Angewandte Chemie International Edition

Cover image for Vol. 44 Issue 25

June 20, 2005

Volume 44, Issue 25

Pages 3787–3941

    1. Cover Picture: Cluster Disorder and Ordering Principles in Al-Stabilized “LaI” (Angew. Chem. Int. Ed. 25/2005) (page 3787)

      Oliver Oeckler, Thomas Weber, Lorenz Kienle, Hansjürgen Mattausch and Arndt Simon

      Version of Record online: 10 JUN 2005 | DOI: 10.1002/anie.200590083

      Diffuse diffraction data from disordered compounds can be interpreted with new numerical algorithms; however, there are few examples of quantitative structure refinement against all data and not only Bragg reflections. In the Communication on page 3917 ff., the authors demonstrate the application of evolutionary algorithms to solve the structure of an aluminum-stabilized lanthanum subiodide. The cover picture shows a diffraction pattern of the compound in the background and a section of the disordered structure model in the center.

    2. You have free access to this content
      Generation of Monodisperse Particles by Using Microfluidics: Control over Size, Shape, and Composition (page 3799)

      Shengqing Xu, Zhihong Nie, Minseok Seo, Patrick Lewis, Eugenia Kumacheva, Howard A. Stone, Piotr Garstecki, Douglas B. Weibel, Irina Gitlin and George M. Whitesides

      Version of Record online: 10 JUN 2005 | DOI: 10.1002/anie.200590085

    3. Shape-Persistent Phenylene-Acetylene Macrocycles: Large Rings—Low Yield? (pages 3806–3808)

      Sigurd Höger

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200500681

      Thumbnail image of graphical abstract

      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.

    4. Liquid Inorganic–Organic Nanocomposites: Novel Electrolytes and Ferrofluids (pages 3809–3811)

      Bernd Smarsly and Helena Kaper

      Version of Record online: 11 MAY 2005 | DOI: 10.1002/anie.200500690

      Thumbnail image of graphical abstract

      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, —N+ is C3H6N+(CH3)(C10H21)2) combine the characteristics of both components in a homogenous material that can be used in batteries and solar cells.

    5. Inhibitors of Protein Tyrosine Phosphatases: Next-Generation Drugs? (pages 3814–3839)

      Laurent Bialy and Herbert Waldmann

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200461517

      Thumbnail image of graphical abstract

      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.

    6. Weak CH⋅⋅⋅F Bridges and Internal Dynamics in the CH3F⋅CHF3 Molecular Complex (pages 3840–3844)

      Walther Caminati, Juan C. López, José L. Alonso and Jens-Uwe Grabow

      Version of Record online: 2 MAY 2005 | DOI: 10.1002/anie.200500775

      Thumbnail image of graphical abstract

      A preferred conformation of the internally highly dynamic fluoromethane–trifluoromethane molecular complex results from the stabilization of the two subunits by three weak CH⋅⋅⋅F 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.

    7. A Metal–Organic Framework with the Zeolite MTN Topology Containing Large Cages of Volume 2.5 nm3 (pages 3845–3848)

      Qianrong Fang, Guangshan Zhu, Ming Xue, Jinyu Sun, Yen Wei, Shilun Qiu and Ruren Xu

      Version of Record online: 29 APR 2005 | DOI: 10.1002/anie.200462260

      Thumbnail image of graphical abstract

      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⋅46 H2O⋅68 DMF greatly expands the original structure of MTN and contains large cages with a volume of about 2522 Å3 (see structure). MTN=zeolite socony mobil – thirty-nine, DMF=N,N-dimethylformamide.

    8. Diffusion of Water in a Nonporous Hydrophobic Crystal (pages 3848–3851)

      Praveen K. Thallapally, Gareth O. Lloyd, Jerry L. Atwood and Leonard J. Barbour

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200500749

      Thumbnail image of graphical abstract

      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-crystal-to-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.

    9. Total Chemical Synthesis and X-ray Crystal Structure of a Protein Diastereomer: [D-Gln 35]Ubiquitin (pages 3852–3856)

      Duhee Bang, George I. Makhatadze, Valentina Tereshko, Anthony A. Kossiakoff and Stephen B. Kent

      Version of Record online: 18 APR 2005 | DOI: 10.1002/anie.200463040

      Thumbnail image of graphical abstract

      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.

    10. Triangular Geometrical and Magnetic Motifs Uniquely Linked on a Spherical Capsule Surface (pages 3857–3861)

      Achim Müller, Ana Maria Todea, Joris van Slageren, Martin Dressel, Hartmut Bögge, Marc Schmidtmann, Marshall Luban, Larry Engelhardt and Mariana Rusu

      Version of Record online: 25 MAY 2005 | DOI: 10.1002/anie.200500697

      Thumbnail image of graphical abstract

      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.

    11. Irreversible Inhibition of Metallo-β-lactamase (IMP-1) by 3-(3-Mercaptopropionylsulfanyl)propionic Acid Pentafluorophenyl Ester (pages 3861–3864)

      Hiromasa Kurosaki, Yoshihiro Yamaguchi, Toshihiro Higashi, Kimitaka Soga, Satoshi Matsueda, Haruka Yumoto, Shogo Misumi, Yuriko Yamagata, Yoshichika Arakawa and Masafumi Goto

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200500835

      Thumbnail image of graphical abstract

      Resistance is futile: Pathogenic bacteria that produce metallo-β-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-β-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 (Nζ) of Lys 224.

    12. Self-Assembly of an Interlaced Triple-Stranded Molecular Braid with an Unprecedented Topology through Hydrogen-Bonding Interactions (pages 3864–3867)

      Xin-Jun Luan, Yao-Yu Wang, Dong-Sheng Li, Ping Liu, Huai-Ming Hu, Qi-Zhen Shi and Shie-Ming Peng

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200500744

      Thumbnail image of graphical abstract

      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 interlaced braid which looks just like a hair plait (see X-ray crystallographic structure). The three strands are held together through hydrogen-bonding interactions.

    13. A Modular Strategy to Artificial Double Helices (pages 3867–3870)

      Yoshie Tanaka, Hiroshi Katagiri, Yoshio Furusho and Eiji Yashima

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200501028

      Thumbnail image of graphical abstract

      No metal required: Double-helical assemblies can be constructed through hydrogen bonds upon formation of amidinium–carboxylate salt bridges (see schematic representation). The double-helical structures formed including the helix sense are predictable by this approach.

    14. Regio- and Stereocontrolled Total Synthesis of Benanomicin B (pages 3871–3874)

      Ken Ohmori, Minoru Tamiya, Mitsuru Kitamura, Hirohisa Kato, Mami Oorui and Keisuke Suzuki

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200501210

      Thumbnail image of graphical abstract

      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).

    15. A Catalytic Asymmetric Three-Component 1,4-Addition/Aldol Reaction: Enantioselective Synthesis of the Spirocyclic System of Vannusal A (pages 3874–3879)

      K. C. Nicolaou, Wenjun Tang, Philippe Dagneau and Raffaella Faraoni

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200500789

      Thumbnail image of graphical abstract

      Three's not always a crowd: A three-component reaction involving α,β-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.

    16. Synthesis of the Putative Structure of 7-Deoxycylindrospermopsin: C7 Oxygenation Is Not Required for the Inhibition of Protein Synthesis (pages 3879–3881)

      Ryan E. Looper, Maria T. C. Runnegar and Robert M. Williams

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200500520

      Thumbnail image of graphical abstract

      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.

    17. Enantioselective Henry Reactions under Dual Lewis Acid/Amine Catalysis Using Chiral Amino Alcohol Ligands (pages 3881–3884)

      Claudio Palomo, Mikel Oiarbide and Antonio Laso

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200463075

      Thumbnail image of graphical abstract

      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.

    18. Axial Ligand Effects: Utilization of Chiral Sulfoxide Additives for the Induction of Asymmetry in (Salen)ruthenium(ii) Olefin Cyclopropanation Catalysts (pages 3885–3889)

      Jason A. Miller, Bradley A. Gross, Michael A. Zhuravel, Wiechang Jin and SonBinh T. Nguyen

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200460887

      Thumbnail image of graphical abstract

      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.

    19. Synthesis of Highly Substituted Pyridazines through Alkynyl Boronic Ester Cycloaddition Reactions (pages 3889–3892)

      Matthew D. Helm, Jane E. Moore, Andrew Plant and Joseph P. A. Harrity

      Version of Record online: 19 MAY 2005 | DOI: 10.1002/anie.200500288

      Thumbnail image of graphical abstract

      A highly regioselective transformation of tetrazines through a cycloaddition reaction with alkynyl boronic esters provides highly substituted pyridazine boronic esters as intermediates for C[BOND]O and C[BOND]C bond-forming reactions (see scheme). Functionalization reactions of the C[BOND]B bond, such as oxidation and the Suzuki cross-coupling, show the versatility of these species.

    20. Total Synthesis of Avrainvillamide (CJ-17,665) and Stephacidin B (pages 3892–3895)

      Phil S. Baran, Carlos A. Guerrero, Benjamin D. Hafensteiner and Narendra B. Ambhaikar

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200500655

      Thumbnail image of graphical abstract

      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.

    21. Construction of Highly Functionalized Medium-Sized Rings: Synthesis of Hyperforin and Perforatumone Model Systems (pages 3895–3899)

      K. C. Nicolaou, Giacomo E. A. Carenzi and Valer Jeso

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200500776

      Thumbnail image of graphical abstract

      Bridging the gap: A sequence of reactions (1[RIGHTWARDS ARROW]2[RIGHTWARDS ARROW]3[RIGHTWARDS ARROW]4) leads to bridged, polyfunctional, medium-sized rings in synthetically useful yields. These rings are reminiscent of the molecular architectures of hyperforin and perforatumone.

    22. Total Synthesis of Cavicularin and Riccardin C: Addressing the Synthesis of an Arene That Adopts a Boat Configuration (pages 3899–3901)

      David C. Harrowven, Timothy Woodcock and Peter D. Howes

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200500466

      Thumbnail image of graphical abstract

      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.

    23. An Artificial Riboflavin Receptor Prepared by a Template Analogue Imprinting Strategy (pages 3902–3906)

      Panagiotis Manesiotis, Andrew J. Hall, Julien Courtois, Knut Irgum and Börje Sellergren

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200500342

      Thumbnail image of graphical abstract

      Cheers! Specificity for riboflavin in water-rich 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>106M−1).

    24. One-Step Synthesis of a Platinum(0)–Gallium(III) Chrysene Complex (pages 3906–3909)

      Mikhail Gorlov, Andreas Fischer and Lars Kloo

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200462373

      Thumbnail image of graphical abstract

      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.

    25. Highly Chemo- and Enantioselective Arylative Cyclization of Alkyne-Tethered Electron-Deficient Olefins Catalyzed by Rhodium Complexes with Chiral Dienes (pages 3909–3912)

      Ryo Shintani, Akihiro Tsurusaki, Kazuhiro Okamoto and Tamio Hayashi

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200500843

      Thumbnail image of graphical abstract

      A rhodium catalyst promotes the arylative cyclization of alkyne-tethered electron-deficient olefins in the presence of aryl boronic acids. High chemoselectivity was attained uniquely by the use of diene ligands, and high enantioselectivity was successfully realized by employing a C2-symmetric chiral bicyclo[2.2.2]octadiene ligand (see scheme).

    26. An Efficient and General Iron-Catalyzed Arylation of Benzyl Alcohols and Benzyl Carboxylates (pages 3913–3917)

      Irina Iovel, Kristin Mertins, Jette Kischel, Alexander Zapf and Matthias Beller

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200462522

      Thumbnail image of graphical abstract

      Green grow the diarylmethanes: Substituted arenes and heteroarenes can be easily benzylated in the presence of inexpensive and relatively nontoxic metal 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.

    27. Cluster Disorder and Ordering Principles in Al-Stabilized “LaI” (pages 3917–3921)

      Oliver Oeckler, Thomas Weber, Lorenz Kienle, Hansjürgen Mattausch and Arndt Simon

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200500594

      Thumbnail image of graphical abstract

      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 La≈0.7I1−xAlx (x≈0.14) given the observed lattice.

    28. Single-Molecule Experiments in Synthetic Biology: An Approach to the Affinity Ranking of DNA-Binding Peptides (pages 3921–3924)

      Rainer Eckel, Sven David Wilking, Anke Becker, Norbert Sewald, Robert Ros and Dario Anselmetti

      Version of Record online: 20 MAY 2005 | DOI: 10.1002/anie.200500152

      Thumbnail image of graphical abstract

      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 single-molecule 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.

    29. Electron Density and Bonding at Inverted Carbon Atoms: An Experimental Study of a [1.1.1]Propellane Derivative (pages 3925–3928)

      Marc Messerschmidt, Stephan Scheins, Lutz Grubert, Michael Pätzel, Günter Szeimies, Carsten Paulmann and Peter Luger

      Version of Record online: 13 MAY 2005 | DOI: 10.1002/anie.200500169

      Thumbnail image of graphical abstract

      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⋅⋅⋅C4a (see picture), which is characteristic for a covalent bond; however, no charge accumulation at the bond critical point was seen.

    30. Nitro(nitroso)cyanomethanides (pages 3929–3932)

      Harald Brand, Peter Mayer, Axel Schulz and Jan J. Weigand

      Version of Record online: 17 MAY 2005 | DOI: 10.1002/anie.200500495

      Thumbnail image of graphical abstract

      More bangs for the buck. Explosive nitro(nitroso)cyanomethanides M′[C(NO2)(NO)(CN)] (M′=alkali metal, NMe4) were prepared in a simple, two-step, 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.

    31. Phosphine-Stabilized Copper–Antimony Clusters: Syntheses, Structures, and Theoretical Investigations of [Cu12(SbSiMe3)6(PiPr3)6], [Cu40Sb12(PMe3)20], and [Cu45Sb16(PEt2Me)16] (pages 3932–3936)

      Reinhart Ahlrichs, Dieter Fenske, Mary McPartlin, Alexander Rothenberger, Claudia Schrodt and Stephan Wieber

      Version of Record online: 18 MAY 2005 | DOI: 10.1002/anie.200500593

      Thumbnail image of graphical abstract

      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.

    32. You have free access to this content