Angewandte Chemie International Edition

Cover image for Vol. 42 Issue 42

November 3, 2003

Volume 42, Issue 42

Pages 5103–5251

    1. Cover Picture: Competitive Binding Assays Made Easy with a Native Marker and Mass Spectrometric Quantification (Angew. Chem. Int. Ed. 42/2003) (page 5103)

      Georg Höfner and Klaus Theodor Wanner

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200390606

      Mass spectrometric methods are on the march in competitive binding studies. In pharmacological research these studies are widely used to characterize ligand–target interactions. However, they usually require the use of radioligands. Now, with the aid of mass spectrometry, it is possible to use native markers instead of radioligands. This method and its use in a binding study on dopamine D1-receptors are described in the Communication by G. Höfner and K. T. Wanner on page 5235 ff.

    2. Nickel-Catalyzed Coupling of Carbonyl Compounds and Alkynes or 1,3-Dienes: An Efficient Method for the Preparation of Allylic, Homoallylic, and Bishomoallylic Alcohols (pages 5120–5122)

      Shin-ichi Ikeda

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200301673

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      Nickel-catalyzed multicomponent coupling of carbonyl compounds with alkynes or 1,3-dienes and organometallic reagents represents an efficient route to allylic, homoallylic, and bishomoallylic alcohols with good regio-, stereo-, and enantioselectivity. The reaction proceeds via the nickelacycle species I or I′ (see scheme), and not by the usual alkenylation, allylation, and homoallylation of carbonyl compounds.

    3. Advances in the Synthesis of Inorganic Nanotubes and Fullerene-Like Nanoparticles (pages 5124–5132)

      Reshef Tenne

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200301651

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      Lamellar inorganic compounds, in analogy with the graphitic form of carbon, are susceptible to folding forces that can lead them to adopt fullerene-like or nanotubular structures. The development of inorganic nanomaterials (such as the assembly of the single-wall MoS2 nanotubes shown) has now reached the stage where many important applications in catalysis, lubrication, and nanotechnology are within reach.

    4. Synthetic Expanded Porphyrin Chemistry (pages 5134–5175)

      Jonathan L. Sessler and Daniel Seidel

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200200561

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      As the name implies: Expanded porphyrins, that is, larger, extended porphyrin derivatives (example shown), are fascinating synthetic additions to the world of natural tetrapyrrolic pigments. Their structural aesthetics, theoretical interest, and potential practical utility have resulted in a rapid blossoming of this field. This Review provides an overview of the latest developments, with a focus on preparative chemistry.

    5. Chirality Transfer from Single Molecules into Self-Assembled Monolayers (pages 5178–5181)

      Roman Fasel, Manfred Parschau and Karl-Heinz Ernst

      Article first published online: 6 OCT 2003 | DOI: 10.1002/anie.200352232

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      One hand is better than two! Chirality transfer from the single molecule into a two-dimensional layer is investigated by STM. The supramolecular handedness in homochiral heptahelicene layers, generated on a single-crystal surface (see picture), results from the orientations of next-neighbor molecules. The intermolecular interaction is dominated by steric repulsive forces between the rigid helices, causing a direct transfer of chirality.

    6. Quantitative Formation of Sandwich-Shaped Trinuclear Silver(I) Complexes and Dynamic Nature of Their PM Flip Motion in Solution (pages 5182–5185)

      Shuichi Hiraoka, Koji Harano, Takaaki Tanaka, Motoo Shiro and Mitsuhiko Shionoya

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200351068

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      Molecular flippers: The Ag3L2 complexes, which are quantitatively formed from two disk-shaped tridentate ligands (thiazolyl- or pyridyl-based) and three Ag+ ions, are helical and twist between the P and M forms (see scheme). The flip motion includes a relative 120° rotation between the two disk-shaped ligands connected by the Ag+ ions.

    7. Glycotentacles: Synthesis of Cyclic Glycopeptides, Toward a Tailored Blocker of Influenza Virus Hemagglutinin (pages 5186–5189)

      Takashi Ohta, Nobuaki Miura, Naoki Fujitani, Fumio Nakajima, Kenichi Niikura, Reiko Sadamoto, Chao-Tan Guo, Takashi Suzuki, Yasuo Suzuki, Kenji Monde and Shin-Ichiro Nishimura

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200351640

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      Blocking flu: A cyclic peptide, cyclo(Ser-Gly-Gly-Gln-Ser-His-Asp)3, is an excellent scaffold for the synthesis of a cyclic glycopeptide carrying GM3 oligosaccharides with a potent inhibitory effect on the hemagglutination induced by the influenza virus. Tridentate binding of the gylcopeptide is shown to produce a much greater inhibitory effect than di- or monodentate binding. The shape of the glycopeptide protein scaffold, which is determined by the amino acid sequence employed, is also found to be significant in determining the inhibitory activity.

    8. [3+3]Cycloalkyne Oligomers: Linking Groups Control Intra- and Intermolecular Aggregation by π–π Interactions (pages 5190–5192)

      Yuto Saiki, Keiichi Nakamura, Yasuko Nigorikawa and Masahiko Yamaguchi

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200351735

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      Molecules get together: Two dimeric and a trimeric [3+3]cycloalkyne (see picture) are synthesized, and their aggregation behavior in CHCl3 examined by 1H NMR spectroscopy, circular dichroism, and vapor pressure osmometry. The aggregate structure of the oligomeric [3+3]cycloalkynes can be controlled by the structures of the linker moiety.

    9. Biomimetic Control of Size in the Polyamine-Directed Formation of Silica Nanospheres (pages 5192–5195)

      Manfred Sumper, Sonja Lorenz and Eike Brunner

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200352212

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      Diatom shells (see picture of cell of Stephanopyxis turris) contain long-chain polyamines attached either to putrescine or to phosphorylated silaffin peptides. These polyamines direct the in vitro formation of silica nanospheres from silicic acid. The concentration of multivalent anions (such as phosphate) defines the diameter of the nanospheres produced.

    10. Conversion of Methane to Syngas by a Membrane-Based Oxidation–Reforming Process (pages 5196–5198)

      Chu-sheng Chen, Shao-jie Feng, Shen Ran, De-chun Zhu, Wei Liu and Henny J. M. Bouwmeester

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200351085

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      Two processes in one space: Methane, the main component of natural gas, can be converted into syngas efficiently in a two-stage oxygen-permeable ceramic membrane reactor by means of integrated oxidation and reforming processes (see picture). This could be a cheaper alternative to the current steam-reforming of methane.

    11. InBr3-Catalyzed Cyclization of Glycals with Aryl Amines (pages 5198–5201)

      Jhillu S. Yadav, Basi V. S. Reddy, Katta V. Rao, Kavuda Saritha Raj, Atlaluri R. Prasad, Singarapu Kiran Kumar, Ajit C. Kunwar, Panjula Jayaprakash and Bulusu Jagannath

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200351267

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      A new class of carbohydrate analogues, benzo-fused heterobicycles 1, can be prepared by cyclization of D-glucals with aryl amines in the presence of 10 mol % indium tribromide under mild and convenient reaction conditions [Eq. (1)]. The structure and configuration of the products were established by extensive NMR experiments and molecular modeling studies.

    12. Gold Is Noble but Gold Hydride Anions Are Stable (pages 5201–5206)

      Xuefeng Wang and Lester Andrews

      Article first published online: 14 OCT 2003 | DOI: 10.1002/anie.200351780

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      Coinage metal hydrides are stabilized by negative charge: Reactions of energized laser-ablated gold, silver, and copper with H2 in excess argon, neon, and pure normal hydrogen during condensation at 3.5 K give the MH molecules, the (H2)MH complexes, the MH2 ions, and the MH4 ion only for gold. The stable linear MH2 ions are unique in that their corresponding neutral MH2 molecules are higher in energy and thus unstable to M + H2 decomposition.

    13. Dicyanocarbodiimide and Trinitreno-s-triazine Generated by Consecutive Photolysis of Triazido-s-triazine in a Low-Temperature Nitrogen Matrix (pages 5206–5209)

      Tadatake Sato, Aiko Narazaki, Yoshizo Kawaguchi, Hiroyuki Niino and Götz Bucher

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200351879

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      Carbon nitride molecules: Photolysis (λ=266 nm) of triazido-s-triazine (C3N12, 1) in a nitrogen matrix at 20 K yielded a succession of reactive species (see scheme), including, in order, an apparent trinitrene, NCN, and a novel C3N4 isomer, dicyanocarbodiimide NC[BOND]N[DOUBLE BOND]C[DOUBLE BOND]N[BOND]CN.

    14. Synthesis of a Carbon-Linked Mimic of the Disaccharide Component of the Tumor-Related SialylTn Antigen (pages 5209–5212)

      Zouleika Abdallah, Gilles Doisneau and Jean-Marie Beau

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200351969

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      The right mix! When one considers the many ways in which a polyfunctional organometallic species may be quenched before any productive C[BOND]C bond formation can occur (two amide protons, five esters), the samarium-promoted coupling between sulfide 1 and aldehyde 2 is remarkably efficient (see scheme). This is shown in the synthesis of a stable mimic of the sialylTn (Tn=GalNAcα1[RIGHTWARDS ARROW]O-Ser/Thr) disaccharide.

    15. Unprecedented Crystalline Super-Lattices of Monodisperse Cobalt Nanorods (pages 5213–5216)

      Frédéric Dumestre, Bruno Chaudret, Catherine Amiens, Marc Respaud, Peter Fejes, Philippe Renaud and Peter Zurcher

      Article first published online: 14 OCT 2003 | DOI: 10.1002/anie.200352090

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      Coalescence of initially produced nanospheres inside 3D super-lattices may be the reason for the formation of ferromagnetic cobalt nanorods, monodisperse in length and diameter, from [Co(η3-C8H13)(η4-C8H12)] in the presence of stearic acid and hexadecylamine. The self-organization of these nanorods into unprecedented hexagonal 2D and 3D super-lattices has been studied by transmission electron microscopy (see picture).

    16. Difluoromethyl Phenyl Sulfone as a Selective Difluoromethylene Dianion Equivalent: One-Pot Stereoselective Synthesis of anti-2,2-Difluoropropane-1,3-diols (pages 5216–5219)

      G. K. Surya Prakash, Jinbo Hu, Thomas Mathew and George A. Olah

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200352172

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      Intramolecular charge–charge repulsion rather than traditional steric control is responsible for the high diastereoselectivity (up to 94 % de) obtained in tBuOK-induced difluoromethylenation of aldehydes 1 with difluoromethyl phenyl sulfone (2) to give symmetrical and unsymmetrical anti-2,2-difluoropropane-1,3-diols 3.

    17. The Effect of Outer-Sphere Acidity on Chemical Reactivity in a Synthetic Heterogeneous Base Catalyst (pages 5219–5222)

      John D. Bass, Sandra L. Anderson and Alexander Katz

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200352181

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      Rational outer-sphere design can be used to optimize heterogeneous catalysts. Thus, imprinting of bulk silica was used to prepare tethered active sites with hydrophilic (1) and hydrophobic environments (2). In the Knoevenagel condensation of isophthalaldehyde with malonitrile, for example, 1 gave rate enhancements of about 50 and 30 relative to 2 and a commercial catalyst consisting of a monolayer of 3-aminopropyl groups on silica, respectively.

    18. Oxidative Addition of Phenylacetylene through C[BOND]H Bond Cleavage To Form the MgII–dpp-bian Complex: Molecular Structure of [Mg{dpp-bian(H)}(C[TRIPLE BOND]CPh)(thf)2] and Its Diphenylketone Insertion Product [Mg(dpp-bian).{OC(Ph2)C[TRIPLE BOND]CPh}(thf)] (pages 5223–5226)

      Igor L. Fedushkin, Natalie M. Khvoinova, Alexandra A. Skatova and Georgy K. Fukin

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200352200

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      The use of a rigid bidentate ligand allows oxidative addition of an acetylene derivative to a non-transition-metal complex, not through oxidation of the metal atom, but through σ-bond metathesis from M[BOND]L: and H[BOND]C to form H[BOND]L⋅⋅⋅M[BOND]C (see scheme; Ar=2,6-iPr2C6H3).

    19. Dynamics of the Simplest Reaction of a Carbon Atom in a Tetrahedral Environment (pages 5227–5230)

      Jon P. Camden, Hans A. Bechtel and Richard N. Zare

      Article first published online: 14 OCT 2003 | DOI: 10.1002/anie.200352642

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      The abstraction reaction H + CD4[RIGHTWARDS ARROW]CD3 + HD is studied at a collision energy of ∼2 eV under single-collision conditions (see picture). Most of the available energy appears in product translational motion, and the CD3 product is scattered sideways and backward with respect to the incident H-atom direction. This behavior is unexpected based on simple atom–diatom models.

    20. A Combinatorial Synthesis of a Macrosphelide Library Utilizing a Palladium-Catalyzed Carbonylation on a Polymer Support (pages 5230–5234)

      Takashi Takahashi, Shin-ichi Kusaka, Takayuki Doi, Toshiaki Sunazuka and Satoshi Ōmura

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200352229

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      Supported total synthesis: The combinatorial synthesis of a 122-membered macrosphelide library including macrosphelides A, C, E, and F (see picture) has been achieved based on a unique strategy for a three-component coupling utilizing a palladium-catalyzed chemoselective carbonylation and an unprecedented macrolactonization on a polymer support.

    21. Competitive Binding Assays Made Easy with a Native Marker and Mass Spectrometric Quantification (pages 5235–5237)

      Georg Höfner and Klaus Theodor Wanner

      Article first published online: 1 SEP 2003 | DOI: 10.1002/anie.200351806

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      MS makes it possible: Competitive binding assays are a widely used tool in drug research to characterize the affinity of a ligand for a biological target. However, these assays generally require special ligands which can be detected with high sensitivity, such as radioligands or ligands coupled to a fluorophore. Now native markers may be employed in conjunction with mass spectrometric quantification. First studies demonstrate this approach in binding experiments at dopamine D1-receptors.

    22. Stable and Highly Water-Dispersible, Highly Unsaturated Carotenoid Phospholipids—Surface Properties and Aggregate Size (pages 5237–5240)

      Bente Jeanette Foss, Stine Nalum Næss, Hans-Richard Sliwka and Vassilia Partali

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200351828

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      No additives are required for the study of hydrophobic carotenoids in aqueous solutions, if these compounds are present as highly unsaturated phospholipids (see structure). These compounds form small, highly water-dispersible carotenoid aggregates.

    23. Hydrogenation on Metal Surfaces: Why are Nanoparticles More Active than Single Crystals? (pages 5240–5243)

      Aidan M. Doyle, Shamil K. Shaikhutdinov, S. David Jackson and Hans-Joachim Freund

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200352124

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      Size matters: Under low-pressure conditions, hydrogenation of alkenes, such as 2-pentene and ethene, is shown to occur on supported palladium nanoparticles, whereas single-crystal palladium surfaces are inactive. This finding is rationalized on the basis of the accessibility of weakly bound subsurface hydrogen (see picture), which is enhanced on particles of nanometer dimensions.

    24. Simple Access to Unsymmetrically Substituted, Saturated N-Heterocyclic Carbenes (pages 5243–5246)

      F. Ekkehardt Hahn, Martin Paas, Duc Le Van and Thomas Lügger

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200352349

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      Secondary amines and imines were used to prepare unsymmetrically substituted, non-aromatic N-heterocyclic carbenes via imidazolidine-2-thiones (rac-1) as intermediates. The presence of only one sterically demanding substituent on one of the N atoms in rac-2 is sufficient to prevent dimerization to the enetetramine.

    25. Preview: Angew. Chem. Int. Ed. 42/2003 (page 5251)

      Article first published online: 30 OCT 2003 | DOI: 10.1002/anie.200390609