Angewandte Chemie International Edition

Cover image for Vol. 43 Issue 1

December 22, 2003

Volume 43, Issue 1

Pages 1–129

    1. Cover Picture: The Evolution of Dip-Pen Nanolithography (Angew. Chem. Int. Ed. 1/2004) (page 1)

      David S. Ginger, Hua Zhang and Chad A. Mirkin

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200390636

      Dip-Pen Nanolithography makes possible rapid patterning of surfaces on the nanometer scale. The cover picture clearly shows the principles of this technique: the deposition of dye molecules from an atomic force microscopy tip onto a substrate. Feymans 1960 dictum on miniturization, shown in nanometer-sized type in the background, is proving to be once again applicable. C. A. Mirkin et al. summarize in their Review on page 30 ff. the current status of dip-pen lithography and predict possible future developments.

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      Editorial: Nothing Stands Still (pages 4–6)

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200390640

    3. Graphical Abstract: Angew. Chem. Int. Ed. 1/2004 (pages 7–14)

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200390641

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      [Ni6(SCH2CH2OH)12]: A Double Crown [12]Metallacrown-6 Nickel(II) Cluster (page 14)

      Fang-Fang Jian, Kui Jiao, Yan Li, Pu-Su Zhao and Lu-De Lu

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200390638

    5. New Mass Spectrometric Methods for the Quantification of Protein–Ligand Binding in Solution (pages 22–25)

      Kathrin Breuker

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200301695

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      At first sight, it is not immediately discernible how molecular-weight measurements can be used for the determination of binding constants for protein–ligand complexes. Nevertheless, successful strategies have been developed for the quantitative analysis of protein–ligand binding by mass spectrometry (see scheme), which offers the distinct advantages of speed and the potential for automation.

    6. Direct Oxidation of Azides to Nitro Compounds (pages 26–28)

      G. K. Surya Prakash and Markus Etzkorn

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200301710

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      The “tamed” hypofluorous acid complex HOF⋅CH3CN has been found to be a convenient reagent for the expedient oxidation of azides to their corresponding nitro compounds. The method is quite versatile with both aromatic and aliphatic azides.

    7. The Evolution of Dip-Pen Nanolithography (pages 30–45)

      David S. Ginger, Hua Zhang and Chad A. Mirkin

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200300608

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      More than scratching the surface: Dip-pen nanolithography (DPN) is a new scanning-probe-based direct-write tool for generating surface-patterned chemical functionality on the sub-100-nm length-scale (see picture). This article introduces DPN and reviews the rapid growth of the field of DPN-related research and its impact on areas ranging from biological nanoarrays to patterned magnetic media to microelectromechanical systems (MEMs).

    8. A Planning Strategy for Diversity-Oriented Synthesis (pages 46–58)

      Martin D. Burke and Stuart L. Schreiber

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200300626

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      Space—the final frontier: A complementary approach to retrosynthetic analysis has been used to develop forward-synthetic analysis which forms the basis of diversity-oriented synthesis (see scheme). The goals of diversity-oriented synthesis include the development of pathways leading to the efficient (three- to five-step) synthesis of collections of small molecules having rich skeletal and stereochemical diversity.

    9. Dynamics of Ordered Water in Interfacial Enzyme Recognition: Bovine Pancreatic Phospholipase A2 (pages 60–63)

      Liang Zhao, Samir Kumar Pal, Tianbing Xia and Ahmed H. Zewail

      Article first published online: 8 DEC 2003 | DOI: 10.1002/anie.200352961

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      Slippery when wet: Water molecules at the interface between a protein (e.g. bovine pancreatic phospholipase A2) and a micellar substrate act as a lubricant and facilitate movement and binding of the protein at the surface (see picture). Studies of the hydration dynamics before and after complexation reveal that these interactions are crucial for enzymatic function.

    10. Synthesis of Crystalline Silicon Tubular Nanostructures with ZnS Nanowires as Removable Templates (pages 63–66)

      Junqing Hu, Yoshio Bando, Zongwen Liu, Jinhua Zhan, Dmitri Golberg and Takashi Sekiguchi

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352483

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      Silicon epitaxy on ZnS nanowires results in the formation of ZnS/Si core/shell nanowires; chemical removal of the zinc blende nanowire templates produces monocrystalline silicon tubular nanostructures with outer diameters of about 60–180 nm, wall thicknesses of about 20–60 nm, and lengths of several micrometers (see picture). The electron diffraction pattern of an individual nanostructure (inset) confirmed the presence of single-crystalline silicon.

    11. Characterization of NovP and NovN: Completion of Novobiocin Biosynthesis by Sequential Tailoring of the Noviosyl Ring (pages 67–70)

      Caren L. Freel Meyers, Markus Oberthür, Hui Xu, Lutz Heide, Daniel Kahne and Christopher T. Walsh

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352626

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      Two steps forward: The glycosylated aminocoumarin antibiotic novobiocin (1) is produced by Streptomyces spheroides and inhibits the bacterial type II topoisomerase DNA gyrase. The sugar-tailoring enzymes NovP and NovN that catalyze the final two steps in novobiocin biosynthesis were overproduced in Escherichia coli and characterized as a methyltransferase and carbamoyltransferase, respectively.

    12. Synthesis of Versatile Chiral N,P Ligands Derived from Pyridine and Quinoline (pages 70–74)

      William J. Drury III, Nicole Zimmermann, Martine Keenan, Masahiko Hayashi, Stefan Kaiser, Richard Goddard and Andreas Pfaltz

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352755

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      Potent transition-metal complexes for asymmetric catalysis are formed from readily accessible N,P ligands constructed from basic N-heteroaryl building blocks (see structure). Their simple assembly should not be misconstrued: they posses several handles by which to tune both steric and electronic parameters. The potential of these ligands is demonstrated by the high levels of enantioselection they induce in such divergent processes as asymmetric hydrogenation and the Heck reaction.

    13. π-Conjugated Oligo-(p-phenylenevinylene) Rosettes and Their Tubular Self-Assembly (pages 74–78)

      Pascal Jonkheijm, Atsushi Miura, Magdalena Zdanowska, Freek J. M. Hoeben, Steven De Feyter, Albertus P. H. J. Schenning, Frans C. De Schryver and E. W. Meijer

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352790

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      Hierarchical self-assembly: Oligo(p-phenylenevinylene)s with pendant diamino triazine moieties can self-assemble through hydrogen-bonding interactions to give hexameric rosettes (see picture, left). These rosettes further organize into large supramolecular tubules (right) with perfect space filling.

    14. Silica–Water Reaction Media: Its Application to the Formation and Ring Opening of Aziridines (pages 79–81)

      Satoshi Minakata, Daisuke Kano, Yoji Oderaotoshi and Mitsuo Komatsu

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352842

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      Olefins can be converted into aziridines by using a chloramine-T/I2 system, and silica and water as the reaction medium (see picture). Moreover, the ring-opening reaction of the resulting aziridine with an azide or a cyanide ion proceeds in the same medium.

    15. Enantioselective Synthesis of the Spirotetracyclic Carbon Core of Mangicols by Using a Stereoselective Transannular Diels–Alder Strategy (pages 81–84)

      Keisuke Araki, Keiji Saito, Hirokazu Arimoto and Daisuke Uemura

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200351750

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      “TADA!” is not the trumpet fanfare but the transannular Diels–Alder reaction concluding the synthesis of the tetracyclic core of the mangicols, a family of marine sesterterpenes. Further highlights in the synthesis include a novel chlorination and an intramolecular Nozaki–Hiyama–Kishi coupling reaction. Bn=benzyl.

    16. Kinetic Resolution of Epoxides by a C[BOND]C Bond-Forming Reaction: Highly Enantioselective Addition of Indoles to cis, trans, and meso Aromatic Epoxides Catalyzed by [Cr(salen)] Complexes (pages 84–87)

      Marco Bandini, Pier Giorgio Cozzi, Paolo Melchiorre and Achille Umani-Ronchi

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352073

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      The high reactivity of indoles has led to a new approach for the kinetic resolution of epoxides. [Cr(salen)] efficiently catalyzes a new C[BOND]C bond-forming reaction that allows the kinetic resolution of cis and trans aromatic epoxides (see scheme). By employing the same catalytic system, different indolyl derivatives were obtained in high enantiomeric excesses (up to 98 %) by asymmetric ring opening of meso-stilbene oxide.

    17. Cubane {CuII4} Cluster as a Precursor for the Preparation of a Mixed-Valent {CuII12CuI2} Core (pages 87–90)

      Arindam Mukherjee, Munirathinam Nethaji and Akhil R. Chakravarty

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352350

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      A molecular octopus: A ferromagnetic cubane cluster [{CuII(HL)}4], which has eight vacant coordination sites on its pendent arms, undergoes metal-driven self-assembly to form an antiferromagnetic mixed-valent tetradecanuclear complex with a prismatic propeller-shaped {CuII12CuI2} core (see scheme).

    18. The Complete Delineation of the Initiation, Propagation, and Termination Steps of the Carbomethoxy Cycle for the Carboalkoxylation of Ethene by Pd–Diphosphane Catalysts (pages 90–94)

      Jianke Liu, Brian T. Heaton, Jonathan A. Iggo and Robin Whyman

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352369

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      An elegant model: The intermediates in both the hydride and carbomethoxy cycles, and in chain transfer for carboalkoxylation of ethene and CO–alkene copolymerization have been characterized for a highly active cationic palladium–diphosphane catalyst (see scheme). In contrast to previous reports on model systems, alkene insertion into the Pd[BOND]C(O)OMe and Pd[BOND]C(O)Me bonds is found to occur at comparable rates.

    19. The Mechanism of Bu3SnH-Mediated Homolytic Aromatic Substitution (pages 95–98)

      Athelstan L. J. Beckwith, Vincent W. Bowry, W. Russell Bowman, Emma Mann, Jonathan Parr and John M. D. Storey

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352419

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      The fate of intermediate π radicals is crucial in Bu3SnH-mediated cyclization by homolytic aromatic substitution, for example, of bromo compound 1 via radical 2 to give oxindole 3 (AIBN=azobisisobutyronitrile). The results indicate that the mechanism requires the abstraction of a hydrogen radical from the intermediate π radical by the radical initiator or a product of initiator breakdown, and also that arene solvents are not always the best solvents for radical reactions.

    20. Characterization of a Dinuclear MnV[DOUBLE BOND]O Complex and Its Efficient Evolution of O2 in the Presence of Water (pages 98–100)

      Yuichi Shimazaki, Taro Nagano, Hironori Takesue, Bao-Hui Ye, Fumito Tani and Yoshinori Naruta

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352564

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      A high valent MnV[DOUBLE BOND]O porphyrin dimer is prepared by peracid oxidation of an MnIII dimer under basic conditions at room temperature (see scheme; mCPBA=m-chloroperbenzoic acid). The addition of an acid to a solution of the MnV[DOUBLE BOND]O complex results in quantitative dioxygen evolution. Water and/or hydroxide ions are the sources of both the oxo ligand and the evolved dioxygen.

    21. Design and Fabrication of a Flexible and Self-Supporting Supramolecular Film by Hierarchical Control of the Interaction between Hydrogen-Bonded Sheet Assemblies (pages 100–103)

      Isao Yoshikawa, Jun Li, Yuka Sakata and Koji Araki

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352641

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      A super film: 2D sheet assemblies of alkylsilylated deoxyguanosine derivatives were formed by double intertape hydrogen bonding between hydrogen-bonded 1D tape motifs. Introduction of polar oxyethylene units at the sheet surface allowed the fabrication of a flexible, self-supporting supramolecular film (see figure) with a well-defined structural hierarchy.

    22. Electrophilic Cleavage of One Silicon–Carbon Bond of Pentacoordinate Tetraorganosilanes: Synthesis of Silalactones (pages 104–106)

      Mitsuru Shindo, Kenji Matsumoto and Kozo Shishido

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352705

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      Dealkylation of trialkylvinylsilanes: The direct electrophilic cleavage of one silicon–carbon bond of tetraorganosilanes activated by the intramolecular pentacoordination of a slightly nucleophilic ester or carboxylic acid group provides a novel route to silalactones (see scheme).

    23. Consecutive Double 1,2-Migration of Two Different Groups in Silyl(dichloromethyl)cuprates (pages 106–108)

      Junichi Kondo, Yuki Ito, Hiroshi Shinokubo and Koichiro Oshima

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352828

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      Very different reactivity of two types of cuprates: Treatment of a silyldichloromethyllithium compound with a copper reagent prepared from BuMgBr and CuCN gives the product of consecutive dibutylation. On the other hand, Bu2CuLi⋅LiCN affords the butylation/cyanation product (see scheme, Si=Ph2MeSi).

    24. Analysis of the Spatial Dimensions of Fully Aromatic Dendrimers (pages 109–112)

      Sabine Rosenfeldt, Nico Dingenouts, Dominic Pötschke, Matthias Ballauff, Alexander J. Berresheim, Klaus Müllen and Peter Lindner

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200351810

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      Do dendrimers in solution have a dense shell or a dense core? This question can be answered with the help of small-angle neutron scattering. The fully aromatic dendrimer G4-M shown here displays the expected rigid structure in solution and represents the first example of a real dense-shell dendrimer.

    25. Rational Design of Nanostructured Copper–Zinc Oxide Catalysts for the Steam Reforming of Methanol (pages 112–115)

      Benjamin L. Kniep, Thorsten Ressler, Annegrit Rabis, Frank Girgsdies, Michael Baenitz, Frank Steglich and Robert Schlögl

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352148

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      Getting under the surface of aging: The bulk structure of copper nanoparticles can be tailored during the preparation by exploiting known structure–activity relationships. Ageing of freshly precipitated precursors leads to characteristic phase transitions and enables control of microstrain and particle size (see picture) properties which influence catalytic activity.

    26. A Short, Atom-Economical Entry to Tetrahydroxanthenones (pages 115–118)

      Bernhard Lesch and Stefan Bräse

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200352154

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      A reaction that takes to water: The domino Michael addition/aldol condensation of salicylic aldehydes like 1 as the nucleophile and 2-cyclohexen-1-one (2) as the Michael acceptor provides 2,3,4,4a-tetrahydroxanthen-1-ones such as 3 in good yields. DABCO=1,4-diazabicyclo[2.2.2]octane.

    27. Do Quantum Size Effects Control CO Adsorption on Gold Nanoparticles? (pages 118–121)

      Celine Lemire, Randall Meyer, Shamil Shaikhutdinov and Hans-Joachim Freund

      Article first published online: 2 DEC 2003 | DOI: 10.1002/anie.200352538

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      Monolayer gold islands with a thickness of one or a few monolayers on an FeO(111) substrate are found to exhibit identical CO adsorption behavior as large gold particles (see picture). This result suggests that particle thickness does not play a significant role in CO adsorption, and therefore size effects seen for the low-temperature CO oxidation reaction are not related to quantum size effects.

    28. Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage-Metal Cations PtM+ (pages 121–124)

      Konrad Koszinowski, Detlef Schröder and Helmut Schwarz

      Article first published online: 5 DEC 2003 | DOI: 10.1002/anie.200352817

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      And they all do it! Like PtAu+, the lighter dinuclear platinum–coinage-metal clusters PtCu+ and PtAg+ also mediate the C–N coupling of methane and ammonia. As the homonuclear clusters Pt2+, Cu2+, Ag2+, and Au2+ are inactive (see scheme), the particular electronic situation of the bimetallic clusters appears to be crucial for the outcome of this intriguing reaction.

    29. Preview: Angew. Chem. Int. Ed. 1/2004 (page 129)

      Article first published online: 17 DEC 2003 | DOI: 10.1002/anie.200390637