Angewandte Chemie International Edition

Cover image for Vol. 44 Issue 27

July 4, 2005

Volume 44, Issue 27

Pages 4103–4269

    1. Cover Picture: Supramolecular Coordination Assemblies of Dinuclear FeIII Complexes (Angew. Chem. Int. Ed. 27/2005) (page 4103)

      Wolfgang Schmitt, Jonathan P. Hill, M. Paula Juanico, Andrea Caneschi, Ferdinando Costantino, Christopher E. Anson and Annie K. Powell

      Version of Record online: 23 JUN 2005 | DOI: 10.1002/anie.200590091

      Busy bees may also find the honeycomb networks shown in the cover picture attractive. The networks are based on dinuclear FeIII subunits, aminocarboxylic acid ligands, and potassium counterions. The properties of the hydrophobic organic ligands strongly influence the structure of the hydrophilic inorganic zone which in turn affects the overall structure of the supramolecular assemblies. For more information on this approach see the Communication by W. Schmitt, A. K. Powell, and co-workers on page 4187 ff.

    2. Many Promising Smells (pages 4118–4119)

      Stefan Schulz

      Version of Record online: 23 JUN 2005 | DOI: 10.1002/anie.200501584

    3. Molecular Motors: Synthetic DNA-Based Walkers Inspired by Kinesin (pages 4124–4127)

      T. Ross Kelly

      Version of Record online: 2 JUN 2005 | DOI: 10.1002/anie.200500568

      Thumbnail image of graphical abstract

      Molecules that walk the walk! As Confucius reputedly said, “a journey of a thousand miles begins with a single step”. Three related strategies that offer initial answers to the challenging design problem of how to control motion across a surface at the molecular scale are highlighted (see diagram).

    4. Strategies for Targeting Protein–Protein Interactions With Synthetic Agents (pages 4130–4163)

      Hang Yin and Andrew D. Hamilton

      Version of Record online: 14 JUN 2005 | DOI: 10.1002/anie.200461786

      Thumbnail image of graphical abstract

      Small-molecule modulators of protein–protein interactions possess significant potential as novel therapeutic compounds. An overview of the strategies for obtaining compounds that disrupt protein–protein interactions is presented. The state of the art in the rational design of mimetics that reproduce the structures and functions of their natural targets is also discussed (see scheme).

    5. A Neutral Mixed-Valent Conducting Polymer Formed by Electron Transfer between Metal d and Ligand π Orbitals (pages 4164–4168)

      Minoru Mitsumi, Hidekazu Goto, Shunsuke Umebayashi, Yoshiki Ozawa, Mototada Kobayashi, Toshihiko Yokoyama, Hisaaki Tanaka, Shin-ichi Kuroda and Koshiro Toriumi

      Version of Record online: 14 JUN 2005 | DOI: 10.1002/anie.200501189

      Thumbnail image of graphical abstract

      Frontier-orbital design aided in the preparation of the novel neutral linear chain rhodium(I,II) complex [Rh(3,6-dbdiox-4,5-Cl2)(CO)2] (see picture), in which the mixed-valent state is formed by electron transfer between metal d and semiquinonate π* orbitals (3,6-dbdiox-4,5-Cl2: semiquinonate or catecholate of 3,6-di-tert-butyl-4,5-dichloro-1,2-benzoquinone). This compound exhibits high conductivity (17–34 S cm−1) at room temperature in spite of its being a neutral molecule.

    6. Preparation and Structural Characterization of Stable Cs2O Closed-Cage Structures (pages 4169–4172)

      Ana Albu-Yaron, Talmon Arad, Ronit Popovitz-Biro, Maya Bar-Sadan, Yehiam Prior, Martin Jansen and Reshef Tenne

      Version of Record online: 3 JUN 2005 | DOI: 10.1002/anie.200500356

      Thumbnail image of graphical abstract

      Fullerene-like Cs2O nanoparticles were prepared by laser ablation of 3R-Cs2O powder in evacuated quartz ampoules. The Cs2O closed cages, such as the faceted nanoparticle shown in the picture, are remarkably stable as compared with the corresponding extremely unstable but technically important bulk compound, which makes them potentially useful in applications involving cesium oxide coatings, for example, photoemissive devices and catalytic converters.

    7. The INPHARMA Method: Protein-Mediated Interligand NOEs for Pharmacophore Mapping (pages 4172–4175)

      Víctor M. Sánchez-Pedregal, Marcel Reese, Jens Meiler, Marcel J. J. Blommers, Christian Griesinger and Teresa Carlomagno

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500503

      Thumbnail image of graphical abstract

      Orientation of a ligand: The first observation of interligand NOEs between two competitive ligands A and B binding consecutively and not simultaneously to the same target is reported for baccatin III and epothilone A in the presence of tubulin. Such effects, which are mediated by spin diffusion through protein protons (see scheme), could be used to determine the relative orientation of competitive ligands in the receptor binding pocket.

    8. Twelve-Connected Net with Face-Centered Cubic Topology: A Coordination Polymer Based on [Cu124-SCH3)6]6+ Clusters and CN Linkers (pages 4175–4178)

      Dan Li, Tao Wu, Xiao-Ping Zhou, Rui Zhou and Xiao-Chun Huang

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500290

      Thumbnail image of graphical abstract

      Globular configuration: a microporous coordination polymer based on a dodecanuclear copper(I) cluster (picture: C black, Cu red, N blue, S yellow) as a twelve-connected node, was synthesized by a simultaneous redox, sulfurization, and self-assembly reaction under solvothermal conditions. The synthesis provides a model reaction to simulate the transformation of inorganic sulfur into organic sulfur.

    9. Supramolecular Assembly and Coordination-Assisted Deaggregation of Multimetallic Macrocycles (pages 4178–4182)

      Cecily Tsz Lui Ma and Mark J. MacLachlan

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200500058

      Thumbnail image of graphical abstract

      Fluorescence switching: Multimetallic fluorescent macrocycles aggregate into supramolecular assemblies on changing the solvent from THF to CH2Cl2. Coordinating bases (e.g., pyridine) cause deaggregation of these assemblies and result in a large enhancement of the fluorescence (see schematic representation of the organization of the macrocycles in THF (left), in CH2Cl2 (middle), and after addition of pyridine (right)).

    10. Route to Cluster Helicates (pages 4182–4187)

      Manuel R. Bermejo, Ana M. González-Noya, Rosa M. Pedrido, María J. Romero and Miguel Vázquez

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500840

      Thumbnail image of graphical abstract

      Self control! A potentially dianionic helicand ligand is used to exert control over the assembly of metal complexes into common helical structures or supramolecular clusters depending on the oxidation state of the metal (see scheme). In the tetranuclear cluster dihelicates, a polyhedron of metal ions is the helical axis. The metal cluster in these complexes is stabilized by two soft donor atoms in the ligand.

    11. Supramolecular Coordination Assemblies of Dinuclear FeIII Complexes (pages 4187–4192)

      Wolfgang Schmitt, Jonathan P. Hill, M. Paula Juanico, Andrea Caneschi, Ferdinando Costantino, Christopher E. Anson and Annie K. Powell

      Version of Record online: 14 JUN 2005 | DOI: 10.1002/anie.200500516

      Thumbnail image of graphical abstract

      Emptying the honeycomb: Hybrid organic–inorganic coordination assemblies are synthesized using modified aminocarboxylic acid ligands as the structure-directing agents. The structure of the networks varies ranging from a lamellar motif through a densely packed hexagonal array, to an open-framework hexagonal assembly (see structure).

    12. Expanding the Range of Substrate Acceptance of Enzymes: Combinatorial Active-Site Saturation Test (pages 4192–4196)

      Manfred T. Reetz, Marco Bocola, José Daniel Carballeira, Dongxing Zha and Andreas Vogel

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500767

      Thumbnail image of graphical abstract

      CASTing for success: The traditional problem of expanding the range of substrate acceptance of enzymes can be solved by creating focused libraries of mutants resulting from randomization of pairs of properly chosen amino acids around the active site (see example with the lipase from Pseudomonas aeruginosa, amino acid pairs are shown in the same color). CAST=combinatorial active-site saturation test.

    13. Single-Crystal Dendritic Micro-Pines of Magnetic α-Fe2O3: Large-Scale Synthesis, Formation Mechanism, and Properties (pages 4197–4201)

      Minhua Cao, Tianfu Liu, Song Gao, Genban Sun, Xinglong Wu, Changwen Hu and Zhong Lin Wang

      Version of Record online: 7 JUN 2005 | DOI: 10.1002/anie.200500448

      Thumbnail image of graphical abstract

      Fractal hematite dendrites with structures resembling pine trees (see picture) were obtained by hydrothermal treatment of K3[Fe(CN)6]. They are formed by a novel process in which fast growth along six crystallographically equivalent directions forms dendritic or snowflakelike single-crystal structures, which differs from the mechanisms reported for other fractal structures.

    14. Synthesis of a Cycloallin Derivative from β-Cyclodextrin: Heptakis(2,3-dideoxy-2,3-epithio)-β-cycloallin (pages 4201–4204)

      Makoto Fukudome, Tomonori Shiratani, Stefan Immel, Yasuyoshi Nogami, De-Qi Yuan and Kahee Fujita

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200462678

      Thumbnail image of graphical abstract

      Made from sugar: Heptakis(2,3-dideoxy-2,3-epithio)-β-cycloallin has been synthesized in a one-pot procedure from a β-cyclodextrin derivative. Molecular modeling studies suggest that the structure of the cycloallin is inverted relative to that of regular cyclodextrins, with the sulfur atoms of the epithio groups pointing inwards to form the narrower aperture (see model; S yellow, O red, C gray, H white).

    15. You have free access to this content
      Highly Enantioselective Catalytic Fluorination and Chlorination Reactions of Carbonyl Compounds Capable of Two-Point Binding (pages 4204–4207)

      Norio Shibata, Junji Kohno, Kazumi Takai, Takehisa Ishimaru, Shuichi Nakamura, Takeshi Toru and Shuji Kanemasa

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200501041

      Thumbnail image of graphical abstract

      New tools in drug development: The catalytic enantioselective fluorination and chlorination reactions of carbonyl compounds containing an additional binding site (see scheme) proceed with extremely high enantioselectivity and require low catalyst loadings (2–10 mol % dbfox-Ph/NiII). Asymmetric amplification is also observed in these enantioselective halogenations.

    16. Heteroligated RhI Tweezer Complexes (pages 4207–4209)

      Aaron M. Brown, Maxim V. Ovchinnikov and Chad A. Mirkin

      Version of Record online: 7 JUN 2005 | DOI: 10.1002/anie.200500689

      Thumbnail image of graphical abstract

      A halide-induced ligand rearrangement around a RhI center can be used for the preparation of heteroligated tweezer-type complexes. By using a variety of P,S- and P,O-hemilabile ligands, the complexes can be interconverted between four different RhI-coordination environments (see scheme).

    17. You have free access to this content
      Achiral Ligands Dramatically Enhance Rate and Enantioselectivity in the Rh/Phosphoramidite-Catalyzed Hydrogenation of α,β-Disubstituted Unsaturated Acids (pages 4209–4212)

      Rob Hoen, Jeroen A. F. Boogers, Heiko Bernsmann, Adriaan J. Minnaard, Auke Meetsma, Theodora D. Tiemersma-Wegman, André H. M. de Vries, Johannes G. de Vries and Ben L. Feringa

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500784

      Thumbnail image of graphical abstract

      Mixing it up: A catalytic system based on a mixed-ligand approach has been developed for the rhodium-catalyzed asymmetric hydrogenation of cinnamic acid derivatives (see scheme, cod= cycloocta-1,5-diene). It is the first time that a catalyst complex based on a heterocombination of a chiral and an achiral monodentate ligand gives dramatically higher enantioselectivity (up to 99 %) than any of the corresponding homocomplexes.

    18. Diphenylprolinol Silyl Ethers as Efficient Organocatalysts for the Asymmetric Michael Reaction of Aldehydes and Nitroalkenes (pages 4212–4215)

      Yujiro Hayashi, Hiroaki Gotoh, Takaaki Hayashi and Mitsuru Shoji

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500599

      Thumbnail image of graphical abstract

      The direct, catalytic, asymmetric Michael addition of aldehydes to nitroolefins in the presence of a chiral diphenylprolinol silyl ether organocatalyst is described (see scheme). The desired 1,4-addition products were obtained in nearly optically pure form in good yield with high syn diastereoselectivity. TMS=trimethylsilyl.

    19. A [70]Fullerene Chloride, C70Cl16, Obtained by the Attempted Bromination of C70 in TiCl4 (pages 4215–4218)

      Sergey I. Troyanov and Alexey A. Popov

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500476

      Thumbnail image of graphical abstract

      Tales of the unexpected: The [70]fullerene chloride C70Cl16 resulted from the reaction of [70]fullerene with a mixture of Br2 and TiCl4. A single-crystal X-ray crystallographic study revealed the presence of two isomers of C70Cl16, both containing a belt of ten chlorine atoms around the equator and a skew pyramidal cap of six chlorine atoms on the pole of the C70Cl16 molecule (see picture).

    20. Divergent Synthesis of Sialylated Glycan Chains: Combined Use of Polymer Support, Resin Capture–Release, and Chemoenzymatic Strategies (pages 4218–4224)

      Shinya Hanashima, Shino Manabe and Yukishige Ito

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500777

      Thumbnail image of graphical abstract

      Carbo loading! The synthesis of α(2,3)- or α(2,6)-sialylated biantennary glycans is possible with a new approach. The common precursor 1 was synthesized with a soluble polymer support strategy (a) in combination with a resin capture–release protocol. Hexasaccharide 1 can then be diverged to various polysaccharides by enzymatic glycosylation (b). Bn=benzyl, TBS=tert-butyldimethylsilyl.

    21. Rhodium-Catalyzed Asymmetric 1,6-Addition of Aryl Zinc Reagents to Dienones (pages 4224–4227)

      Tamio Hayashi, Shohei Yamamoto and Norihito Tokunaga

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500678

      Thumbnail image of graphical abstract

      A highly enantioselective methodology allows the preparation of α,β-unsaturated ketones that contain a new stereogenic center at the C5 position. This approach is realized through the title reaction in the presence of chlorotrimethylsilane as a Lewis acid and a rhodium/(S)-binap complex as the catalyst followed by acidic hydrolysis (see scheme). binap=2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl.

    22. Self-Assembled Monolayers of Isocyanides on Nickel Electrodes (pages 4228–4231)

      Youngu Lee, Gustavo M. Morales and Luping Yu

      Version of Record online: 2 JUN 2005 | DOI: 10.1002/anie.200500942

      Thumbnail image of graphical abstract

      Alligator clip on a nickel electrode: Monolayers of ferrocenyl-terminated isocyanides are strongly chemisorbed on nickel surfaces (see picture). The nickel–isocyanide interaction has a parallel binding mode, and the monolayers have higher thermal stability in boiling ethanol than thiol monolayers on gold. The nickel–isocyanide monolayers could be useful in molecular electronics.

    23. Dimerization of Indanediyl Fragments: An Alkene Analogue for Group 13? (pages 4231–4235)

      Michael S. Hill, Peter B. Hitchcock and Ruti Pongtavornpinyo

      Version of Record online: 2 JUN 2005 | DOI: 10.1002/anie.200500764

      Thumbnail image of graphical abstract

      A β-diketiminate complex of indium, [In{N(2,4,6-Me3C6H2)C(Me)}2CH], dimerizes in the solid state (see space-filling model) to provide an indium species that is formally isoelectronic to the historically significant bis(stannane)diyls. A direct In[BOND]In bond is formed yielding a centrosymmetric dimer that possesses approximate C2h symmetry with a mutual trans-bent orientation of the N-chelating ligands.

    24. Mechanistic Insight into Alcohol Oxidation by High-Valent Iron–Oxo Complexes of Heme and Nonheme Ligands (pages 4235–4239)

      Na Young Oh, Yumi Suh, Mi Joo Park, Mi Sook Seo, Jinheung Kim and Wonwoo Nam

      Version of Record online: 2 JUN 2005 | DOI: 10.1002/anie.200500623

      Thumbnail image of graphical abstract

      Iron-mediated oxidation: High-valent iron(IV)–oxo complexes of heme and nonheme ligands are generated in situ and are used in mechanistic studies of alcohol oxidation (see scheme). It is proposed that the oxidation of alcohols occurs by an α-CH hydrogen atom abstraction followed by electron transfer. Porp=porphyrin.

    25. Effect of Pressure on the Magnetic Anisotropy in the Single-Molecule Magnet Mn12-Acetate: An Inelastic Neutron Scattering Study (pages 4239–4242)

      Andreas Sieber, Roland Bircher, Oliver Waldmann, Graham Carver, Grégory Chaboussant, Hannu Mutka and Hans-Ulrich Güdel

      Version of Record online: 7 JUN 2005 | DOI: 10.1002/anie.200500171

      Thumbnail image of graphical abstract

      The pressure-dependence of the zero-field splitting of the S=10 ground state of the single-molecule magnet Mn12-acetate was studied by inelastic neutron scattering (INS) at hydrostatic pressures up to 12 kbar (see picture). The anisotropy increases with increasing pressure, and a pressure-dependent minority species of Mn12-acetate was observed. The increased anisotropy arises from increases in the single-ion anisotropy of the Mn3+ building blocks.

    26. Design, Construction, and Intracellular Activation of an Intramolecularly Self-Silenced Signal Transduction Inhibitor (pages 4242–4244)

      Seung-Yub Lee, Fubo Liang, Xiao-Ling Guo, Laiping Xie, Sean M. Cahill, Michael Blumenstein, Heyi Yang, David S. Lawrence and Zhong-Yin Zhang

      Version of Record online: 2 JUN 2005 | DOI: 10.1002/anie.200462004

      Thumbnail image of graphical abstract

      Ricin, diphtheria toxin, and other cytotoxic proteins are two-component systems which contain a carrier protein that biochemically silences the activity of the appended “warhead” protein until it is delivered into the cell. A cell-penetrating peptide (CPP) has been used in an analogous fashion (see picture) to suppress the activity of a PTP1B inhibitor that becomes activated by cleavage of the disulfide bridge upon cellular entry.

    27. Quantification of the Cellular Uptake of Cell-Penetrating Peptides by MALDI-TOF Mass Spectrometry (pages 4244–4247)

      Fabienne Burlina, Sandrine Sagan, Gérard Bolbach and Gérard Chassaing

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500477

      Thumbnail image of graphical abstract

      The ins and outs of peptides: The internalization efficiencies of three cell-penetrating peptides (CPPs; penetratin, (Arg)9, and Tat48–59) have been measured by MALDI-TOF MS (see scheme). The method leads to direct detection of the CPPs and allows unambiguous discrimination between membrane-bound and internalized CPP. Furthermore, the cellular uptake efficiencies of several CPPs can be compared in a single experiment.

    28. Prediction of Novel Phases of Tantalum(V) Nitride and Tungsten(VI) Nitride That Can Be Synthesized under High Pressure and High Temperature (pages 4249–4254)

      Peter Kroll, Timon Schröter and Martina Peters

      Version of Record online: 6 JUN 2005 | DOI: 10.1002/anie.200462980

      Thumbnail image of graphical abstract

      A combination of quantum-chemical and thermochemical calculations leads to the prediction of novel polymorphs of Ta3N5 and WN2. Based on thermochemical data the fugacity of nitrogen at very high pressures is estimated which facilitates a detailed assessment of the synthesis conditions. The modifications of Ta3N5-II and WN2-II have metal centers the are eight- and nine-fold coordinate (see picture: red W, green N).

    29. Stability of Gaseous Thallium Monofluoride as TlF0, TlF+, and TlF2+ (pages 4254–4257)

      Detlef Schröder, Christoph van Wüllen, Helmut Schwarz and Thomas M. Klapötke

      Version of Record online: 7 JUN 2005 | DOI: 10.1002/anie.200461334

      Thumbnail image of graphical abstract

      Probing a shallow minimum with a sledgehammer can be said to characterize the present experimental studies, which reveal the existence of thallium fluoride in three different charge states. High-level theory provides a quantitative description of the redox energetics of TlF0/+/2+ (see picture: potential curve for TlF+).

    30. Preparation of Functionalized Aryl Magnesium Reagents by the Addition of Magnesium Aryl Thiolates and Amides to Arynes (pages 4258–4261)

      Wenwei Lin, Ioannis Sapountzis and Paul Knochel

      Version of Record online: 7 JUN 2005 | DOI: 10.1002/anie.200500443

      Thumbnail image of graphical abstract

      Reactive arynes, which are readily generated by the reaction of ortho-iodoarylsulfonates with iPrMgCl, undergo the smooth addition of various magnesium nucleophiles like magnesium thiolates, selenides, and amides. In all cases the resulting functionalized aryl magnesium species can be trapped by an electrophile leading to highly functionalized aromatic compounds (see scheme).

    31. The Molecules AlO2, Al(O2)2, and Al(O2)3: Experimental and Quantum-Chemical Investigations on the Oxidation of Aluminum Atoms (pages 4261–4264)

      Gregor Stößer and Hansgeorg Schnöckel

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200500512

      Thumbnail image of graphical abstract

      On the route to alumina, oxygen-rich oxides such as Al(O2)3 (see picture) are detected spectroscopically during the stepwise oxidation of aluminum atoms and confirmed structurally by quantum-chemical calculations.

    32. You have free access to this content

SEARCH

SEARCH BY CITATION