16]; Sb red, Cu blue,
P green) and confirmed by density
functional theory (DFT) calculations.
R. Ahlrichs, D. Fenske,* M. McPartlin,
A. Rothenberger, C. Schrodt,
S. Wieber
3932 ? 3936
Phosphine-Stabilized Copper?Antimony
Clusters: Syntheses, Structures, and
Theoretical Investigations of
[Cu12(SbSiMe3)6(PiPr3)6],
[Cu40Sb12(PMe3)20], and
[Cu45Sb16(PEt2Me)16]
The issues for May 2005 appeared online on the following dates
Issue 21: May 17 � Issue 22: May 24 � Issue 23: May 30 � Issue 24: June 6
Service
Keywords
3938
Authors
3939
Angewandte?s Sister Journals
3940
Preview
3941
Corrigendum
*
We failed to reference the interesting and relevant work of Gan-Calvo and co-workers:
A. M. Gan-Calvo, Phys. Rev. Lett. 1998, 80, 285; A. M. Gan-Calvo, J. M. Gordillo,
Phys. Rev. Lett. 2001, 87, 274 501; I. G. Loscertales, A. Barrero, I. Guerrero, R. Cortijo, M.
Marquez, A. M. Gan-Calvo, Science 2002, 295, 1695. We would also like to point the
interested reader to other relevant reports, such as: I. Cohen, H. Li, J. L. Hougland, M.
Mrksich, S. R. Nagel, Science 2001, 292, 265; S. Sugiura, M. Nakajima, H. Itou, M. Seki,
Macromol. Rapid. Commun. 2001, 22, 773; T. Nisisako, T. Torii, T. Higuchi, Chem. Eng. J.
2004, 101, 23. Although the details of the fluid physics and the specific applications of
our paper differ from those of the reports cited herein, the prior work of these authors
illustrates the value of flow-focusing systems in making highly uniform droplets and the
potential for using these droplets in materials science.
In addition, following the submission of our report, two other articles that document the
use of microfluidic channels for the in situ preparation of anisotropic polymeric
particles were published: W. Jeong, J. Kim, S. Kim, S. Lee, G. Mensing, D. J. Beebe, Lab
Chip 2004, 4, 576; D. Dendukuri, K. Tsoi, T. A. Hatton, P. S. Doyle, Langmuir 2005, 21,
2113.
Angew. Chem. Int. Ed. 2005, 44, 3790 ? 3799
www.angewandte.org
Generation of Monodisperse Particles by
Using Microfluidics: Control over Size,
Shape, and Composition
S. Xu, Z. Nie, M. Seo, P. Lewis,
E. Kumacheva,* H. A. Stone, P. Garstecki,
D. B. Weibel, I. Gitlin,
G. M. Whitesides*
724?728
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200462226
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3799
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