Angewandte Chemie International Edition

Cover image for Vol. 47 Issue 49

November 24, 2008

Volume 47, Issue 49

Pages 9357–9573

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: Solid-Supported Synthesis and Biological Evaluation of the Lantibiotic Peptide Bis(desmethyl) Lacticin 3147 A2 (Angew. Chem. Int. Ed. 49/2008) (page 9357)

      Vijaya R. Pattabiraman, Shaun M. K. McKinnie and John C. Vederas

      Article first published online: 21 NOV 2008 | DOI: 10.1002/anie.200890251

      Thumbnail image of graphical abstract

      A two-peptide lantibiotic … is active against certain pathogenic bacteria in nanomolar concentrations. In their Communication on page 9472 ff., J. C. Vederas and co-workers describe the first solid-supported synthesis of lacticin 3147, the bis(desmethyl) analogue of lacticin A2. This compound shows potent synergistic antimicrobial activity in the presence of lacticin A1. Other lantibiotics can be prepared for the study of structure–activity relationships by using this strategy. Annie Tykwinski is thanked for the cover graphic design.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: A Synthetic Analogue of Rieske-Type [2Fe-2S] Clusters (Angew. Chem. Int. Ed. 49/2008) (page 9358)

      Joachim Ballmann, Antonia Albers, Serhiy Demeshko, Sebastian Dechert, Eckhard Bill, Eberhard Bothe, Ulf Ryde and Franc Meyer

      Article first published online: 21 NOV 2008 | DOI: 10.1002/anie.200890252

      Thumbnail image of graphical abstract

      Iron–sulfur proteins of the Rieske type contain a redox-active [2Fe-2S] site that can be described as a variant of the related ferredoxins, but with unsymmetrical Cys2His2 coordination. This unusual Fe/S cluster could now be emulated in a synthetic model for the first time, using relatively simple ligands. In their Communication on page 9537 ff., F. Meyer and co-workers report the successful synthesis as well as the spectroscopic and structural characterization of the biomimetic analogue, which was also analyzed by DFT calculations.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Graphical Abstract: Angew. Chem. Int. Ed. 49/2008 (pages 9361–9372)

      Article first published online: 21 NOV 2008 | DOI: 10.1002/anie.200890253

  4. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
  5. Book Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
  6. Correspondence

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Polyoxometalates (1)

      Platinum-Containing Polyoxometalates (pages 9380–9382)

      Rui Cao, Travis M. Anderson, Daniel A. Hillesheim, Paul Kögerler, Kenneth I. Hardcastle and Craig L. Hill

      Article first published online: 6 NOV 2008 | DOI: 10.1002/anie.200800919

      Late-transition-metal terminal oxo compounds: criticisms, analysis, and responses concerning the Pt-containing polyoxovanadate [H2PtIVV9O28]5− reported by Lee, Kortz, and their co-workers are presented. It is also deduced that a terminal platinum oxo compound from one of their groups, reported elsewhere but cited in connection with [H2PtIVV9O28]5−, is miss-assigned.

    2. Polyoxometalates (2)

      Platinum-Containing Polyoxometalates (pages 9383–9384)

      Ulrich Kortz, Uk Lee, Hea-Chung Joo, Ki-Min Park, Sib Sankar Mal, Michael H. Dickman and Geoffrey B. Jameson

      Article first published online: 6 NOV 2008 | DOI: 10.1002/anie.200804795

      The comments of Hill and co-workers regarding the platinum-containing polyoxovanadate [H2PtIVV9O28]5− are responded to by Kortz, Lee and co-workers. In addition, the existence of the anion α-[SiW10PtIV2O40]8− and the platinum oxo complex [O[DOUBLE BOND]PtIV(H2O)(PW9O34)2]16− are discussed.

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Biosynthesis

      Extending the Biosynthetic Repertoire in Ribosomal Peptide Assembly (pages 9386–9388)

      Bradley S. Moore

      Article first published online: 8 OCT 2008 | DOI: 10.1002/anie.200803868

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      An extended family: The addition of microviridin B (see structure) and trunkamide to the ribosomal peptide biosynthetic family extends the molecular basis of posttranslational modifying reactions to include ω-ester/ω-amide linkage by ATP-grasp ligases (red) and prenylation. The discovery of these novel secondary metabolic reactions may presage the bioengineering of new antimicrobial peptide libraries.

    2. Cortistatin A

      Highlights in Steroid Chemistry: Total Synthesis versus Semisynthesis (pages 9389–9391)

      Carl F. Nising and Stefan Bräse

      Article first published online: 9 OCT 2008 | DOI: 10.1002/anie.200803720

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      Many routes to the destination: Cortistatins are steroids of marine origin of which cortistatin A has the highest antiangiogenetic action. Several total syntheses of this natural product have recently been achieved, based on biosynthesis, biomimetic synthesis, semisynthesis, and de novo synthesis, which are compared in this Highlight.

  8. Essay

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. History of Science

      Lord Rutherford (1871–1937): The Newton of the Atom and the Winner of the Nobel Prize for Chemistry, 1908 (pages 9392–9401)

      John Meurig Thomas

      Article first published online: 6 NOV 2008 | DOI: 10.1002/anie.200803876

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      On the shoulders of giants: Lord Rutherford, who developed the theory of nuclear disintegration and a model of the nuclear atom, was lauded as one of the greatest scientists of all time. His research career witnessed the beginning of the atomic age, and his research group was a hotbed of talented, young scientists.

  9. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Natural Product Synthesis

      The Azadirachtin Story (pages 9402–9429)

      Gemma E. Veitch, Alistair Boyer and Steven V. Ley

      Article first published online: 21 NOV 2008 | DOI: 10.1002/anie.200802675

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      Long and winding road: The natural product azadirachtin (see figure) was first isolated in 1968 from the neem tree, and has been the focus of intense research efforts ever since. With numerous obstacles now overcome, the international efforts towards the total synthesis of this fascinating molecule have now achieved their long-standing goal.

  10. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Correspondence
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Hypervalent Compounds

      Structure and Properties of a Sulfur(IV)[BOND]Sulfur(II)-Bond Compound: Reversible Conversion of a Sulfur-Substituted Organosulfurane into a Thiol (pages 9430–9433)

      Naokazu Kano, Yusuke Itoh, Yuki Watanabe, Shinpei Kusaka and Takayuki Kawashima

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200803945

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      A highly polar hypervalent SIV[BOND]SII bond was formed in the synthesis of a sulfur-substituted sulfurane (see scheme), which was crystallographically characterized. Reduction of the 1,2-dithietane gives the corresponding thiol, and reoxidation gives the sulfurane by S[BOND]S bond reformation. Thermal decomposition leads to a cyclic sulfenate and a thiirane.

    2. Homogeneous Catalysis

      Early Main-Group Metal Catalysts for the Hydrogenation of Alkenes with H2 (pages 9434–9438)

      Jan Spielmann, Frank Buch and Sjoerd Harder

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200804657

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      Transition-metal-free hydrogenation of alkenes can be carried out with simple organocalcium catalysts (20 bar H2, 20 °C). Both steps in the proposed catalytic cycle, hydride addition to the double bond and σ-bond metathesis with H2, have been confirmed. Alkenes sensitive to polymerization are also hydrogenated in good yields.

    3. Synthetic Methods

      Approach to Spirocyclohexadienimines and Corresponding Dienones through Radical ipso Cyclization onto Aromatic Azides (pages 9439–9442)

      Tommaso Lanza, Rino Leardini, Matteo Minozzi, Daniele Nanni, Piero Spagnolo and Giuseppe Zanardi

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200804333

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      Ipsoeasy: Cyclization of aryl radicals at the ipso-position of p-azido-substituted benzamides or 2-phenylacetamides results in effective production of spirocyclohexadieniminyl radicals through prompt elimination of molecular nitrogen by transient azidocyclohexadienyl radicals. The resultant iminyl radicals can be exploited for the synthesis of oxindoles or quinolones bearing spiro-cyclohexadienimine/cyclohexadienone rings (see picture, TTMSS=tris(trimethylsilyl)silane).

    4. Radical Reactions

      Radical Allylation with α-Branched Allyl Sulfones (pages 9443–9446)

      Nicolas Charrier and Samir Z. Zard

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200804298

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      Branching out with sulfones: The use of allyl isopropyl sulfones solves the problem of premature isomerization and allows the radical addition of xanthates to α-branched allyl sulfones (see scheme; DCE=1,2-dichloroethane, TMS=trimethylsilyl). Highly functionalized structures can thus be rapidly assembled under mild reaction conditions by using cheap and readily available substrates and reagents.

    5. Carboranes

      Reaction of 13-Vertex Carboranes with Nucleophiles: Unprecedented Cage-Carbon Extrusion and Formation of Monocarba-closo-dodecaborate Anions (pages 9447–9449)

      Jian Zhang, Hoi-Shan Chan and Zuowei Xie

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200804249

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      In contrast to icosahedral carboranes, instead of deboration, 13-vertex carboranes undergo cage-carbon extrusion and cluster contraction to give icosahedral monocarborane anions on reaction with nucleophiles. In the proposed mechanism, nucleophilic attack on a cage carbon atom cleaves the Ccage[BOND]Ccage bond, new Ccage[BOND]B bonds form to preserve cluster integrity, and hydrogen migration generates the final icosahedral product (see scheme).

    6. Natural Products

      An Efficient Substrate-Controlled Approach Towards Hypoestoxide, a Member of a Family of Diterpenoid Natural Products with an Inside-Out [9.3.1]Bicyclic Core (pages 9450–9453)

      Nicholas A. McGrath, Christopher A. Lee, Hiroshi Araki, Matthew Brichacek and Jon T. Njardarson

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200804237

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      The bicycle works: A versatile route to the verticillane family of natural products has been devised, utilizing a strategically rigidified relay ring-closing metathesis reaction. The shape of the bicyclic product was used to stereoselectively control the bisepoxidation reaction towards hypoestoxide, a member of this natural product family.

    7. Asymmetric Synthesis

      Asymmetric Synthesis of 5-(1-Hydroxyalkyl)tetrazoles by Catalytic Enantioselective Passerini-Type Reactions (pages 9454–9457)

      Tao Yue, Mei-Xiang Wang, De-Xian Wang and Jieping Zhu

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200804213

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      Three-part harmony: Three-component Passerini reactions (P-3CR, see Scheme) of a wide range of aldehydes 2 and isocyanides 3, with hydrazoic acid 4 in toluene, in the presence of a [(salen)AlMe]-complex catalyst afford 5-(1-hydroxyalkyl)tetrazoles 1 in good-to-excellent yields and enantiomeric excess. A tandem Michael addition/enantioselective P-3CR, using an acrolein substrate, affords highly functionalized tetrazoles.

    8. Asymmetric Catalysis

      Effecient Kinetic Resolution of Racemic Amino Aldehydes by Oxidation with N-Iodosuccinimide (pages 9458–9461)

      Daishirou Minato, Yoko Nagasue, Yosuke Demizu and Osamu Onomura

      Article first published online: 30 OCT 2008 | DOI: 10.1002/anie.200804188

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      Selective recognition: The first efficient method for the kinetic resolution of racemic amino aldehydes (see scheme, PG=protecting group) is based on a copper(II)/(R,R)-Ph-BOX complex. The coordinated amino aldehydes were transformed into optically active amino acid methyl esters, and the non-coordinated amino aldehydes were converted into optically active amino aldehyde dimethyl acetals.

    9. Synthetic Methods

      Synthesis of Fluorenones from Aromatic Aldoxime Ethers and Aryl Halides by Palladium-Catalyzed Dual C[BOND]H Activation and Heck Cyclization (pages 9462–9465)

      Vedhagiri S. Thirunavukkarasu, Kanniyappan Parthasarathy and Chien-Hong Cheng

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200804153

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      Highway to Heck: An efficient new one-pot palladium-catalyzed synthesis is described which affords a wide range of 9-fluorenone derivatives in good to excellent yields. A mechanism for the two distinct catalytic steps, C[BOND]H bond activation followed by oxidative intramolecular Heck cyclization, is proposed and reaction intermediates supporting this mechanism have been isolated.

    10. Phase-Transfer Catalysis

      Binaphthyl-Modified Quaternary Phosphonium Salts as Chiral Phase-Transfer Catalysts: Asymmetric Amination of β-Keto Esters (pages 9466–9468)

      Rongjun He, Xisheng Wang, Takuya Hashimoto and Keiji Maruoka

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200804140

      Thumbnail image of graphical abstract

      A reliable phosphonium-based PTC: For the first time a chiral quaternary tetraalkylphosphonium salt has successfully been used as a phase-transfer catalyst (PTC) for asymmetric amination of β-keto esters, in high yield and with high ee (see scheme). Asymmetric amination of a cyclic five-membered β-keto ester is a valuable method for preparing a key intermediate for asymmetric synthesis of aldose reductase inhibitor AS-3201 (Ranirestat).

    11. Semiconductors

      p-Type Field-Effect Transistors of Single-Crystal Zinc Telluride Nanobelts (pages 9469–9471)

      Jun Zhang, Po-Chiang Chen, Guozhen Shen, Jibao He, Amar Kumbhar, Chongwu Zhou and Jiye Fang

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200804073

      Thumbnail image of graphical abstract

      Is ZnTe it great: Controlling the crystal-growth direction leads to formation of single-crystal ZnTe nanobelts along the 〈equation image00〉 direction. The nanobelts, which were synthesized in oleylamine at 250 °C, have a narrow thickness (<6 nm). The ZnTe nanobelts behave as p-type semiconductors in field-effect transistors (see picture).

    12. Lantibiotic Synthesis

      Solid-Supported Synthesis and Biological Evaluation of the Lantibiotic Peptide Bis(desmethyl) Lacticin 3147 A2 (pages 9472–9475)

      Vijaya R. Pattabiraman, Shaun M. K. McKinnie and John C. Vederas

      Article first published online: 20 OCT 2008 | DOI: 10.1002/anie.200802919

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      Lan-tastic! A lanthionine analogue of lacticin 3147 A2 (Lan-A2, 2) containing multiple thioether bridges (see picture) has been successfully synthesized by a combination of solid- and solution-phase peptide synthesis. Chemically synthesized Lan-A2 (2) exhibits synergistic biological activity similar to natural lacticin A2 (1) in the presence of natural lacticin A1 against Gram-positive bacteria.

    13. Nanostructures

      Emergent Hybrid Nanostructures Based on Non-Equilibrium Block Copolymer Self-Assembly (pages 9476–9479)

      Mei Li and Stephen Mann

      Article first published online: 23 OCT 2008 | DOI: 10.1002/anie.200803231

      Thumbnail image of graphical abstract

      Catching the worm: Long myelin-like tubules of a polyethylene oxide-polybutylene oxide block copolymer are kinetically unstable but can be trapped by silica incorporation to produce hybrid nanostructures with high shape anisotropy (see TEM image). Sequestration of mixtures of organosilanes and metal alkoxides or drug molecules in the polymer mesophase gives rise to a range of novel functional nanomaterials.

    14. Organic Magnets

      Structural Study of a Dimerization Process in an Organic Radical Magnet, BBDTA⋅InBr4 (pages 9480–9483)

      Wataru Fujita, Koichi Kikuchi and Kunio Awaga

      Article first published online: 23 OCT 2008 | DOI: 10.1002/anie.200803249

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      A magnetic coordination polymer, BBDTA⋅InBr4, undergoes a spin-Peierls-like phase transition at 250 K. X-ray crystal analysis illustrates that the lattice dimerization accompanies elongation and contraction of the In[BOND]N coordination bonds. Inhomogeneity of the spin and charge distribution on the organic radical increases progressively as the temperature decreases below the transition temperature.

    15. Nanoclusters

      Synthesis of Heterometallic Group 13 Nanoclusters and Inks for Oxide Thin-Film Transistors (pages 9484–9486)

      Zachary L. Mensinger, Jason T. Gatlin, Stephen T. Meyers, Lev N. Zakharov, Douglas A. Keszler and Darren W. Johnson

      Article first published online: 30 OCT 2008 | DOI: 10.1002/anie.200803514

      Thumbnail image of graphical abstract

      Cluster's last stand: The hydrated gallium/indium nanocluster [Ga7In63-OH)6(μ-OH)18(H2O)24(NO3)15] was prepared in a facile, high-yielding synthesis. The use of a key nitroso-containing organic compound as an additive allows for the isolation of multiple grams of the cluster. This larger-scale synthesis facilitates use of the cluster as a single-source precursor for effective thin-film transistors.

    16. Porous Materials

      Hierarchically Micro- and Mesoporous Metal–Organic Frameworks with Tunable Porosity (pages 9487–9491)

      Ling-Guang Qiu, Tao Xu, Zong-Qun Li, Wei Wang, Yun Wu, Xia Jiang, Xing-You Tian and Li-De Zhang

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200803640

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      A new hierarchy: A supramolecular template strategy is used to synthesize hierarchical micro- and mesoporous metal–organic frameworks. The mesopore walls are constructed from a microporous framework (see picture). The porosity can be tuned by using different templates at various molar ratios.

    17. Enzyme Models

      Synthetic Support of De Novo Design: Sterically Bulky [FeFe]-Hydrogenase Models (pages 9492–9495)

      Michael L. Singleton, Nattamai Bhuvanesh, Joseph H. Reibenspies and Marcetta Y. Darensbourg

      Article first published online: 27 OCT 2008 | DOI: 10.1002/anie.200803939

      Thumbnail image of graphical abstract

      A twisted mimic: Upon oxidation of [(μ-SCH2C(CH3)2CH2S-){FeI(CO)2PMe3}2], rearrangement yields the mixed-valent FeIFeII cation in a square-pyramid/inverted square-pyramid geometry with a semibridging CO ligand, closely mimicking the [FeFe] hydrogenase enzyme active site. According to de novo design principles, the steric effect of bridgehead bulk in the S–S bridging ligand stabilizes this structure in the absence of the protein matrix.

    18. Ultrafast Diffraction

      Ultrafast Electron Diffraction Reveals Dark Structures of the Biological Chromophore Indole (pages 9496–9499)

      Sang Tae Park, Andreas Gahlmann, Yonggang He, Jonathan S. Feenstra and Ahmed H. Zewail

      Article first published online: 5 NOV 2008 | DOI: 10.1002/anie.200804152

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      Shedding a light on the dark: Ultrafast electron diffraction of the tryptophan chromophore, indole (see determined structure; C orange, N blue, H white), reveals the involvement of dark structures in the nonradiative pathways of the isolated molecule. Such dark structures have to be part of the understanding of biological chromophore stability.

    19. Near-Infrared Emitter

      3-Hydroxypyridin-2-one Complexes of Near-Infrared (NIR) Emitting Lanthanides: Sensitization of Holmium(III) and Praseodymium(III) in Aqueous Solution (pages 9500–9503)

      Evan G. Moore, Géza Szigethy, Jide Xu, Lars-Olof Pålsson, Andrew Beeby and Kenneth N. Raymond

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200802337

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      Ho ho ho! Characteristic visible and near-infrared (NIR) emission bands of the PrIII and HoIII complexes of the tetradentate 1-methyl-3-hydroxypyridin-2-one chromophore are observed in aqueous solution. The HoIII complex has been structurally characterized and, for the first time for a HoIII complex, the kinetics of the luminescence decay in the NIR region have been determined in solution.

    20. Hollow Nanoparticles

      Single-Crystalline Hollow Face-Centered-Cubic Cobalt Nanoparticles from Solid Face-Centered-Cubic Cobalt Oxide Nanoparticles (pages 9504–9508)

      Ki Min Nam, Jae Ha Shim, Hosung Ki, Sang-Il Choi, Gaehang Lee, Jae Kwon Jang, Younghun Jo, Myung-Hwa Jung, Hyunjoon Song and Joon T. Park

      Article first published online: 27 OCT 2008 | DOI: 10.1002/anie.200803048

      Thumbnail image of graphical abstract

      Hollow nan': Hollow face-centered cubic (fcc) Co nanoparallelepipeds were prepared by thermolysis of solid fcc CoO nanoparallelepipeds in oleylamine (see TEM image). The solid fcc CoO nanoparallelepipeds are reduced by the oleylamine surfactant to form hollow fcc Co nanoparallelepipeds. Voids and fcc Co are generated on the surface of the solid fcc CoO nanoparallelepipeds by the removal of oxide as carbon monoxide.

    21. DNA Damage

      Bond- and Energy-Selective Carbon Abstraction from D-Ribose by Hyperthermal Nitrogen Ions (pages 9509–9512)

      Zongwu Deng, Ilko Bald, Eugen Illenberger and Michael A. Huels

      Article first published online: 27 OCT 2008 | DOI: 10.1002/anie.200803235

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      Stealing C: Scattering of hyperthermal nitrogen ions from a D-ribose film efficiently abstracts carbon from the molecule to form CN (see scheme). The reaction is strongly bond and energy selective for C5 of D-ribose in its pyranose form. The sugar moiety of the DNA/RNA backbone will thus be a vulnerable point for damage caused by reactive scattering of secondary atomic nitrogen ions produced by energetic heavy ions.

    22. Porous Materials

      Amino Acid Silica Hybrid Materials with Mesoporous Structure and Enantiopure Surfaces (pages 9513–9517)

      Andreas Kuschel, Heiko Sievers and Sebastian Polarz

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200803405

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      Pure and porous: Several hundreds of square meters of enantiopure surface per gram of material were generated by introducing amino acids into periodically ordered mesoporous organosilica materials. The stereochemical nature of the surfaces was probed by measuring adsorption isotherms with chiral gases.

    23. Signal Amplification

      Mass Spectrometry Signal Amplification Method for Attomolar Detection of Antigens Using Small-Molecule-Tagged Gold Microparticles (pages 9518–9521)

      Jung Rok Lee, Juhee Lee, Sang Kyung Kim, Kwang Pyo Kim, Hyung Soon Park and Woon-Seok Yeo

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200803893

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      Small but more than enough: Proteins are detected in solution without additional amplification or labeling steps by using a small molecule as a reporter of the protein (see picture, Am-tag=amplification tag). The combination of self-assembled monolayers on gold with matrix-free laser desorption/ionization time-of-flight mass spectrometry offers ultrahigh sensitivity with a detection limit of several attomoles.

    24. Luminescence Switching

      Switching of Polymorph-Dependent ESIPT Luminescence of an Imidazo[1,2-a]pyridine Derivative (pages 9522–9524)

      Toshiki Mutai, Haruhiko Tomoda, Tatsuya Ohkawa, Yuji Yabe and Koji Araki

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200803975

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      Reproducible switching of the polymorph-dependent excited-state intramolecular proton-transfer (ESIPT) luminescence of an imidazo[1,2-a]pyridine between blue-green and yellow (see picture) is achieved by thermal control of its solid-state molecular packing. Thus, ESIPT is a promising mechanism for packing-to-luminescence transduction and amplification that offers a novel design concept for tunable organic luminescent solids.

    25. Two-Photon Photolysis

      Molecular Engineering of Photoremovable Protecting Groups for Two-Photon Uncaging (pages 9525–9529)

      Sylvestre Gug, Frédéric Bolze, Alexandre Specht, Cyril Bourgogne, Maurice Goeldner and Jean-François Nicoud

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200803964

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      Open the cage: Symmetrical photoremovable bis-glutamate cages have been designed, synthesized, and characterized that can release a neurotransmitter with unprecedented two-photon efficiencies (see picture), up to 5 GM for BNSF–Glu (BNSF=2,7-bis-{4-nitro-8-[3-(2-propyl)-styryl]}-9,9-bis-[1-(3,6-dioxaheptyl)]-fluorene) at 800 nm, the optimal window both for tissue transparency and classically available laser sources.

    26. Bismuth–Nitrogen Cations

      A Blue Homoleptic Bismuth–Nitrogen Cation (pages 9530–9532)

      Wolfgang Baumann, Axel Schulz and Alexander Villinger

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200803987

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      Bi and N form a W: An acyclic Bi–N cation (synthesized as its GaCl4 salt) was prepared from lithium N,N′,N′-tris(trimethylsilyl)hydrazide and BiCl3 by chloride abstraction. The W-shaped NNBiNN structure and the bonding of this deep blue cation, which can be regarded a bismapentazenium cation, is discussed on the basis of experimental and theoretical data.

    27. Enzymatic Halogenation

      New Insights into the Mechanism of Enzymatic Chlorination of Tryptophan (pages 9533–9536)

      Silvana Flecks, Eugenio P. Patallo, Xiaofeng Zhu, Aliz J. Ernyei, Gotthard Seifert, Alexander Schneider, Changjiang Dong, James H. Naismith and Karl-Heinz van Pée

      Article first published online: 31 OCT 2008 | DOI: 10.1002/anie.200802466

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      It takes two: Both a lysine and a glutamate residue in the active site of tryptophan halogenase are essential for its chlorination activity. A mechanism for the regioselective enzymatic chlorination of tryptophan involving both amino acids is suggested (see scheme).

    28. Bioinorganic Chemistry

      A Synthetic Analogue of Rieske-Type [2Fe-2S] Clusters (pages 9537–9541)

      Joachim Ballmann, Antonia Albers, Serhiy Demeshko, Sebastian Dechert, Eckhard Bill, Eberhard Bothe, Ulf Ryde and Franc Meyer

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200803418

      Thumbnail image of graphical abstract

      Copycat: An accurate synthetic model for Rieske type [2Fe-2S] cluster has been prepared that emulates structural and spectroscopic features of the natural protein sites, including the characteristic low gav value in the EPR spectra of the reduced [2Fe-2S]+ species. The picture shows the crystal structure of the molecule (C gray, Fe red, N blue, S yellow), its EPR spectrum after reduction (bottom) and its Mössbauer spectrum (top).

    29. Polyoxometalates

      Self-Assembly of a Heteropolyoxopalladate Nanocube: [PdII13AsV8O34(OH)6]8− (pages 9542–9546)

      Elena V. Chubarova, Michael H. Dickman, Bineta Keita, Louis Nadjo, Frédéric Miserque, Maria Mifsud, Isabel W. C. E. Arends and Ulrich Kortz

      Article first published online: 10 OCT 2008 | DOI: 10.1002/anie.200803527

      Thumbnail image of graphical abstract

      Not like the others: A molecular palladium oxide cluster was formed by self-assembly of palladium(II) and arsenic(V) using mild reaction conditions. The resulting heteropolypalladate [PdII13AsV8O34(OH)6]8− has a distorted cubic shape and edge lengths of about 1 nm. The thirteen PdII ions retain four-coordinate square-planar geometry, in marked contrast to all other known discrete polyoxometalates.

    30. Synthetic Methods

      Oxidative Homocoupling of Aryl, Alkenyl, and Alkynyl Grignard Reagents with TEMPO and Dioxygen (pages 9547–9550)

      Modhu Sudan Maji, Thorben Pfeifer and Armido Studer

      Article first published online: 3 NOV 2008 | DOI: 10.1002/anie.200804197

      Thumbnail image of graphical abstract

      Without a transition metal, unsaturated organomagnesium compounds undergo homocoupling in the presence of a substoichiometric amount of the oxidant 2,2,6,6-tertramethylpiperidine-N-oxyl radical (TEMPO) and oxygen. Alkynyl Grignard reagents can even be coupled to give the corresponding diynes with dioxygen in the absence of a catalyst (see scheme).

    31. Aqueous Catalysis

      Modular Chemoenzymatic One-Pot Syntheses in Aqueous Media: Combination of a Palladium-Catalyzed Cross-Coupling with an Asymmetric Biotransformation (pages 9551–9554)

      Edyta Burda, Werner Hummel and Harald Gröger

      Article first published online: 22 OCT 2008 | DOI: 10.1002/anie.200801341

      Thumbnail image of graphical abstract

      Two breeds of cat: A palladium-catalyzed Suzuki cross-coupling and an enzymatic reduction with an alcohol dehydrogenase from Rhodococcus sp. together enable the efficient and highly enantioselective synthesis of chiral biaryl alcohols in a one-pot process (see scheme).

    32. Molecular Beacons

      Low-Noise Stemless PNA Beacons for Sensitive DNA and RNA Detection (pages 9555–9559)

      Elke Socher, Lucas Bethge, Andrea Knoll, Nadine Jungnick, Andreas Herrmann and Oliver Seitz

      Article first published online: 23 OCT 2008 | DOI: 10.1002/anie.200803549

      Thumbnail image of graphical abstract

      A change of the energy transfer mechanism (from contact quenching to FRET) increases the responsiveness of fluorescent hybridization probes. The communication between a responsive fluorescent base surrogate (see picture, green) and a near-infrared dye (red) in peptide nucleic acid provides probes that are extremely dark in the single strand. Hybridization furnishes strong fluorescence increase with a 200 nm shift in emission maximum.

    33. Rare-Earth Metal Complexes

      A Rare-Earth Metal Variant of the Tebbe Reagent (pages 9560–9564)

      Rannveig Litlabø, Melanie Zimmermann, Kuburat Saliu, Josef Takats, Karl W. Törnroos and Reiner Anwander

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200803856

      Thumbnail image of graphical abstract

      The Trofimenko–Tebbe alliance: The sterically crowded, monoanionic scorpionate ligand TptBu,Me provides a unique environment for the isolation of discrete rare-earth metal complexes with Y[BOND](CH3){Al(CH3)4} and La[BOND](CH2) moieties (see structure; C gray, H white, Al orange, B red, La pink, N blue); the latter shows promising reactivity as a Tebbe reagent analogue.

    34. Photoaffinity Labeling

      Affinity-Based Labeling of Cytohesins with a Bifunctional SecinH3 Photoaffinity Probe (pages 9565–9568)

      Xihe Bi, Anton Schmitz, Alaa M. Hayallah, Jin-Na Song and Michael Famulok

      Article first published online: 29 OCT 2008 | DOI: 10.1002/anie.200803962

      Thumbnail image of graphical abstract

      The specific binding of the cytohesin inhibitor SecinH3 to Sec7 domains of cytohesins was shown by the use of a bifunctional photoaffinity probe (see structure) on guanine nucleotide exchange factors (GEFs) and GTPases. This probe should be useful for the proteome-wide profiling of cytohesin complexes and the identification of the binding site.

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      Preview: Angew. Chem. Int. Ed. 50/2008 (page 9573)

      Article first published online: 21 NOV 2008 | DOI: 10.1002/anie.200890255

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