Angewandte Chemie International Edition

Cover image for Vol. 42 Issue 45

November 24, 2003

Volume 42, Issue 45

Pages 5527–5651

    1. Cover Picture: Self-Assembled Microarrays of Attoliter Molecular Vessels (Angew. Chem. Int. Ed. 45/2003) (page 5527)

      Dimitrios Stamou, Claus Duschl, Emmanuel Delamarche and Horst Vogel

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200390618

      Parallel, fast, and effortless self-assembly of nanosized components results in their organization of into functional objects. In their Communication on page 5580 ff., Stamou, Vogel, et al. describe how receptor–ligand recognition allows the assembly of single attoliter molecular vessels in a two-dimensional array format, thus allowing the rapid detection, identification, and manipulation of biologically active compounds in a parallel manner.

    2. From Amorphous to Crystalline by Design: Bio-Inspired Fabrication of Large Micropatterned Single Crystals (pages 5544–5546)

      Dario Braga

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200301677

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      Clear as crystal? There are still many questions to be answered before we can truly understand the mysteries of crystallization. However, there has been some remarkable progress towards finding some of these answers; for example, the use of ordered, functionalized templates to prepare oriented single crystals (see the polarized-light image of a single micropatterned calcite crystal)

    3. Atomic Layer Deposition Chemistry: Recent Developments and Future Challenges (pages 5548–5554)

      Markku Leskelä and Mikko Ritala

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200301652

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      One step at a time: Atomic layer deposition (ALD) is a most promising technique for the design of future integrated circuits. The self-limiting mechanism of ALD lends itself to the preparation of pure high-permittivity oxides for gate dielectrics and memory capacitors, and transition-metal nitride and metal films for interconnects (the picture shows a 300-nm layer of Al2O3 deposited onto a patterned Si substrate).

    4. Strained Heterocycles in Radical Chemistry (pages 5556–5573)

      Andreas Gansäuer, Thorsten Lauterbach and Sanjay Narayan

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200300583

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      Unusual radicals efficiently prepared by the ring opening of heterocycles have enormous potential in organic synthesis. Three different types of valuable radical intermediates can be generated from strained heterocycles by properly choosing the reaction conditions (see scheme; X=O, NR). Applications in the synthesis of complex molecules amply demonstrate the usefulness of the methods.

    5. Nanoparticle Nanotubes (pages 5576–5579)

      Michal Lahav, Tali Sehayek, Alexander Vaskevich and Israel Rubinstein

      Version of Record online: 23 OCT 2003 | DOI: 10.1002/anie.200352216

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      Electrically conducting nanoparticle nanotubes (NPNTs) with a high surface area are obtained by a novel procedure. The assembly of gold nanoparticles on the pore walls of surface-modified nanoporous alumina membrane templates under flow conditions is accompanied by spontaneous room-temperature coalescence of the bound nanoparticles, which results, after membrane dissolution, in self-sustained NPNTs that preserve the nanoparticle morphology (see picture).

    6. Self-Assembled Microarrays of Attoliter Molecular Vessels (pages 5580–5583)

      Dimitrios Stamou, Claus Duschl, Emmanuel Delamarche and Horst Vogel

      Version of Record online: 5 NOV 2003 | DOI: 10.1002/anie.200351866

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      High-density microarrays of attoliter volume elements can be created (see figure) within minutes in a parallel and effortless manner by using self-assembly of nanometer-size components based on biological recognition. These ultrasmall volumes allow localization of single molecules, screening for (bio)chemical properties, and assessing the performance of confined chemical reactions.

    7. Immobilization of Natural Products on Glass Slides by Using a Photoaffinity Reaction and the Detection of Protein–Small-Molecule Interactions (pages 5584–5587)

      Naoki Kanoh, Saori Kumashiro, Siro Simizu, Yasumitsu Kondoh, Satoru Hatakeyama, Hideo Tashiro and Hiroyuki Osada

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352164

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      Library on a glass slide: A variety of small molecules, including complex natural products, are introduced to glass slides using a photoaffinity reaction (see picture). The small molecules retain the inherent ability to interact with the relevant binding proteins. Importantly, this immobilization procedure does not require a specific functional group, and can be applied for use with a diverse small-molecule library.

    8. Temperature-Dependent Interconversion of an Anthracene Radical Cation/Electron Moiety to an Electron–Hole Pair in the Pores of Al-ZSM-5 Zeolites (pages 5587–5591)

      Hervé Vezin, Alain Moissette and Claude Brémard

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352269

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      Trappings of success: The reversible interconversion between an anthracene radical cation and its ejected electron, and an electron–hole pair in the acidic zeolite Al-ZSM-5 was thermally induced. The void space of the porous material facilitates anthracene ionization at room temperature and the electron–hole formation under gentle heating.•=trapped electron•+=electron-deficient site in the radical cation or hole

    9. Flux Closure in Self-Assembled Cobalt Nanoparticle Rings (pages 5591–5593)

      Steven L. Tripp, Rafal E. Dunin-Borkowski and Alexander Wei

      Version of Record online: 3 NOV 2003 | DOI: 10.1002/anie.200352825

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      Closing the circle: Chiral magnetic domains are observed when ferromagnetic Co nanoparticles self-assemble into bracelet-like rings (see picture). The magnetic dipoles of the particles collectively contribute toward flux closure, a bistable state with potential utility for nonvolatile data storage.

    10. Ligand and Metal Effects on the Formation of Main-Group Polyhedral Clusters (pages 5593–5596)

      Sally R. Boss, Martyn P. Coles, Robert Haigh, Peter B. Hitchcock, Ronald Snaith and Andrew E. H. Wheatley

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200351921

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      The reaction of AlMe3or ZnMe2with hppH (hppH=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) and then with tBuLi affords [Li8(H)m(hpp)6]n+[X]n, X=[ZntBu3], m=n=1 (the cation core of which is shown); X=[Li(Me2AltBu2)2], m=0, n=2, as the major product in each case. These data reveal that non-aromatic heterocycle hppH and ZnMe2 can be employed to generate novel hydride-encapsulation main-group-metal clusters, and that related polylithium architectures can also incorporate a central void.

    11. Complexation of Carbon Nanorings with Fullerenes: Supramolecular Dynamics and Structural Tuning for a Fullerene Sensor (pages 5597–5600)

      Takeshi Kawase, Kenji Tanaka, Yohko Seirai, Nami Shiono and Masaji Oda

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352033

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      Tuning up: Carbon nanorings are structurally tuned to optimize their complexation with fullerenes (C60 and C70; see picture). The affinity of carbon nanorings with fullerenes correlates with the width of the contact area. As the intense fluorescence emission of the cyclic-paraphenyleneacetylene host is quenched by the complexation of a fullerene, this effect can be used as a basis of a fullerene sensor.

    12. Facile Fabrication of Inorganic-Polymer Core–Shell Nanostructures by a One-Step Vapor Deposition Polymerization (pages 5600–5603)

      Jyongsik Jang and Byungkwon Lim

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352113

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      A variety of polymer shells with controlled and uniform thickness are easily formed on the surfaces of silica and titania colloids by vapor deposition polymerization (VDP; see picture of silica–PMMA core–shell nanoparticles). Carbon capsules derived from polydivinylbenzene shells can be used in applications such as the encapsulation of pyrene molecules, which is a photochromic dye. These results demonstrate the usefulness of VDP as a simple method to fabricate various capsule materials as well as core–shell nanoparticles.

    13. Self-Assembling Peptide Polyelectrolyte β-Sheet Complexes Form Nematic Hydrogels (pages 5603–5606)

      Amalia Aggeli, Mark Bell, Neville Boden, Lisa M. Carrick and Andrew E. Strong

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352207

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      Fibrillar networks built up from polyelectrolyte β-sheet complexes (see picture) are formed by spontaneous self-assembly when solutions of appropriately designed cationic and anionic oligopeptides are mixed. At the macroscopic level the resulting solutions are nematic hydrogels, which are quite robust to variations in pH or peptide concentration.

    14. Aluminoborate-Based Molecular Sieves with 18-Octahedral-Atom Tunnels (pages 5607–5610)

      Jing Ju, Jianhua Lin, Guobao Li, Tao Yang, Hongmei Li, Fuhui Liao, Chun-K. Loong and Liping You

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352263

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      A framework of AlO6octahedra is present in the microporous aluminoborate HAl3B6O12(OH)4 (PKU-1; see picture), which was synthesized from AlCl3 in a boric acid flux. The octahedra share two or three edges with neighboring octahedra to form a framework with 18-ring tunnels along [001] and 10-ring tunnels along {100}. The borate groups share vertices with the octahedra, compensating the negative charge of the octahedral framework and almost completely blocking the 10-ring channels.

    15. Ruthenium-Stabilized Low-Coordinate Phosphorus Atoms: Structural Evidence for Monomeric Metaphosphonate (pages 5610–5612)

      Richard Menye-Biyogo, Fabien Delpech, Annie Castel, Heinz Gornitzka and Pierre Rivière

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352306

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      Monomeric metaphosphonate is generated and stabilized within the coordination sphere of a ruthenium atom. The π system of a PO moiety coordinates to the transition metal center and this allows thermodynamic stabilization to give the first structural evidence for monomeric dioxophosphorane.

    16. Base-Induced Condensation of α-Chloro Oxime Derivatives Furnishes Alkynes (pages 5613–5615)

      Takayuki Tsuritani, Kazunari Yagi, Hiroshi Shinokubo and Koichiro Oshima

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352317

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      A one-carbon unit is lost in the condensation of α-chloro oxime ethers induced by lithium diisopropylamide [Eq. (1)]. This reaction, which provides alkynyl oxime ethers in good yields, is proposed to proceed via a 2-(iminomethyl)azacyclobutadiene intermediate.

    17. Highly Selective Synthesis of Enamines from Olefins (pages 5615–5619)

      Moballigh Ahmed, Abdul Majeed Seayad, Ralf Jackstell and Matthias Beller

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352320

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      Astonishing chemoselectivity is observed in the rhodium-catalyzed formation of enamines from olefins, CO, H2, and amines (see scheme). This new reaction can be used with a broad range of substrates and is high-yielding and highly selective (n/iso=99:1 in most cases).

    18. Multicomponent Porphyrin Assemblies as Functional Bidentate Phosphite Ligands for Regioselective Rhodium-Catalyzed Hydroformylation (pages 5619–5623)

      Vincent F. Slagt, Piet W. N. M. van Leeuwen and Joost N. H. Reek

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352525

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      Selectivity from a rigid sandwich-type complex: A supramolecular approach was used to prepare chelating ligands that give high selectivity for the linear aldehyde in the rhodium-catalyzed hydroformylation of 1-octene. The multicomponent assembly consists of two tris(zinc(II) porphyrin)phosphite ligands (blue) and three ditopic templates (red) with the rhodium complex (green) in the middle of the structure.

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      Catalytic Dihydroxylation of Olefins with Hydrogen Peroxide: An Organic-Solvent- and Metal-Free System (pages 5623–5625)

      Yoko Usui, Kazuhiko Sato and Masato Tanaka

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352568

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      Green and convenient: Olefins are oxidized to 1,2-diols in high yield with 30 % H2O2 in the presence of resin-supported sulfonic acid (see scheme) under metal-free conditions without any organic solvent. The catalyst can be recycled easily and is effective for at least 10 cycles.

    20. Studies Directed toward the Total Synthesis of Lactonamycin: Control of the Sense of Cycloaddition of a Quinone through Directed Intramolecular Catalysis (pages 5625–5629)

      Christopher D. Cox, Tony Siu and Samuel J. Danishefsky

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352591

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      The rapid assembly of the ABCD tetracyclic ring system of lactonamycin involved the strong-base-induced regioselective Diels–Alder reaction of 1 and 2 to form advanced precursor 3. Regiochemical control results from the suitably positioned hydroxy group, and thus only the desired isomer of 3 is obtained.

    21. Total Synthesis of Lactonamycinone (pages 5629–5634)

      Tony Siu, Christopher D. Cox and Samuel J. Danishefsky

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352592

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      A revised strategy was required for the installation of the remaining polyoxygenated E and F rings of lactonamycinone (2). Key features in the successful route include dihydroxylation of a ketoquinone, the use of a furanone as a lactone surrogate (see 1), and an acid-induced ketalization reaction to install the angular methoxy substituent.

    22. Affinity-Based Tagging of Protein Families with Reversible Inhibitors: A Concept for Functional Proteomics (pages 5635–5638)

      Miriam C. Hagenstein, Jan H. Mussgnug, Kirsten Lotte, Regina Plessow, Andreas Brockhinke, Olaf Kruse and Norbert Sewald

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352084

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      Kinases can be tagged with an engineered chemical probe that comprises a reversibly binding protein ligand, a photoreactive group (4-benzoylphenylalanine), and a fluorescent reporter group (carboxyfluorescein). This principle, which does not require irreversible inhibitors, allows affinity-based detection of protein families in functional proteomics.

    23. [3,3] Sigmatropic Rearrangement of Boron-Containing Allyl Alcohols: Synthesis of Allyl Addition Reagents (pages 5638–5641)

      Jörg Pietruszka and Niklas Schöne

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352210

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      Enantiomerically pure reagents for allyl additions were prepared by [3,3] sigmatropic rearrangements (see scheme) followed by a separation of the diastereoisomers. The highly stable allylboronic esters with a stereogenic center α to a boron atom were used to synthesize Z-configured homoallylic alcohols with an enantiomeric excess >94 %.

    24. A Versatile Metathesis Reaction for the Formation of Labile Bonds between Group 13 and Group 15 Atoms (pages 5641–5644)

      Florian Thomas, Stephan Schulz, Heidi Mansikkamäki and Martin Nieger

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200352332

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      The heterocycles [{Me2AlE(SiMe3)2}x] (E=P–Bi) are powerful metathesis reagents in the presence of 4-dimethylaminopyridine (dmap), thus allowing the synthesis of previously unknown Group 13/15 compounds. Reactions with [Me3M[BOND]dmap] (M=In, Tl) proceed with E(SiMe3)2 transfer to form the corresponding heterocycles [{Me2InBi(SiMe3)2}3] and [{Me2TlE(SiMe3)2}2] (E=P, As), which were characterized by NMR and MS analysis, and by single-crystal X-ray diffraction.

    25. Preview: Angew. Chem. Int. Ed. 45/2003 (page 5651)

      Version of Record online: 18 NOV 2003 | DOI: 10.1002/anie.200390621