Angewandte Chemie International Edition

Cover image for Vol. 42 Issue 23

June 16, 2003

Volume 42, Issue 23

Pages 2559–2691

    1. Cover Picture: Novel Ruthenium- and Platinum-Catalyzed Sequential Reactions: Synthesis of Tri- and Tetrasubstituted Furans and Pyrroles from Propargylic Alcohols and Ketones (Angew. Chem. Int. Ed. 23/2003) (page 2559)

      Yoshiaki Nishibayashi, Masato Yoshikawa, Youichi Inada, Marilyn Daisy Milton, Masanobu Hidai and Sakae Uemura

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200390485

      A One-Pot Sequential Reaction for the ruthenium- and platinum-catalyzed preparation of a trisubstituted furan from a propargylic alcohol and acetone in good yield with high regioselectivity is shown. Two different catalysts, the thiolate-bridged diruthenium complex [Cp*RuCl(μ2-SMe)RuCp*Cl] (Cp*=C5Me5) and PtCl2, sequentially promote each catalytic cycle in the same medium. For more information, see the Communication by M. Hidai, S. Uemura, and co-workers on pp. 2681 ff.

    2. Molecule-Based Magnetic Materials (pages 2570–2572)

      Eugenio Coronado, Fernando Palacio and Jaume Veciana

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200390487

    3. Supertetrahedra in Sulfides: Matter against Mathematical Series? (pages 2576–2579)

      Gérard Férey

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200201621

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      The game continues… Self-assembled sulfide supertetrahedra can be used to generate porous solids with unusual electoluminescence and semiconducting properties. Recent advances, including the discovery of corner-linked superclusters (see picture) and super-supertetrahedral clusters, may lead to materials, the properties of which could be superior to the best quantum dots known to date.

    4. Pd-Catalyzed Enantioselective Allylic Substitution: New Strategic Options for the Total Synthesis of Natural Products (pages 2580–2584)

      Timm Graening and Hans-Günther Schmalz

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200301644

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      As versatile as Nature: Pd-catalyzed enantioselective allylic substitution is a powerful reaction in modern synthetic chemistry. The reactions of cyclic allylic substrates (see figure) have recently been proven to be of particular value as they lead to novel and highly efficient strategies in the total synthesis of various natural products.

    5. Metal Alkynyl σ Complexes: Synthesis and Materials (pages 2586–2617)

      Nicholas J. Long and Charlotte K. Williams

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200200537

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      The M[BOND]C[TRIPLE BOND]C structural unit, which can be used to establish a wide variety of molecular topologies (see, for example, the tris(ferrocenylalkynyl) complex and the molecular rigid-rod polymer shown), together with the increasing importance of material properties such as electron transfer, nonlinear optical behavior, and luminescence, combine to make transition-metal alkynyl complexes, especially as oligomers and polymers, of particular current interest.

    6. Reversible Enantiofacial Differentiation of a Single Heterocyclic Substrate by Supramolecular Receptors (pages 2620–2623)

      Matthias C. Schopohl, Carsten Siering, Olga Kataeva and Siegfried R. Waldvogel

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351102

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      Telling top and bottom apart: Supramolecular receptors can discriminate between the “top” and “bottom” sides of a single guest molecule, such as caffeine (see picture). This reversible enantiofacial differentiation results in the preferential formation of the α or β complexes.

    7. [Ge9{Si(SiMe3)3}3]: A Soluble Polyhedral Ge9 Cluster Stabilized by Only Three Silyl Ligands (pages 2624–2625)

      Andreas Schnepf

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200250683

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      Naked” but refined! The reaction of germanium(I) bromide with Li{Si(SiMe3)3} gives the polyhedral Ge9 cluster ion [Ge9{Si(SiMe3)3}3] (see structure), in which only three of the nine germanium atoms are bound to a ligand, the remaining germanium atoms are naked. The unusually high solubility of this cluster opens the possibility of using it as a starting material for further reactions.

    8. Coordination Geometry of the Discrete Pentafluoroaluminate Dianion [AlF5]2− (pages 2626–2629)

      Udo Groß, Dirk Müller and Erhard Kemnitz

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200350885

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      Welcome to the family: The previously unknown discrete pentafluoroaluminate [(CH3)4N]+2[AlF5]2− salt, a missing link of the homoleptic fluoroaluminate family, is synthesized from [(CH3)4N]+[AlF4] and [(CH3)4N]+F. IR and Raman spectroscopic data along with 27Al MAS NMR spectroscopy investigations reveal a perfect and unperturbed trigonal-bipyramidal structure (see picture).

    9. A Pseudotetrahedral, High-Oxidation-State Organonickel Compound: Synthesis and Structure of Bromotris(1-norbornyl)nickel(IV) (pages 2631–2633)

      Vladimir Dimitrov and Anthony Linden

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200219383

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      A breath of fresh air: Air oxidation of [nBu4N]2[NiII(1-nor)3Br], prepared from [nBu4N]2[NiIIBr4] and 1-norbornyllithium generates the title pseudotetrahedral organometallic complex in which a nickel center with the formal oxidation state of +4 is present (see structure; Ni purple, Br brown, C black, H green).

    10. Biogenesis of 3-Alkylpyridine Alkaloids in the Marine Mollusc Haminoea Orbignyana (pages 2633–2636)

      Adele Cutignano, Annabella Tramice, Salvatore De Caro, Guido Villani, Guido Cimino and Angelo Fontana

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200250642

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      Fruits of the sea: Alkylpyridine alkaloids are a family of marine natural products, the structures of which are all related to each other by the presence of a biogenetically common motif, an alkyl chain linked to C-3 of a six-membered nitrogen heterocycle. We report the first experimental evidence for the biosynthesis of alkylpyridines (see scheme).

    11. Hydrogenation of Arenes over Catalysts that Combine a Metal Phase and a Grafted Metal Complex: Role of the Single-Site Catalyst (pages 2636–2639)

      Claudio Bianchini, Vladimiro Dal Santo, Andrea Meli, Simonetta Moneti, Marta Moreno, Werner Oberhauser, Rinaldo Psaro, Laura Sordelli and Francesco Vizza

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200250667

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      Cooperating catalysts: The combined single-site/dispersed-metal catalyst [Rh(cod)(sulphos)]–Pd0/SiO2 (cod=cyclooctadiene; sulphos=O3S(C6H4)CH2C(CH2PPh2)3) is more efficient than the dispersed-metal catalyst Pd0/SiO2 for the hydrogenation of arenes to cycloalkanes. The grafted rhodium moieties and the palladium particles in [Rh(cod)(sulphos)]–Pd0/SiO2 cooperate to speed up the hydrogenation of arenes (see scheme).

    12. Highly Ordered Mesoporous Silicon Oxynitride Materials as Base Catalysts (pages 2639–2644)

      Yongde Xia and Robert Mokaya

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200350978

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      Basically, a good catalyst: The introduction of NHx species into the framework of mesoporous silicas results in silicon oxynitride materials and generates basic sites, which exhibit considerable catalytic activity for the Knoevenagel condensation reaction (see scheme). The well-ordered mesoporous oxynitrides have a high surface area and pore volume and are attractive as alternative basic catalysts, especially for large-molecule transformations.

    13. Self-Healing Systems Having a Design Stimulated by the Vertebrate Spine (pages 2644–2647)

      Mila Boncheva and George M. Whitesides

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351010

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      The organization of the vertebrate spine was the source of the concepts used to design self-healing structures. These structures comprise mm-sized beads self-assembled on elastomeric threads and connected by solder joints. The structures spontaneously realign and heal (top) after breaking and dislocation (bottom).

    14. Palladium(0)-Catalyzed Tandem Cyclization of Allenenes (pages 2647–2650)

      Hiroaki Ohno, Kumiko Miyamura, Yusuke Takeoka and Tetsuaki Tanaka

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351011

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      Tri- and tetracyclic heterocycles were formed through the tandem cyclization of allenenes 1 upon treatment with an aryl iodide, potassium carbonate, and catalytic [Pd(PPh3)4] (see scheme). The reactivity of the palladium(II) intermediates could be controlled by substitution (R′) at the olefin terminus (Mts=2,4,6-trimethylphenylsulfonyl).

    15. Phenyl{bis(triphenylphosphanemethylenido)}borane: A Zwitterionic Chelating Ligand Exhibiting Allyl-Type Coordination (pages 2651–2653)

      Feilong Jiang, Pamela J. Shapiro, Faysal Fahs and Brendan Twamley

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351056

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      When complexed to transition-metal atoms, the zwitterionic ligand phenyl{bis(triphenylphosphanemethylenido)}borane behaves like a neutral analogue of the η3-allyl ligand. Syntheses and X-ray crystal structures of the ligand and its complexes with ZrCl4 and PdCl2 (depicted) are described (Pd=cyan, B=yellow, P=pink, Cl=green, C=white).

    16. Total Synthesis of TMC-95A (pages 2654–2657)

      Masayuki Inoue, Hayato Sakazaki, Hidetomo Furuyama and Masahiro Hirama

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351130

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      A Suzuki–Miyaura coupling reaction to form C1[BOND]C20, macrolactamization at N9[BOND]C10, and a mild decarboxylative anti elimination to selectively introduce the (Z)-1-propenylamide are key steps in a highly convergent and completely stereoselective synthesis of the potent proteasome inhibitor TMC-95A (see structure).

    17. Tin-Free Radical Allylation of B-Alkylcatecholboranes (pages 2658–2660)

      Arnaud-Pierre Schaffner and Philippe Renaud

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351171

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      Organoboranes, prepared in situ by hydroboration of olefins with catecholborane, are efficiently allylated with allyl sulfones by a radical fragmentation process (see scheme). This hydroallylation of alkenes proved to be general for a wide range of alkenes and allyl sulfones.

    18. Synthesis and Structural Characterization of Thermally Stable Group 13 Hydride Complexes Derived from a Gallium(I) Carbene Analogue (pages 2660–2663)

      Robert J. Baker, Cameron Jones, Marc Kloth and Jamie A. Platts

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351281

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      The first covalently bonded metal complexes derived from an anionic gallium carbene analogue (see picture) show remarkable thermal stability in the solid state. This fact suggests that gallium(I) heterocycles should prove to be versatile ligands towards both main-group and transition-metal fragments.

    19. Membership Rules for a Molecular Box: The Admission Process and Protection Provided to Guest Molecules (pages 2663–2666)

      Sodio C. N. Hsu, Maya Ramesh, James H. Espenson and Thomas B. Rauchfuss

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200219562

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      Crate chemistry: The inclusion dynamics of molecular boxes has been studied by virtue of the synthesis of the voided ionophilic packing crate [{CpCo(CN)3}4(Cp*Ru)4] (Cp=C5H5 Cp*=C5Me5). Numerous ions can then be inserted into the box (see scheme). The box exhibits the highest formation constant known for Cs+ ions. Once inside, ions are insulated from chemical attack, such as amine-deprotonation or H–D exchange.

    20. Targeted Gene Delivery to Cancer Cells: Directed Assembly of Nanometric DNA Particles Coated with Folic Acid (pages 2666–2669)

      Guy Zuber, Liliane Zammut-Italiano, Emmanuel Dauty and Jean-Paul Behr

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200250446

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      A synthetic viruslike particle: Monomolecular condensation of a gene into a 30-nm particle was performed by the DNA-templated air oxidation of a cationic thiol detergent to a gemini lipid (depicted in yellow). A folic acid coating was added (in the form of the DNA-binding folate-containing compounds represented schematically by 2) and the resulting DNA particles 1 were shown to be nanometric and stable, and to enter cells through the folic acid receptor.

    21. Modular Assembly of Two-Dimensional Metal–Organic Coordination Networks at a Metal Surface (pages 2670–2673)

      Alexandre Dmitriev, Hannes Spillmann, Nian Lin, Johannes V. Barth and Klaus Kern

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200250610

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      Impressive iron networks: Two-dimensional metal–organic coordination networks have been prepared by the vacuum deposition of organic polytopic linkers and metal atoms on a copper surface. This unprecedented technique enabled the modular assembly of open Fe–carboxylate grids (see image, Fe atoms in green) that possess regularly spaced, identically shaped cavities. The structure and composition of the networks can be tuned by controlling the deposition parameters.

    22. X-ray Structures of Binary and Ternary Enzyme-Product-Inhibitor Complexes of Matrix Metalloproteinases (pages 2673–2676)

      Ivano Bertini, Vito Calderone, Marco Fragai, Claudio Luchinat, Stefano Mangani and Beatrice Terni

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200350957

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      A helicoidal filament results from the approach of the N-terminus of the mutated variant of the catalytic domain of MMP-12 with the catalytic zinc center of another molecule (see X-ray structure); adjacent filaments are arranged in double helices. The N-terminal fragment is proposed to be analogous to an N-terminal polypeptide product after cleavage. Crystals yield two contrasting structures, in which the NH3+ ion is either triply hydrogen bonded, or only exhibits van der Waals interactions.

    23. Synthesis, Photophysical Properties, and Nanocrystal Formation of a New Class of Tetra-N-Substituted Perylenes (pages 2677–2681)

      Lutz H. Gade, Christian H. Galka, René M. Williams, Luisa De Cola, Mary McPartlin, Bin Dong and Lifeng Chi

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351348

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      A new class of perylene-derived dyes, tetra(carboxamido)perylenes, has been obtained by a generally applicable synthetic method. Derivative A is shown to form nanocrystalline aggregates in DMSO which display significantly modified photophysical behavior with respect to the monomer and were studied by using atomic force microscopy techniques.

    24. Novel Ruthenium- and Platinum-Catalyzed Sequential Reactions: Synthesis of Tri- and Tetrasubstituted Furans and Pyrroles from Propargylic Alcohols and Ketones (pages 2681–2684)

      Yoshiaki Nishibayashi, Masato Yoshikawa, Youichi Inada, Marilyn Daisy Milton, Masanobu Hidai and Sakae Uemura

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351170

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      Two cats. in the same pot: The two catalysts [Cp*RuCl(μ2-SMe)2RuCp*Cl] (1) and PtCl2 (2) promote a sequence of catalytic cycles in the same medium. Tri- or tetrasubstituted furans or pyrroles are afforded in moderate to good yields with high regioselectivities from the catalyzed reactions of propargylic alcohols with ketones or with ketones and anilines, respectively (see scheme; cats.=catalysts).

    25. Ferrous Wheels, Ellipse [(tBu3SiS)FeX]n, and Cube [(tBu3SiS)Fe(CCSitBu3)]4 (pages 2685–2687)

      Orson L. Sydora, Peter T. Wolczanski and Emil B. Lobkovsky

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200351143

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      The shapes of things to come: The use of the extremely bulky tBu3SiS ligand has enabled the synthesis of rare ferrous wheels (depicted), a unique ellipse, and an uncommon ferrous cube based on tetrahedral coordination. Fe=red, Cl=green, S=orange, Si=blue, C=gray.

    26. Preview: Angew. Chem. Int. Ed. 23/2003 (page 2691)

      Version of Record online: 12 JUN 2003 | DOI: 10.1002/anie.200390490

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