Angewandte Chemie International Edition

Cover image for Vol. 42 Issue 2

January 13, 2003

Volume 42, Issue 2

Pages 129–241

    1. Cover Picture: Angew. Chem. Int. Ed. 2/2003 (page 129)

      Christophe Copéret, Mathieu Chabanas, Romain Petroff Saint-Arroman and Jean-Marie Basset

      Version of Record online: 20 JAN 2003 | DOI: 10.1002/anie.200390090

      Catalysis research builds bridges between disciplines. The cover picture shows the linking position of surface organometallic chemistry between the two traditional areas of catalysis. The transfer of the concepts and tools of molecular organometallic chemistry to surfaces leads to the generation of well-defined surface species. The success of this approach results from understanding the reactions of organometallic complexes with the support. More about this field can be found in the review by Copéret, Basset, et al. on page 156ff.

    2. Recent Advances in Applications of Room-Temperature Ionic Liquid/Supercritical CO2 Systems (pages 148–150)

      Sergei V. Dzyuba and Richard A. Bartsch

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390070

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      Duet of Extremes: Efficient and environmentally benign, biphasic systems consisting of ionic liquids and supercritical CO2 (scCO2) have been employed in lipase-catalyzed esterifications (see scheme). The reaction takes place in the ionic liquid with or without a solid support, and the products are removed by means of either batchwise or continuous-flow extraction with supercritical CO2.

    3. Asymmetric Catalytic Aza-Henry Reactions Leading to 1,2-Diamines and 1,2-Diaminocarboxylic Acids (pages 151–153)

      Bernhard Westermann

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390071

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      In the wake of the aldol and Mannich reactions, textbook examples of asymmetric reactions, comes the aza-Henry reaction (aka nitro-Mannich reaction), which leads to 1,2-diamines or α,β-diaminocarboxylic acids (see scheme, PG=protecting group). Recent developments point to a bright future for this transformation.

    4. Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry (pages 156–181)

      Christophe Copéret, Mathieu Chabanas, Romain Petroff Saint-Arroman and Jean-Marie Basset

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390072

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      All sorts of improvements to heterogeneous catalysts are possible through surface organometallic chemistry. This method allows the structures of complexes grafted onto silica surfaces to be studied (see scheme). From this data, the elementary steps of the catalytic process can be deduced and structure–activity relationships developed, which results in a better understanding of the catalytic process.

    5. Tuning the Regioselectivity in the Palladium(II)-Catalyzed Isomerization of Alkylidene Cyclopropyl Ketones: A Dramatic Salt Effect (pages 183–187)

      Shengming Ma and Junliang Zhang

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390073

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      Useful building blocks are formed in this [PdCl2(CH3CN)2]-catalyzed regioselective isomerization reaction of alkylidene cyclopropyl ketones, in which a dramatic salt effect was observed. In the presence of NaI, the reaction in refluxing acetone afforded furans, while 4H-pyrans were formed at RT in the absence of NaI (see scheme).

    6. Mono-Tetrathiafulvalene Calix[4]pyrrole in the Electrochemical Sensing of Anions (pages 187–191)

      Kent A. Nielsen, Jan O. Jeppesen, Eric Levillain and Jan Becher

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390074

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      A redox-responsive receptor based on the annulation of the calix[4]pyrrole-receptor unit and the redox-active tetrathiafulvalene transducer unit is able to bind anions (see scheme) and act as an efficient chemosensor for the detection of anions by electrochemical means.

    7. Towards Multistep Nanostructure Synthesis: Programmed Enzymatic Self-Assembly of DNA/Gold Systems (pages 191–194)

      Antonios G. Kanaras, Zhenxin Wang, Andrew D. Bates, Richard Cosstick and Mathias Brust

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390075

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      Enzyme-dependent assembly of DNA/gold nanostructures is achieved using DNA-capped gold colloids and DNA processing enzymes. Particle-bound DNA double strands are cleaved at designated sites by a restriction endonuclease (see picture). In a subsequent step the particles are linked to each other through these activated sites by a DNA ligase. This new strategy enables the multistep synthesis of nanostructures.

    8. Catalytic Oxidation of Alcohols in Water under Atmospheric Oxygen by Use of an Amphiphilic Resin-Dispersion of a Nanopalladium Catalyst (pages 194–197)

      Yasuhiro Uozumi and Ryu Nakao

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390076

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      A step closer to the ideal oxidation of alcohols: Catalytic oxidation of alcohols in water under atmospheric oxygen was achieved by use of an amphiphilic resin-dispersion of a nanopalladium catalyst (see scheme). This system combines high catalytic activity owing to the large surface area of the nanoparticles and water-based reactivity provided by the amphiphilicity of the polystyrene—poly(ethylene glycol) matrix.

    9. Crystalline Structures of Sb4 Molecules in Antimony Thin Films (pages 199–202)

      Thorsten M. Bernhardt, Bert Stegemann, Bernhard Kaiser and Klaus Rademann

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390077

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      Sb4: The building block of a new solid-state modification of antimony. This is a somewhat provocative description of the fact that nanocrystalline structures of Sb4 tetrahedrons exist on the substrates AuSb2(100) and MoS2(0001). Scanning tunneling microscopy images (see picture, (a) and (b), respectively, each 39×39 Å2) of thin amorphous antimony films show such local well-ordered areas with nearly cubic symmetry.

    10. Analogues of Neuropeptide Y Containing β-Aminocyclopropane Carboxylic Acids are the Shortest Linear Peptides That Are Selective for the Y1 Receptor (pages 202–205)

      Norman Koglin, Chiara Zorn, Raphael Beumer, Chiara Cabrele, Christian Bubert, Norbert Sewald, Oliver Reiser and Annette G. Beck-Sickinger

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390078

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      Unique, conformationally restricted β-amino acids are a constituent of truncated linear peptides such as 1, which have been obtained for the first time; these species show high and selective affinity toward the Y1 receptor. The high affinity of these ligands is dependent on the position and the configuration of this β-aminocyclopropane carboxylic acid.

    11. [(η5-C5H5)(OC)3V[DOUBLE BOND]B[DOUBLE BOND]N(SiMe3)2: A Half-Sandwich Complex with a Terminal Borylene Ligand (pages 205–208)

      Holger Braunschweig, Miriam Colling, Chunhua Hu and Krzysztof Radacki

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390079

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      A vanadium–boron distance of 1.971 Å characterizes the first classical bond between these two elements. The novel half-sandwich complex 1 was obtained from [(OC)5Cr[DOUBLE BOND]B[DOUBLE BOND]N(SiMe3)2] by photochemically induced intermetallic borylene transfer.

    12. Archaea Analogue Thiolipids for Tethered Bilayer Lipid Membranes on Ultrasmooth Gold Surfaces (pages 208–211)

      Stefan M. Schiller, Renate Naumann, Katherine Lovejoy, Horst Kunz and Wolfgang Knoll

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390080

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      Simple vesicle fusion allowed the formation of a bilayer lipid membrane from the self-assembled monolayer of lipoic acid ester 1 (see formula). Film thicknesses determined by surface plasmon resonance (SPR) spectroscopic measurements agree with the theoretical thicknesses of the stretched conformation. Electrochemical impedance spectroscopy (EIS) of the model system shows that the latter exhibits similar electrical properties to biological membranes.

    13. Multiple Ion Cores in Anthracene Anion Clusters (pages 213–216)

      Jae Kyu Song, Nam Ki Lee and Seong Keun Kim

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390081

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      Spreading the charge: Anion clusters of anthracene, (An)n, with n values of up to 6 were studied and found to contain a distinctly monomeric, dimeric, or trimeric ion core with a delocalized electronic charge (see figure). Coexistence of dimeric and trimeric ion cores was observed in (An)4, but the ion core reverts to a monomeric one in (An)5, with the completion of a solvation shell around the monomer anion.

    14. Polyhydrido(silylene)osmium and Silyl(dinitrogen)ruthenium Products Through Redistribution of Phenylsilane with Osmium and Ruthenium Pincer Complexes (pages 216–219)

      Dmitry G. Gusev, Frédéric-Georges Fontaine, Alan J. Lough and Davit Zargarian

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390082

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      Migration/Redistribution Galore! The reaction of phenylsilane with a series of Os and Ru pincer complexes has led to the isolation of complexes 13, thus allowing the direct observation of 1,2-addition and redistribution reactions that are so fundamental in the transformations of organosilanes in catalysis. Complex 1 represents a rare example of a complex containing a donor-stabilized SiH2 ligand.

    15. Soil Fungal Hyphae Bind and Attack Asbestos Fibers (pages 219–222)

      Elena Martino, Laura Prandi, Ivana Fenoglio, Paola Bonfante, Silvia Perotto and Bice Fubini

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390083

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      Possible agents for the decontamination and bioremediation of asbestos-polluted soils: selected soil fungi modify and bind asbestos fibers. The picture shows a single asbestos fiber in intimate contact with the hyphae of Fusarium oxysporum (the bar in the upper left corresponds to 20 μm). The fungi produce metal chelators which extract iron ions from the fibers.

    16. High-Spin Wheel of a Heptanuclear Mixed-Valent FeII,III Complex (pages 223–225)

      Hiroki Oshio, Norihisa Hoshino, Tasuku Ito, Motohiro Nakano, Franz Renz and Philipp Gütlich

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390084

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      Wheels with high spins: The reaction of a tridentate Schiff base ligand with iron(II) chloride, and subsequent oxidation with [(tBu4N)MnO4] yielded a heptanuclear mixed-valent iron wheel (see picture) with a spin ground state of S=29/2.

    17. Beyond the Icosahedron: The First 13-Vertex Carborane (pages 225–228)

      Anthony Burke, David Ellis, Barry T. Giles, Bruce E. Hodson, Stuart A. Macgregor, Georgina M. Rosair and Alan J. Welch

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390085

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      Cornering the 13th vertex: The first 13-vertex carborane (see picture, B: brown, C: gray, H: white) has been prepared by a methodology that can in principle be applied repeatedly, leading to 14-, 15-, 16-, … vertex carboranes in the future. The 13-vertex species has a henicosahedral geometry, not the docosahedral one expected, but the two forms are found to be very close in energy by DFT calculations.

    18. Macrocycle Synthesis by Olefin Metathesis on a Nanosized, Shape-Persistent Tricationic Platinum Template (pages 228–230)

      Aleksey V. Chuchuryukin, Harm P. Dijkstra, Bart M. J. M. Suijkerbuijk, Robertus J. M. Klein Gebbink, Gerard P. M. van Klink, Allison M. Mills, Anthony L. Spek and Gerard van Koten

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390086

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      A 69-membered ring (see picture) results from a metathesis reaction that uses a metalated tris(pincer)-substituted benzene as scaffold. The macrocyclic product can be detached by the addition of Cl after which the template is recovered quantitatively.

    19. [3+2] and [4+1] Cycloaddition Reactions of Fischer Alkoxy(alkenyl)carbene Complexes with Electronically Neutral 1,3-Dienes (pages 231–233)

      José Barluenga, Salomé López and Josefa Flórez

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390087

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      Regio- and stereochemically controlled formation of cyclopentenes has been achieved through the reaction of transition-metal–alkoxy(alkenyl)carbene complexes and neutral 1,3-dienes (see scheme; BHT=2,6-di-tert-butyl-4-methylphenol). Reaction conditions dictate whether [3+2] or [4+1] cycloaddition products are obtained; alkenyl-substituted cyclopentanones of high enantiomeric purity are synthesized by using 8-phenylmenthyloxycarbene complexes.

    20. A Catalytic and Enantioselective Desymmetrization of meso Cyclic Allylic Bisdiethylphosphates with Organozinc Reagents (pages 234–236)

      Umberto Piarulli, Philippe Daubos, Christelle Claverie, Maryline Roux and Cesare Gennari

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390088

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      The chosen one: The desymmetrization of meso-2 is possible with the use of diethylzinc in the presence of the CuI complex of 1 (10 mol %; Tf=CF3SO2). Ligand 1 was optimized from a screen of a library of 125 compounds. Other ligands from the same library favor the formation of the opposite enantiomer 4.

    21. Preview: Angew. Chem. Int. Ed. 2/2003 (page 241)

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/anie.200390089

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