Angewandte Chemie International Edition

Cover image for Vol. 46 Issue 28

July 9, 2007

Volume 46, Issue 28

Pages 5247–5447

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    14. Preview
    1. Cover Picture: Development of a T1 Contrast Agent for Magnetic Resonance Imaging Using MnO Nanoparticles (Angew. Chem. Int. Ed. 28/2007) (page 5247)

      Hyon Bin Na, Jung Hee Lee, Kwangjin An, Yong Il Park, Mihyun Park, In Su Lee, Do-Hyun Nam, Sung Tae Kim, Seung-Hoon Kim, Sang-Wook Kim, Keun-Ho Lim, Ki-Soo Kim, Sun-Ok Kim and Taeghwan Hyeon

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200790130

      Thumbnail image of graphical abstract

      Manganese oxide nanoparticles … … have emerged as a powerful contrast agent for molecular and cellular magnetic resonance imaging (MRI). In their Communication on page 5397 ff., J. H. Lee, T. Hyeon, and co-workers demonstrate manganese oxide nanoparticle contrast-enhanced MRI (MONEMRI) with the clear imaging of various mice brain structures as well as the selective imaging of cancer cells (see contrast-enhanced MRI images on the right side of the cover picture; center: “Woman with a Parasol” by Claude Monet, Copyright: Board of Trustees, National Gallery of Art, Washington, DC).

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
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    1. Inside Cover: [Au3Ge45]9−—A Binary Anion Containing a {Ge45} Cluster (Angew. Chem. Int. Ed. 28/2007) (page 5248)

      Annette Spiekermann, Stephan D. Hoffmann, Thomas F. Fässler, Ingo Krossing and Ulrich Preiss

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200790131

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      Starting from elemental gold and germanium a five-step synthetic route leads to the mixed anionic cluster [Au3Ge45]9−, as described by T. F. Fässler et al. in their Communication on page 5310 ff. [Au(PPh3)Cl], obtained from Au metal via tetrachloroauric acid, reacts in solution with the Zintl phase K4Ge9, which had been synthesized from the elements in a solid-state reaction. The unusual complex represents the largest Ge cluster known so far, and some of the 45 Ge atoms exhibit extraordinary modes of Ge coordination.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
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  4. Corrigenda

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
    14. Preview
    1. You have free access to this content
      The Aggregated State of Amyloid-β Peptide In Vitro Depends on Cu2+ Ion Concentration (page 5263)

      Sangmi Jun and Sunil Saxena

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200790133

      This article corrects:

      The Aggregated State of Amyloid-β Peptide In Vitro Depends on Cu2+ Ion Concentration1

      Vol. 46, Issue 21, 3959–3961, Article first published online: 10 APR 2007

    2. You have free access to this content
      Carbodiphosphoranes: The Chemistry of Divalent Carbon(0) (page 5263)

      Ralf Tonner, Florian Öxler, Bernhard Neumüller, Wolfgang Petz and Gernot Frenking

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200790136

      This article corrects:

      Carbodiphosphoranes: The Chemistry of Divalent Carbon(0)

      Vol. 45, Issue 47, 8038–8042, Article first published online: 31 OCT 2006

  5. Retraction

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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
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    10. Highlight
    11. Essay
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      Ring Expansion of a 4,4′-Bipyridyl Derivative into π-Conjugated Azepinoazepines (page 5263)

      Isao Yamaguchi, Saori Tsutsui and Moriyuki Sato

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200790137

      This article corrects:

      Ring Expansion of a 4,4′-Bipyridyl Derivative into π-Conjugated Azepinoazepines

      Vol. 46, Issue 28, 5263, Article first published online: 30 MAR 2007

    2. You have free access to this content
      Ring Expansion of a 4,4′-Bipyridyl Derivative into π-Conjugated Azepinoazepines (page 5263)

      Isao Yamaguchi, Saori Tsutsui and Moriyuki Sato

      Article first published online: 30 MAR 2007 | DOI: 10.1002/anie.200700170

  6. News

    1. Top of page
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    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
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  7. Meeting Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
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    1. Chemistry Unprotected (pages 5268–5271)

      Matthias Köck and Thomas Lindel

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200702455

  8. Book Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
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  9. Highlight

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
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    1. Carbon Radicals of Low Reactivity against Oxygen: Radically Different Antioxidants (pages 5274–5276)

      Hans-Gert Korth

      Article first published online: 21 JUN 2007 | DOI: 10.1002/anie.200701569

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      Radical antioxidants: Carbon-centered radicals, which exist in thermal equilibrium with their dimers in solution, show unexpectedly low reactivity with molecular oxygen. Nevertheless their high reactivity with peroxyl radicals makes them a promising new class of chain-breaking antioxidants (see scheme).

  10. Essay

    1. Top of page
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    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
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    1. On the Structure of Maitotoxin (pages 5278–5282)

      K. C. Nicolaou and Michael O. Frederick

      Article first published online: 27 APR 2007 | DOI: 10.1002/anie.200604656

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      The right way round? Biosynthetic considerations have put the reported structure of maitotoxin in doubt, in particular the stereochemistry of its J/K ring junction (C51/C52, see structure). Further considerations on the basis of computational techniques lead, however, to the conclusion that the originally proposed structure is most likely correct.

  11. Review

    1. Top of page
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    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
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    11. Essay
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    1. The Possible Role of Proton-Coupled Electron Transfer (PCET) in Water Oxidation by Photosystem II (pages 5284–5304)

      Thomas J. Meyer, My Hang V. Huynh and H. Holden Thorp

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200600917

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      Wired for protons: The absorption of light in green plants by photosystem II results in oxidation of water to oxygen at the oxygen-evolving complex (OEC). It is now possible to suggest an important role for proton-coupled electron transfer in this mechanism (see picture). Crucial overall in a complex sequence of reactions is a combination of coupled electron–proton transfer and long-range proton transfer by sequential local proton transfers.

  12. Communications

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. Retraction
    7. News
    8. Meeting Review
    9. Book Review
    10. Highlight
    11. Essay
    12. Review
    13. Communications
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    1. Hard-X-ray-Induced Excited-Spin-State Trapping (pages 5306–5309)

      György Vankó, Franz Renz, Gábor Molnár, Thomas Neisius and Szilvia Kárpáti

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200604432

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      All Xcited: At low temperatures, an intense beam of hard X-rays excites photoswitchable molecular spin-crossover systems to generate metastable high-spin states (see picture). These states have spectroscopic properties similar to those of the states generated by light-induced excited-spin-state trapping. The new approach offers an excitation source with greater penetration.

    2. [Au3Ge45]9−—A Binary Anion Containing a {Ge45} Cluster (pages 5310–5313)

      Annette Spiekermann, Stephan D. Hoffmann, Thomas F. Fässler, Ingo Krossing and Ulrich Preiss

      Article first published online: 4 JUN 2007 | DOI: 10.1002/anie.200603389

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      The golden era of germanium: The largest known germanium cluster [Au3Ge45]9− consists of 45 Ge atoms coordinated to three Au atoms and is obtained by the reaction of K4Ge9 and [AuCl(PPh3)]. DFT calculations reveal the large variety of chemical-bond character in the {Ge45} moiety; localized two-center, two-electron bonds coexist with delocalized polyhedral and three-center, two-electron bonds.

    3. [AuGe18{Si(SiMe3)3}6]: A Soluble Au–Ge Cluster on the Way to a Molecular Cable? (pages 5314–5316)

      Christian Schenk and Andreas Schnepf

      Article first published online: 20 JUN 2007 | DOI: 10.1002/anie.200700530

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      Well-protected: The first successful reaction with a metalloid cluster compound of Group 14 provides the new cluster species [AuGe18{Si(SiMe3)3}6] (see picture; Ge blue, Au yellow, Si(SiMe3)3 groups are shown as a faded space-filling model), which can be considered as a first element on the way to a molecular cable.

    4. Controlling the Bonding of CO on Cobalt Clusters by Coadsorption of H2 (pages 5317–5320)

      Ingmar Swart, André Fielicke, David M. Rayner, Gerard Meijer, Bert M. Weckhuysen and Frank M. F. de Groot

      Article first published online: 4 JUN 2007 | DOI: 10.1002/anie.200605165

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      H in control (of the electrons): The bond strength of CO on small cationic cobalt clusters, as indicated by the C[BOND]O stretching band in the IR spectrum, can be precisely controlled by coadsorption of H2 molecules. Each coadsorbed H atom reduces the electron density available for back-donation by about 0.09–0.25 electrons, depending on cluster size.

    5. Catalytic C[BOND]F Bond Activation of Hexafluoropropene by Rhodium: Formation of (3,3,3-Trifluoropropyl)silanes (pages 5321–5324)

      Thomas Braun, Falk Wehmeier and Kai Altenhöner

      Article first published online: 4 JUN 2007 | DOI: 10.1002/anie.200700711

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      A clean break: The novel catalytic conversion of hexafluoropropene into (3,3,3-trifluoropropyl)silanes by C[BOND]F activation has been developed (see scheme). The reactions are catalyzed by the rhodium complex [Rh{(Z)-CF[DOUBLE BOND]CF(CF3)}(PEt3)3], proceed at room temperature, and are highly selective.

    6. Catalytic Asymmetric Formation of δ-Lactones by [4+2] Cycloaddition of Zwitterionic Dienolates Generated from α,β-Unsaturated Acid Chlorides (pages 5325–5328)

      Paolo S. Tiseni and René Peters

      Article first published online: 1 JUN 2007 | DOI: 10.1002/anie.200700859

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      Smooth elaboration: Versatile δ-lactone building blocks are provided by tertiary-amine-catalyzed asymmetric [4+2] cycloadditions of α,β-unsaturated acid chlorides and the electron-poor aldehyde chloral (see scheme). Silyl-substituted acid chlorides (R1=R3Si) can be used for the diastereoselective synthesis of β-hydroxy-δ-lactones possessing quaternary stereocenters.

    7. Solvent-Dependent Oxidation of a (Pyridylmethyl)amino Ligand by FeCl3 To Give a Water-Soluble Blue Fluorophore (pages 5329–5331)

      Marc Ostermeier, Christian Limberg, Burkhard Ziemer and Venugopal Karunakaran

      Article first published online: 1 JUN 2007 | DOI: 10.1002/anie.200700389

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      When having the blues isn't so bad: While normal coordination chemistry is observed when FeCl3 and the potential ligand 1 (see scheme) are mixed in dichloromethane, redox chemistry occurs in acetonitrile, which involves C[BOND]H activation and C[BOND]N bond formation, and finally leads to a water-soluble blue fluorophore 2.

    8. The Chemical Composition of Animal Cells and Their Intracellular Compartments Reconstructed from 3D Mass Spectrometry (pages 5332–5335)

      Daniel Breitenstein, Christina E. Rommel, Rudolf Möllers, Joachim Wegener and Birgit Hagenhoff

      Article first published online: 5 JUN 2007 | DOI: 10.1002/anie.200604468

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      A peek inside: A C60+ sputter ion source integrated into a time-of-flight secondary-ion mass spectrometer was used to dissect animal cells in a layer-by-layer fashion and analyze the spatial distribution of endogenous molecules. Repeated cycles of sputter erosion and SIMS analysis provided molecular information from the inside of the cells (see picture; red: amino acids, green: phospholipids, blue: glass substrate).

    9. Searching for Drug Scaffolds with 3D Pharmacophores and Neural Network Ensembles (pages 5336–5339)

      Steffen Renner, Mirko Hechenberger, Tobias Noeske, Alexander Böcker, Claudia Jatzke, Michael Schmuker, Christopher G. Parsons, Tanja Weil and Gisbert Schneider

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200604125

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      No longer lost in space: A virtual screening approach for the mapping of chemical space using supervised and unsupervised neural networks is presented. Novel scaffolds of allosteric antagonists for mGluR 5 were identified in regions of chemical space that were not covered by active molecules from the training set.

    10. High-Throughput Screening for Methionyl-tRNA Synthetases That Enable Residue-Specific Incorporation of Noncanonical Amino Acids into Recombinant Proteins in Bacterial Cells (pages 5340–5343)

      Tae Hyeon Yoo and David A. Tirrell

      Article first published online: 14 JUN 2007 | DOI: 10.1002/anie.200700779

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      A change for the better: An efficient method for the identification of mutant methionyl-tRNA synthetases (MetRS) has been developed that enables global incorporation of noncanonical amino acids into recombinant proteins. By using the method, an MetRS variant has been identified that enables near-quantitative replacement of methionine by 6,6,6-trifluoronorleucine (see scheme).

    11. A Low-Dimensional Iron(II) Phosphate Exhibiting Field-Dependent Magnetization Steps (pages 5344–5347)

      Wendy L. Queen, Shiou-Jyh Hwu and Lei Wang

      Article first published online: 14 JUN 2007 | DOI: 10.1002/anie.200604236

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      A step forward: Large single crystals of the new magnetic solid RbNa3Fe7(PO4)6 can be grown in a salt flux. Below the ferro-to-antiferromagnetic transition temperature of 6 K, the field (H) dependence of the magnetization (M) of an oriented crystal of the compound (see graph) exhibits equally spaced steps (arrows), which are probably a result of spin frustration.

    12. Supramolecular Helical Structure of the Stereocomplex Composed of Complementary Isotactic and Syndiotactic Poly(methyl methacrylate)s as Revealed by Atomic Force Microscopy (pages 5348–5351)

      Jiro Kumaki, Takehiro Kawauchi, Kento Okoshi, Hiroshi Kusanagi and Eiji Yashima

      Article first published online: 6 JUN 2007 | DOI: 10.1002/anie.200700455

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      A long-standing question in polymer chemistry has been addressed by AFM, which revealed the helical conformation, handedness, and helical pitch (0.92 nm) of the title stereocomplex formed from a 1:2 mixture of the named polymers (it- and st-PMMA). The results provide convincing evidence for a triple-stranded helix (see structure against a background of the AFM image) as a plausible model for the stereocomplex.

    13. Synthesis of Diverse Lactam Carboxamides Leading to the Discovery of a New Transcription-Factor Inhibitor (pages 5352–5355)

      Pui Yee Ng, Yuchen Tang, Wendy M. Knosp, H. Scott Stadler and Jared T. Shaw

      Article first published online: 14 JUN 2007 | DOI: 10.1002/anie.200700762

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      Diversity is the key: Skeletal diversity is a useful starting point in the search for compounds that modulate protein–biopolymer interactions. A library of 400 lactam carboxamides has been synthesized in a short synthetic sequence and a new compound that inhibits the interaction of a transcription factor (HOXA13) with its DNA target has been discovered, and inhibition of transcription is demonstrated in cells.

    14. Rhodium Dispersion during NO/CO Conversions (pages 5356–5358)

      Andrew J. Dent, John Evans, Steven G. Fiddy, Bhrat Jyoti, Mark A. Newton and Moniek Tromp

      Article first published online: 11 JUN 2007 | DOI: 10.1002/anie.200701419

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      Change and change again: Under catalytic conditions for NO/CO conversion, simultaneous time-resolved extended X-ray absorption fine structure spectroscopy and IR studies show that the rhodium atoms in 5 wt % Rh/Al2O3 rapidly migrate between CO-covered Rh particles and mononuclear Rh–NO sites depending on the changing gas composition. At lower temperatures (473 K), there is interconversion between mononuclear Rh(CO)2 and Rh(NO) centers.

    15. Palladium-Catalyzed Borylation of Aryl Chlorides: Scope, Applications, and Computational Studies (pages 5359–5363)

      Kelvin L. Billingsley, Timothy E. Barder and Stephen L. Buchwald

      Article first published online: 11 JUN 2007 | DOI: 10.1002/anie.200701551

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      From chloride to boronate: Catalysts comprising palladium and biaryl monophosphine ligands provide highly active systems for the borylation of aryl and heteroaryl chlorides (see scheme). Symmetrical and unsymmetrical biaryl products can also be prepared directly from two aryl chlorides without isolation of the intermediate boronate esters. Computational studies provide insight into the roles of the biaryl phosphine ligand and the KOAc base in the catalytic cycle.

    16. Orientational Control of Hexagonally Packed Silica Mesochannels in Lithographically Designed Confined Nanospaces (pages 5364–5368)

      Chia-Wen Wu, Tetsu Ohsuna, Tomohiro Edura and Kazuyuki Kuroda

      Article first published online: 19 JUN 2007 | DOI: 10.1002/anie.200700689

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      A top-down/bottom-up approach has been developed to fabricate mesoporous silica with well-aligned mesochannels of controlled orientation by means of cooperative assembly of an amphiphilic triblock copolymer (P123) and silica species within lithographically designed confined nanospaces. Some mesochannel patterns that can be prepared by this technique are shown schematically in the picture. TEOS=tetraethoxysilane.

    17. Exploiting Organocatalysis: Enantioselective Synthesis of Vinyl Glycines by Allylic Sulfimide [2,3] Sigmatropic Rearrangement (pages 5369–5372)

      Alan Armstrong, Lee Challinor and Jennifer H. Moir

      Article first published online: 11 JUN 2007 | DOI: 10.1002/anie.200701459

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      Have it both ways: Enantiomerically enriched E vinyl glycines may be accessed from aldehydes in a concise sequence that combines an organocatalytic α sulfenylation, stereoselective olefination, a sulfimidation, and a [2,3] sigmatropic rearrangement (see scheme, Boc=tert-butoxycarbonyl, nHex=n-hexyl). Either enantiomeric series can be accessed by control of the alkene geometry in the olefination step.

    18. Highly Enantioselective Aryl Additions of [AlAr3(thf)] to Ketones Catalyzed by a Titanium(IV) Catalyst of (S)-Binol (pages 5373–5376)

      Chien-An Chen, Kuo-Hui Wu and Han-Mou Gau

      Article first published online: 6 JUN 2007 | DOI: 10.1002/anie.200701201

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      Chiral transfer: Novel asymmetric aryl transfers from [AlAr3(thf)] to a wide variety of ketones are catalyzed by an in situ generated titanium species with (S)-binol as the chiral ligand. The reaction affords tertiary alcohols with enantioselectivities up to 97 % ee (see scheme). Binol=2,2′-dihydroxy-1,1′-binaphthyl.

    19. Formal Synthesis of (−)-Aphanorphine Using Sequential Photomediated Radical Reactions of Dithiocarbamates (pages 5377–5380)

      Richard S. Grainger and Emma J. Welsh

      Article first published online: 6 JUN 2007 | DOI: 10.1002/anie.200701055

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      Time to change the light bulb: An alkyl dithiocarbamate, itself formed through a photoinitiated group-transfer cyclization of a carbamoyl radical, undergoes a second photomediated radical process initiated with a different light source. These two reactions, which proceed through the same cyclohexenyl radical intermediate, are key steps in a new asymmetric synthesis of the alkaloid aphanorphine. TEMPO=2,2,6,6-tetramethyl-1-piperidinoxyl radical.

    20. Monocoordinating, Compact Phosphane Immobilized on Silica Surface: Application to Rhodium-Catalyzed Hydrosilylation of Hindered Ketones (pages 5381–5383)

      Go Hamasaka, Atsuko Ochida, Kenji Hara and Masaya Sawamura

      Article first published online: 19 JUN 2007 | DOI: 10.1002/anie.200700947

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      Activity without mobility: A compact trialkylphosphane, chemically immobilized on a silica gel surface (see picture), exhibited unique coordination behavior to form a 1:1 Rh/P complex. The monophosphane–{RhCl(cod)} species on the surface was highly active for catalysis of the hydrosilylation of ketones, allowing the conversion of di(tert-butyl) ketone into the corresponding TBS-protected alcohol. TBS=tert-butyldimethylsilyl; cod=1,5-cyclooctadiene.

    21. How to Predict the Physical Properties of Ionic Liquids: A Volume-Based Approach (pages 5384–5388)

      John M. Slattery, Corinne Daguenet, Paul J. Dyson, Thomas J. S. Schubert and Ingo Krossing

      Article first published online: 14 JUN 2007 | DOI: 10.1002/anie.200700941

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      The molecular volumeVm (that is, the sum of the ionic volumes Vion of the constituent ions) of an ionic liquid (IL) in combination with an anion-dependent empirical relationship is all one needs to predict physical properties such as viscosity, conductivity, and density of [N(CN)2], [BF4], [PF6], and [N(SO2CF3)2] ionic liquids, including those which may as yet only exist on paper.

    22. Double Inversion of Emulsions By Using Nanoparticles and a Di-Chain Surfactant (pages 5389–5392)

      Bernard P. Binks and Jhonny A. Rodrigues

      Article first published online: 4 JUN 2007 | DOI: 10.1002/anie.200700880

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      Two shakes: Double phase inversion of emulsions stabilized by a mixture of silica nanoparticles and a di-chain cationic surfactant can be induced by surfactant concentration alone. The picture shows emulsions of dodecane and water stabilized by silica nanoparticles (left, unstable), di-chain cationic surfactant (right, oil-in-water), and a mixture of the two (middle, water-in-oil).

    23. Hybrid Silica–Nanocrystal–Organic Dye Superstructures as Post-Encoding Fluorescent Probes (pages 5393–5396)

      Chuanliu Wu, Jinsheng Zheng, Chaobiao Huang, Jinping Lai, Shuyan Li, Chen Chen and Yibing Zhao

      Article first published online: 6 JUN 2007 | DOI: 10.1002/anie.200700847

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      Dual control: Hybrid silica–nanocrystal–organic dye superstructures comprising fluorescein isothiocyanate (FITC)-doped silica cores, embedded CdTe quantum dots, and an outer silica shell display well-resolved dual fluorescence emission. Multicolor encoding fluorescent probes are generated by modulating the fluorescence intensity ratio of the dual emission by a simple post-encoding strategy (see picture).

    24. Development of a T1 Contrast Agent for Magnetic Resonance Imaging Using MnO Nanoparticles (pages 5397–5401)

      Hyon Bin Na, Jung Hee Lee, Kwangjin An, Yong Il Park, Mihyun Park, In Su Lee, Do-Hyun Nam, Sung Tae Kim, Seung-Hoon Kim, Sang-Wook Kim, Keun-Ho Lim, Ki-Soo Kim, Sun-Ok Kim and Taeghwan Hyeon

      Article first published online: 13 MAR 2007 | DOI: 10.1002/anie.200604775

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      Contrasting images: A new T1 contrast agent for magnetic resonance imaging (MRI) based on MnO nanoparticles reveals a bright signal enhancement and fine anatomic structures in the T1-weighted MR image of a mouse brain (see picture; left MRI, right MnO-enhanced MRI (MONEMRI)). Furthermore, MnO nanoparticles conjugated with a tumor-specific antibody were used for selectively imaging breast cancer cells in a metastatic tumor in brain.

    25. Approaches to the Design of Better Low-Dosage Gas Hydrate Inhibitors (pages 5402–5404)

      Huang Zeng, Virginia K. Walker and John A. Ripmeester

      Article first published online: 5 JUN 2007 | DOI: 10.1002/anie.200605027

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      Covering up: The greater ability of antifreeze proteins (AFPs), relative to polyvinyl pyrrolidone (PVP), to inhibit the reformation of gas hydrates, despite their smaller adsorption mass, has been explained by using a quartz crystal microbalance equipped with the ability to measure the dissipation factor (D). Whereas AFPs can form a rigid and compact film on the nucleating surface (A), PVP forms a porous and loose film (B).

    26. Ligand-Driven G-Quadruplex Conformational Switching By Using an Unusual Mode of Interaction (pages 5405–5407)

      Raphaël Rodriguez, G. Dan Pantoş, Diana P. N. Gonçalves, Jeremy K. M. Sanders and Shankar Balasubramanian

      Article first published online: 11 JUN 2007 | DOI: 10.1002/anie.200605075

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      Under control: An anthracene polyammonium derivative induces folding of the highly polymorphic human telomeric DNA into a single parallel G-quadruplex conformer through an unusual mode of interaction. The sequential use of this ligand and a porphyrazine allows controlled conformational switching of the quadruplex between parallel and antiparallel conformations.

    27. High-Throughput Identification of Substrate Specificity for Protein Kinase by Using an Improved One-Bead-One-Compound Library Approach (pages 5408–5411)

      Yun-Gon Kim, Dong-Sik Shin, Eun-Mi Kim, Hyung-Yeon Park, Chang-Soo Lee, June-Hyung Kim, Bon-Su Lee, Yoon-Sik Lee and Byung-Gee Kim

      Article first published online: 6 JUN 2007 | DOI: 10.1002/anie.200700195

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      Pick and choose: The identification of the substrate specificity of a protein kinase is critical in understanding its role and function in a cellular signal transduction network. A high-throughput platform was developed for the identification of tyrosine kinase substrate specificity by using an improved one-bead-one-compound ladder peptide library and MALDI-TOF MS.

    28. Real-Time Control of a Catalytic Solid in a Fixed-Bed Reactor Based on In Situ Spectroscopy (pages 5412–5416)

      Simona M. Bennici, Bas M. Vogelaar, T. Alexander Nijhuis and Bert M. Weckhuysen

      Article first published online: 6 JUN 2007 | DOI: 10.1002/anie.200700499

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      A reality check: Reactor control by online spectroscopy is illustrated for a Cr/Al2O3 alkane dehydrogenation catalyst and a vanadium phosphorus oxide catalyst used in the selective oxidation of n-butane to maleic anhydride. Rather than testing the product composition alone, the methodology monitors the state of the catalyst in the reactor, and changes the reaction conditions to keep the catalyst in its optimal state (see picture).

    29. Self-Assembly of Positively Charged Discotic PAHs: From Nanofibers to Nanotubes (pages 5417–5420)

      Dongqing Wu, Linjie Zhi, Graham J. Bodwell, Guanglei Cui, Nok Tsao and Klaus Müllen

      Article first published online: 11 JUN 2007 | DOI: 10.1002/anie.200700515

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      Mind your PQPs: 1D nanostructures were fabricated by the self-assembly of amphiphilic centrally charged discotic 9-alkyl-2-phenylbenzo[8,9]quinolizino[4,5,6,7-fed]phenanthridinylium (PQP) salts. Increasing the alkyl chain length of the PQP salts resulted in nanoscaled lamellar structures, whereas changing the counterion of the PQP salts from Cl to BF4 led to a change from nanoribbons to helices and tubes.

    30. Giant Vesicles Containing Magnetic Nanoparticles and Quantum Dots: Feasibility and Tracking by Fiber Confocal Fluorescence Microscopy (pages 5421–5424)

      Grégory Beaune, Benoit Dubertret, Olivier Clément, Catherine Vayssettes, Valérie Cabuil and Christine Ménager

      Article first published online: 11 JUN 2007 | DOI: 10.1002/anie.200700581

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      Hybrid vesicles: Magnetic nanoparticles (γ-Fe2O3) and quantum dots (CdSe/ZnS) can be entrapped in stable vesicles by emulsion processes. The hybrid vesicles (HVs) have distinct magnetic and fluorescence properties (see images; scale bars: 10 μm). Fluorescence detection allows magnetic manipulation and tracking of the HVs in vivo by both magnetic resonance and fluorescence imaging.

    31. Trapping of Oligomeric Cyclopentadienyllithium Cationic and Anionic Fragments by a V[TRIPLE BOND]V-Bonded Ligand (pages 5425–5427)

      Cecilia Fernández-Cortabitarte, Felipe García, James V. Morey, Mary McPartlin, Sanjay Singh, Andrew E. H. Wheatley and Dominic S. Wright

      Article first published online: 5 JUN 2007 | DOI: 10.1002/anie.200700925

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      Breaking up: The first triple-decker sandwich anion [(η5-Cp)Li(η5-Cp)Li(η5-Cp)] of lithocene (Cp=C5H5) (observed in the charge-separated complex [(L)Li(μ-Cp)Li(μ-Cp)Li(L)]+[(η5-Cp)Li(η5-Cp)Li(η5-Cp)]) is formed in the reaction of [Cp2V] with hppLi (hppH=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). The V[TRIPLE BOND]V-bonded complex [V2(hpp)4] (L) effectively acts as a ligand to intercept the polymeric structure of [CpLi] (see scheme).

    32. Site-Isolated Base- and Acid-Mediated Michael-Initiated Cyclization Cascades (pages 5428–5430)

      Adam W. Pilling, Jutta Boehmer and Darren J. Dixon

      Article first published online: 11 JUN 2007 | DOI: 10.1002/anie.200701079

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      One thing leads to another: Site-isolated base and acid catalysts have been exploited in Michael addition, N-acyl iminium ion cyclization cascades with amide pronucleophiles and α,β-unsaturated carbonyl compounds. The reaction sequence has broad scope, uses commercially available catalysts, is atom efficient, and can be scaled by way of a flow-reactor setup.

    33. Isolation of a Cubane-Type Metal Sulfido Cluster with a Molecular Nitrogen Ligand (pages 5431–5434)

      Hiroyuki Mori, Hidetake Seino, Masanobu Hidai and Yasushi Mizobe

      Article first published online: 4 JUN 2007 | DOI: 10.1002/anie.200701044

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      An end-on N2ligand is the outstanding feature in [{η5-C5Me5)Ir}3{Ru(tmeda)(N2)}(μ3-S)4] (tmeda=Me2NCH2CH2NMe2), the first cubane-type metal sulfido cluster with a dinitrogen ligand, which has been isolated and fully characterized by single-crystal X-ray analysis. The picture shows the cluster core with the Ru-bound N2 ligand (Ir blue, N gray, Ru red, S yellowish green).

    34. Asymmetric Fluorination of α-Aryl Acetic Acid Derivatives with the Catalytic System NiCl2–Binap/R3SiOTf/2,6-Lutidine (pages 5435–5439)

      Toshiaki Suzuki, Yoshitaka Hamashima and Mikiko Sodeoka

      Article first published online: 14 JUN 2007 | DOI: 10.1002/anie.200701071

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      Not binary, but trinary: A binary system consisting of Ni(OTf)2–binap complex and 2,6-lutidine failed to promote the asymmetric fluorination of ester equivalents. However, upon the addition of a substoichiometric amount of Et3SiOTf to the NiCl2–binap/2,6-lutidine catalyst, the monofluorinated products were obtained in good yield with high enantioselectivity (see example). NFSI=N-fluorobenzenesulfonimide, Tf=trifluoromethanesulfonyl.

    35. Discrete Triangular Tripalladium Sandwich Complexes of Arenes (pages 5440–5443)

      Tetsuro Murahashi, Mayu Fujimoto, Yurika Kawabata, Ryou Inoue, Sensuke Ogoshi and Hideo Kurosawa

      Article first published online: 14 JUN 2007 | DOI: 10.1002/anie.200701665

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      Sandwich triangles: A bis([2.2]paracyclophane)tripalladium complex (1) was isolated and characterized by NMR spectroscopy, and a mixed-ligand derivative was structurally characterized. These complexes are the first isolated μ3-arene trimetal complexes of a Group 10 metal. Complex 1 undergoes facile release of a Pd0 atom (see scheme) and as such may be regarded as a Pd0 reservoir.

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      Preview: Angew. Chem. Int. Ed. 29/2007 (page 5447)

      Article first published online: 2 JUL 2007 | DOI: 10.1002/anie.200790135

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