Angewandte Chemie International Edition

Cover image for Vol. 42 Issue 29

July 28, 2003

Volume 42, Issue 29

Pages 3311–3441

    1. Cover Picture: Transition-Metal Complexes of an Open Geodesic Polyarene (Angew. Chem. Int. Ed. 29/2003) (page 3311)

      Marina A. Petrukhina, Kristian W. Andreini, James Mack and Lawrence T. Scott

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200390527

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    3. “Chemical Bonding and Molecular Geometry”: Comments on a Book Review (pages 3331–3334)

      R. J. Gillespie and P. L. A. Popelier

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200320066

      A model debate: The recent review of the book “Chemical Bonding and Molecular Geometry” has led to a discussion between the authors and the reviewer regarding the validity of the models chosen and the conclusions drawn.

    4. Reply to the Comments of Gillespie and Popelier (page 3335)

      Gernot Frenking

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200320070

      A model debate: The recent review of the book “Chemical Bonding and Molecular Geometry” has led to a discussion between the authors and the reviewer regarding the validity of the models chosen and the conclusions drawn.

    5. Immobilizing Enzymes: How to Create More Suitable Biocatalysts (pages 3336–3337)

      Uwe T. Bornscheuer

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200301664

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      More immobile and more stable: The advantages of the immobilization of biocatalysts, for example, through the formation of aggregates or linking to iron oxide nanoparticles and organic supports (see scheme), include an enhanced stability, simple separation from the reaction mixture, and often an increased activity of the immobilizate.

    6. NMR Studies of Structure and Function of Biological Macromolecules (Nobel Lecture) (pages 3340–3363)

      Kurt Wüthrich

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200300595

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      The structure of proteins (such as that of bovine prion protein, see picture) and further information on the dynamics and structural, thermodynamic, and kinetic aspects of their interactions with other components in solution can be obtained by NMR methods developed by K. Wüthrich and his group. In his Nobel Lecture, Wüthrich delves into the past, present, and future of these techniques, and offers us a glimpse into his life.

    7. Solvent-Free Synthesis of Rechargeable Solid Oxygen Reservoirs for Clean Hydrogen Oxidation (pages 3366–3368)

      Gadi Rothenberg, E. A. (Bart) de Graaf and Alfred Bliek

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351545

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      Cutting out the coke: The concept of catalytic oxidative dehydrogenation by using solid oxygen exchangers and a solvent-free parallel synthesis of a set of ten bimetallic catalysts is described. The compounds were tested in the selective oxidation of hydrogen in the presence of ethane and ethylene (HCs) at 600 °C. Cerium tungsten oxide was found to be a superb rechargeable “oxygen reservoir” (see picture), with 97 % chemoselectivity and negligible coking levels.

    8. Plasticity in Self-Assembly: Templating Generates Functionally Different Circuits from a Single Precursor (pages 3368–3371)

      Mila Boncheva, Rosaria Ferrigno, Derek A. Bruzewicz and George M. Whitesides

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351533

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      The structures and patterns of electrical connections within 3D self-assembled aggregates can be templated by the geometry of the space in which the self-assembly proceeds. This finding demonstrates that, in principle, multiple functions can be derived from the same set of components by controlling a macroscopic variable (see picture).

    9. Efficient Methano[70]fullerene/MDMO-PPV Bulk Heterojunction Photovoltaic Cells (pages 3371–3375)

      Martijn M. Wienk, Jan M. Kroon, Wiljan J. H. Verhees, Joop Knol, Jan C. Hummelen, Paul A. van Hal and René A. J. Janssen

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351647

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      Owing to their increased absorption of light in the visible region, [70]fullerene derivatives provide a high photocurrent when incorporated as the electron acceptor in thin-film polymer photovoltaic cells. An incident-photon-to-current efficiency of 66 % is obtained when [70]PCBM (see picture) is used in combination with a poly(p-phenylene vinylene). These high currents originate from an ultrafast charge transfer that occurs upon photoexcitation of either the fullerene or the polymer.

    10. Transition-Metal Complexes of an Open Geodesic Polyarene (pages 3375–3379)

      Marina A. Petrukhina, Kristian W. Andreini, James Mack and Lawrence T. Scott

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351403

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      Corannulene, the smallest subunit of C60 that retains a curved surface, forms crystalline η2-coordinated π complexes with dirhodium(II) tetrakis(trifluoroacetate) by using solvent-free gas-phase deposition. As many as three metal atoms coordinate to the double bonds found at the rim of each corannulene, with one such atom always located on the concave surface (see picture).

    11. Rotaxane Building Blocks bearing Blocked Isocyanate Stoppers: Polyrotaxanes through Post-Assembly Chain Extension (pages 3379–3383)

      Timothy J. Kidd, Ton J. A. Loontjens, David A. Leigh and Jenny K. Y. Wong

      Version of Record online: 3 JUL 2003 | DOI: 10.1002/anie.200351458

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      A simple versatile route to polyrotaxanes with a variety of topologies is described through the synthesis and subsequent polymerization of readily accessible and stable rotaxane monomers containing bulky blocked isocyanate stopper groups.

    12. Asymmetric Desymmetrization of meso-1,2-Diols by Phosphinite Derivatives of Cinchona Alkaloids (pages 3383–3385)

      Shinya Mizuta, Mikito Sadamori, Tetsuya Fujimoto and Iwao Yamamoto

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200250719

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      An effective catalyst for the asymmetric monobenzoylation of meso-1,2-diols was designed—the phosphinite derivative of cinchonine (see formula). In the presence of 30 mol % of this catalyst the monobenzoylated products were obtained with high yields and enantioselectivities.

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      First Observation of Alkali Metal Ion Induced TransCis Isomerization of Palladium(II) Phosphane Complexes Containing Crown Ether Moieties (pages 3385–3388)

      Vivian Wing-Wah Yam, Xiao-Xia Lu and Chi-Chiu Ko

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351178

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      Ion switches: The addition of small metal ions (such as Li+ and Na+) to trans-palladium(II) complexes of PPh2-substituted benzo[15]crown-5 and benzo[18]crown-6 results in the formation of 1:1 trans adducts. However, the addition of large alkali ions (such as K+, Rb+, and Cs+) enforces the complexes to undergo a transcis isomerization to enable formation of intramolecular sandwich adducts (see schematic representation).

    14. Quantitative Correlation of Solvent Polarity with the α-/310-Helix Equilibrium: A Heptapeptide Behaves as a Solvent-Driven Molecular Spring (pages 3388–3392)

      Paolo Pengo, Lucia Pasquato, Stefano Moro, Alessandro Brigo, Federico Fogolari, Quirinus B. Broxterman, Bernard Kaptein and Paolo Scrimin

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351015

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      The long and the short of it: Just by changing the polarity of the solvent the highly folded heptapeptide Ac-[Aib-L-(αMe)Val-Aib]2-L-His-NH2 converts from an α into a 310 helix (see picture). The equilibrium constant between the two conformations correlates with the empirical solvent polarity parameter Eequation image. Molecular dynamics calculations show that the peptide elongates (310 helix) or shortens (α helix) on switching from one conformation to the other.

    15. Pd-Catalyzed Nucleophilic Alkylation of Aliphatic Aldehydes with Allyl Alcohols: Allyl, 2-Tetrahydrofuryl, and 2-Tetrahydropyranyl Ethers as Useful C3, C4, and C5 Sources (pages 3392–3395)

      Masanari Kimura, Masamichi Shimizu, Kazufumi Shibata, Minoru Tazoe and Yoshinao Tamaru

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351182

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      A combination of Pd0and Et2Zn generates an allyl anion species from allyl alcohols which can be used for the allylation of aliphatic aldehydes to provide homoallyl alcohols in good yields (see scheme). The reaction proceeds at room temperature in poor coordination solvents, such as a mixture of toluene and n-hexane.

    16. Olefin Metathesis in the Ionic Liquid 1-Butyl-3-methylimidazolium Hexafluorophosphate Using a Recyclable Ru Catalyst: Remarkable Effect of a Designer Ionic Tag (pages 3395–3398)

      Qingwei Yao and Yiliang Zhang

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351222

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      Designer labels: Ruthenium carbene complex 1 bearing an ionic tag was shown to be a highly reactive catalyst for the ring-closing metathesis of various diene and enyne substrates in minimally ionic solvent systems (see scheme; Bmim=1-butyl-3-methylimidazolium, Ts=toluene-4-sulfonyl). The catalyst can be repeatedly recycled and reused (up to at least 10 cycles) without significant loss of its activity, whereas other catalysts tested exhibited a dramatic diminishment in their activity upon recovery from the ionic layer.

    17. Di(isopropylprenyl)borane: A New Hydroboration Reagent for the Synthesis of Alkyl and Alkenyl Boronic Acids (pages 3399–3404)

      Alexey V. Kalinin, Stefan Scherer and Victor Snieckus

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351312

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      The best of the old: The new hydroboration reagent 1 combines the selectivity of disiamylborane (2) with the reactivity towards carbonyls of allyl boranes 3. Conventional oxidative workup conditions are avoided, as facile hydrolysis in protic media provides the corresponding boronic acids with up to 99 % anti-Markovnikov selectivities. A one-pot hydroboration/Suzuki–Miyaura protocol adds to the synthetic value of 1.

    18. Highly Efficient Peptide Bond Formation to Functionalized Wells-Dawson-Type Polyoxotungstates (pages 3404–3406)

      Sébastian Bareyt, Stergios Piligkos, Bernold Hasenknopf, Pierre Gouzerh, Emmanuel Lacôte, Serge Thorimbert and Max Malacria

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351346

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      Making derivatives of organic side chains on polyoxometalates is an important prerequisite for their application in biology. Compounds α1- and α2-[P2W17O61{Sn(CH2)2CO2H}]7− (depicted) were prepared for the first time and coupled with alcohols and amines, including C-protected amino acids.

    19. Stereospecific Total Synthesis of the Antiviral Agent Hamigeran B—Use of Large Silyl Groups to Enforce Facial Selectivity and to Suppress Hydrogenolysis (pages 3406–3409)

      Derrick L. J. Clive and Jian Wang

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351519

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      Stereoselective hydrogenation of the tetrasubstituted double bond in enone 1 is possible, provided the keto group at C7 is first removed and the α face is blocked by tert-butyldimethylsiloxy groups at positions 10 and 11. The resulting product 2 is easily converted into hamigeran B (3), a marine natural product with powerful activity against herpes and polio viruses. Si*=tBuMe2Si.

    20. Design and Synthesis of Paromomycin-Related Heterocycle-Substituted Aminoglycoside Mimetics Based on a Mass Spectrometry RNA-Binding Assay (pages 3409–3412)

      Yili Ding, Steven A. Hofstadler, Eric E. Swayze, Lisa Risen and Richard H. Griffey

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351354

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      A good starting point for the design of potent bactericidal compounds is the aminoglycoside paromomycin (1). The A-ring (shown in red) was replaced with a range of heterocycles. An ESIMS-based RNA-binding assay was used to screen the binding affinities of the products.

    21. Nickel-Catalyzed Dimerization and Carbosilylation of 1,3-Butadienes with Chlorosilanes and Grignard Reagents (pages 3412–3414)

      Jun Terao, Akihiro Oda, Aki Ikumi, Akifumi Nakamura, Hitoshi Kuniyasu and Nobuaki Kambe

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351579

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      In a multicomponent coupling reaction, 1,3-butadienes underwent Ni-catalyzed dimerization and carbosilylation in the presence of a chlorosilane and a Grignard reagent at −20 °C (see scheme). The coupling product was obtained regio- and stereoselectively when unsubstituted 1,3-butadiene was used. (R=H, Me, or C9H19; R′, R′′=hydrocarbon substituent.)

    22. Regioselective Hydrosilylation of Propargylic Alcohols: An Aldol Surrogate (pages 3415–3418)

      Barry M. Trost, Zachary T. Ball and Thomas Jöge

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351587

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      Aldol products from a non-aldol reaction: A one-pot protocol effects hydrosilylation of propargyl alcohols and subsequent oxidative cleavage to yield β-hydroxy ketones in a chemo-, regio-, and enantioselective fashion. Further structural elaboration of the intermediate γ-hydroxyvinylsilane is possible before the carbonyl group is unmasked (see scheme).

    23. Synthetic Studies on Thiostrepton: Construction of Thiostrepton Analogues with the Thiazoline-Containing Macrocycle (pages 3418–3424)

      K. C. Nicolaou, Marta Nevalainen, Mark Zak, Stephan Bulat, Marco Bella and Brian S. Safina

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351745

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      Leading the way: The novel thiostrepton analogue 1 and its 5S,6S diastereomer were synthesized through macrolactamization reactions. Forays towards the total synthesis of the natural product itself should follow a similar strategy.

    24. Sulfur as the Key Element for Quantitative Protein Analysis by Capillary Liquid Chromatography Coupled to Element Mass Spectrometry (pages 3425–3427)

      Mathias Wind, Ansgar Wegener, Andreas Eisenmenger, Roland Kellner and Wolf D. Lehmann

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200250547

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      The impact of32S quantification by capillary chromatography coupled to element mass spectrometry was demonstrated for three areas in proteomic analysis: for absolute quantification of a peptide, for the characterization of a protein digest (see chromatogram), and for the estimation of the efficiency of electrospray ionization.

    25. Electrodeposition of Nanocrystalline Metals and Alloys from Ionic Liquids (pages 3428–3430)

      Frank Endres, Mirko Bukowski, Rolf Hempelmann and Harald Natter

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200350912

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      Better than water: A method for the electrodeposition of nanocrystalline metals and alloys from ionic liquids has been developed (see schematic representation). This method enables the synthesis of aluminum nanocrystals with average grain sizes of about 10 nm, Al-Mn alloys, as well as Fe and Pd nanocrystals.

    26. Intramolecular C–H Activation in Alkaline-Earth Metal Complexes (pages 3430–3434)

      Sjoerd Harder

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351055

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      A heteroleptic benzylcalcium complex decomposes by means of C–H activation (see picture), a reaction typical for d0-metal complexes. This finding closes the gap between the chemistry of the heavier alkaline-earth and the early d- and f-block metals. The product, a dimeric calcium complex, was characterized by X-ray crystallography.

    27. The Sudden-Polarization Effect and its Role in the Ultrafast Photochemistry of Ethene (pages 3434–3436)

      Alexandra Viel, Robert P. Krawczyk, Uwe Manthe and Wolfgang Domcke

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200351193

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      Surprisingly polar: The single-sided scissoring-induced sudden-polarization effect in D2d ethene is first order (see picture). The important role of this coordinate was until now overlooked, although it was known for a long time that each geometrical distortion that leads to a breakage of the D2d symmetry results in a charge separation.

    28. Preview: Angew. Chem. Int. Ed. 29/2003 (page 3441)

      Version of Record online: 24 JUL 2003 | DOI: 10.1002/anie.200390533

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