Angewandte Chemie International Edition

Cover image for Vol. 49 Issue 16

April 6, 2010

Volume 49, Issue 16

Pages 2803–2947

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: A Small and Compact Chiral Molecule with Large Parity-Violation Effects in the Vibrational Spectrum (Angew. Chem. Int. Ed. 16/2010) (page 2803)

      Detlev Figgen, Anton Koers and Peter Schwerdtfeger

      Version of Record online: 26 MAR 2010 | DOI: 10.1002/anie.201001498

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      The large parity violation effects predicted for the chiral molecule N[TRIPLE BOND]WHClI from relativistic density functional theory are shown as a broken mirror image. The energy difference of 0.7 Hz for the N–W stretching frequency, described by P. Schwerdtfeger et al. in their Communication on page 2941 ff., conveniently lies in the frequency range of CO2 lasers and may be revealed by future high-resolution spectroscopy experiments.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: A Silyl Radical formed by Muonium Addition to a Silylene (Angew. Chem. Int. Ed. 16/2010) (page 2804)

      Amitabha Mitra, Jean-Claude Brodovitch, Clemens Krempner, Paul W. Percival, Pooja Vyas and Robert West

      Version of Record online: 16 MAR 2010 | DOI: 10.1002/anie.201001222

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      Irradiation of the stable silyleneN,N′-bis(2,6-diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene with muons produces a radical that R. West and co-workers have identified, on the basis of its muon spin rotation spectrum, as the monomeric muonium adduct. As described in the Communication on page 2893 ff., the muon hyperfine constant is 931 MHz, which is by far the largest ever recorded for a free radical.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Dirk Trauner (page 2822)

      Version of Record online: 18 MAR 2010 | DOI: 10.1002/anie.201000719

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      “My favorite piece of research is the Fischer proof. A perfect combination of a rather specialized technical advance with brilliant reasoning. When I was eighteen I wanted to be an architect …” This and more about Dirk Trauner can be found on page 2822.

  6. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Plastic Fantastic. How the Biggest Fraud in Physics Shook the Scientific World. By Eugenie Samuel Reich. (pages 2823–2824)

      Gerhard Wegner

      Version of Record online: 30 MAR 2010 | DOI: 10.1002/anie.201000602

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      Palgrave Macmillan 2009. 272 pp., hardcover $ 26.95.—ISBN 978-0230224674

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Raman Scattering

      Nanoparticle Clusters Light Up in SERS (pages 2826–2829)

      Rongchao Jin

      Version of Record online: 19 MAR 2010 | DOI: 10.1002/anie.200906462

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      Seeing double: Nanoparticle clusters (dimers, trimers, etc.) have long been pursued as enhancers in surface-enhanced Raman spectroscopy research. A recent report presents an elegant approach for the high-yielding fabrication of dimers of silver nanospheres from nanocubes by controlled chemical etching. These nanoparticle dimers are capable of strongly enhancing Raman signals of surface adsorbates (see picture).

    2. Alkaloid Synthesis

      Concise Synthesis of (−)-Nakadomarin A (pages 2830–2832)

      David B. C. Martin and Christopher D. Vanderwal

      Version of Record online: 18 MAR 2010 | DOI: 10.1002/anie.201000045

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      The beautiful orchestration of new methods and synthesis design was instrumental to the very efficient synthesis of the manzamine alkaloid (−)-nakadomarin A. In only six operations, the two relatively simple compounds shown were converted into the hexacyclic natural product.

  8. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Ionic Liquids

      Task-Specific Ionic Liquids (pages 2834–2839)

      Ralf Giernoth

      Version of Record online: 12 MAR 2010 | DOI: 10.1002/anie.200905981

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      The sky is the limit: Ionic liquids (ILs) are well-known as modern solvents, but they can be so much more! This Minireview gives an overview of the wide variety of applications of ILs beyond their use as solvents and provides insight into the field of so-called task-specific ionic liquids.

  9. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Ynamides

      Ynamides: Versatile Tools in Organic Synthesis (pages 2840–2859)

      Gwilherm Evano, Alexis Coste and Kévin Jouvin

      Version of Record online: 30 MAR 2010 | DOI: 10.1002/anie.200905817

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      A world of possibilities: Ynamides display an exceptionally fine balance between stability and reactivity, and they offer multiple opportunities for the inclusion of nitrogen-based functionalities into organic molecules (see scheme; EWG=electron-withdrawing group). Recent breakthroughs in the preparation of these substrates have revitalized interest in nitrogen-substituted alkynes. Recent developments in this area are highlighted.

  10. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Drug Discovery

      Structure-Based Discovery of Natural-Product-like TNF-α Inhibitors (pages 2860–2864)

      Daniel Shiu-Hin Chan, Ho-Man Lee, Fang Yang, Chi-Ming Che, Catherine C. L. Wong, Ruben Abagyan, Chung-Hang Leung and Dik-Lung Ma

      Version of Record online: 16 MAR 2010 | DOI: 10.1002/anie.200907360

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      Small but effective: Two natural-product-like inhibitors of tumor necrosis factor α (TNF-α; represented in green in the picture) have been identified using structure-based virtual screening. These compounds represent only the third and fourth examples of direct targeting of TNF-α by a small molecule, and display potency comparable to that of the strongest TNF-α inhibitor reported to date.

    2. Surface Plasmon Resonance

      Plasmonic Modulation of the Upconversion Fluorescence in NaYF4:Yb/Tm Hexaplate Nanocrystals Using Gold Nanoparticles or Nanoshells (pages 2865–2868)

      Hua Zhang, Yujing Li, Ivan A. Ivanov, Yongquan Qu, Yu Huang and Xiangfeng Duan

      Version of Record online: 16 MAR 2010 | DOI: 10.1002/anie.200905805

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      Automatic upgrade: Attachment of gold nanoparticles (NPs) onto upconversion nanocrystals (NCs) results in plasmonic interactions that lead to a significant enhancement of upconversion emission of more than 2.5. Conversely, formation of a gold shell greatly suppresses the NC emission because of considerable scattering of excitation irradiation (see picture; a=NC before seed attachment; b, c=NC with attached Au NPs; c=NC with Au shell; scale bar=50 nm).

    3. Labeling of Live Cells

      Bioorthogonal Turn-On Probes for Imaging Small Molecules inside Living Cells (pages 2869–2872)

      Neal K. Devaraj, Scott Hilderbrand, Rabi Upadhyay, Ralph Mazitschek and Ralph Weissleder

      Version of Record online: 19 MAR 2010 | DOI: 10.1002/anie.200906120

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      Glowing tags: A series of activatable (“turn-on”) tetrazine-conjugated fluorescent probes was developed, which react rapidly in an inverse-electron-demand [4+2] cycloaddition with strained dienophiles such as trans-cyclooctene, thereby strongly increasing the fluorescence intensity (see picture). The novel turn-on probes were applied for intracellular live-cell imaging of a microtubuli-binding trans-cyclooctene modified taxol.

    4. Transmetalation

      Transmetalation Supported by a PtII[BOND]CuI Bond (pages 2873–2877)

      Marc-Etienne Moret, Daniel Serra, Andreas Bach and Peter Chen

      Version of Record online: 15 MAR 2010 | DOI: 10.1002/anie.200906480

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      Passing Me over: Platinum-to-copper methyl transfer is observed upon collision-induced dissociation (CID) of the cations formed by the interaction of the [(R3P)Cu]+ fragment with [(dmpe)PtMe2] (R=Me, Ph, Cy, tBu; dmpe=bis(dimethylphosphino)ethane; see X-ray crystal structure of coordination spheres for R=tBu). The thermochemistry of these processes for R=Me is investigated by mass-spectrometric methods.

    5. Inorganic Composites

      Modular Inorganic Nanocomposites by Conversion of Nanocrystal Superlattices (pages 2878–2882)

      Ravisubhash Tangirala, Jessy L. Baker, A. Paul Alivisatos and Delia J. Milliron

      Version of Record online: 18 MAR 2010 | DOI: 10.1002/anie.200906642

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      Inorganic nanocomposites have been prepared by assembling colloidal nanocrystals and then replacing the organic ligands with precursors to an inorganic matrix phase. Separate synthesis and processing of the nanocrystal and matrix phases allows complete compositional modularity and retention of the superlattice morphologies for sphere (see scheme; top) or rod (bottom) assemblies.

    6. Synthetic Methods

      Multistep Phase-Switch Synthesis by Using Liquid–Liquid Partitioning of Boronic Acids: Productive Tags with an Expanded Repertoire of Compatible Reactions (pages 2883–2887)

      Sam Mothana, Jean-Marie Grassot and Dennis G. Hall

      Version of Record online: 9 FEB 2010 | DOI: 10.1002/anie.200906710

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      Tagging along: A system for phase-switch synthesis has been developed. The boronic acid functionality is used as a phase tag that complexes to sorbitol and facilitates compound transfer from an organic solvent to water at high pH. The phase tag can then be used in a productive reaction step to generate targeted products, thereby eliminating purification by silica gel chromatography.

    7. Nanostructures

      Asymmetric Dumbbells from Selective Deposition of Metals on Seeded Semiconductor Nanorods (pages 2888–2892)

      Sabyasachi Chakrabortty, Jie An Yang, Yee Min Tan, Nimai Mishra and Yinthai Chan

      Version of Record online: 19 MAR 2010 | DOI: 10.1002/anie.200906783

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      Sowing the seeds: The growth of Au and Ag2S nanoparticles at distinct positions on CdSe-seeded CdS heterostructured nanorods can be precisely controlled by variations in the concentration of the Au and Ag precursors, respectively. The ability to direct growth on the nanorods can lead to “Janus-type” structures where Au is located at the more reactive end of the nanorod, whilst Ag2S is located at the other (see picture; CdSe dark blue, CdS light blue, Au yellow, Ag2S gray).

    8. Organosilicon Radicals

      A Silyl Radical formed by Muonium Addition to a Silylene (pages 2893–2895)

      Amitabha Mitra, Jean-Claude Brodovitch, Clemens Krempner, Paul W. Percival, Pooja Vyas and Robert West

      Version of Record online: 12 MAR 2010 | DOI: 10.1002/anie.201000166

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      Muonraker: Irradiation of the stable silylene N,N′-bis(2,6-diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene with muons produced a radical that was identified as the monomeric muonium adduct from its muon spin rotation (μSR) spectrum. The muon hyperfine constant for this radical is 931 MHz, the largest ever recorded for a free radical.

    9. Supramolecular Cages

      Cages with Tetrahedron-Like Topology Formed from the Combination of Cyclotricatechylene Ligands with Metal Cations (pages 2896–2899)

      Brendan F. Abrahams, Nicholas J. FitzGerald and Richard Robson

      Version of Record online: 12 MAR 2010 | DOI: 10.1002/anie.201000149

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      Cage the elephant: Anionic tetrahedral assemblies, formed from the combination of cyclotricatechylene anions with transition metal ions, such as vanadium (see picture), contain large internal cavities that can act as hosts for alkali metal ions and solvent molecules. With appropriate metal centers, the anionic units can be linked together to form highly symmetric coordination polymers (V blue, O red, C black).

    10. Heterocycles

      Lithiation–Electrophilic Substitution of N-Thiopivaloylazetidine (pages 2900–2903)

      David M. Hodgson and Johannes Kloesges

      Version of Record online: 16 MAR 2010 | DOI: 10.1002/anie.201000058

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      The fourth protocol: The rarely studied N-thiopivaloyl group plays a crucial role in mediating efficient α lithiation and incorporation of diverse electrophiles onto an azetidine ring; in the presence of chiral ligands, this chemistry also provides the first example of an enantioselective electrophilic substitution on a four-membered ring.

    11. Charge Transfer

      Comparing Spin-Selective Charge Transport through Donor–Bridge–Acceptor Molecules with Different Oligomeric Aromatic Bridges (pages 2904–2908)

      Amy M. Scott, Annie Butler Ricks, Michael T. Colvin and Michael R. Wasielewski

      Version of Record online: 15 MAR 2010 | DOI: 10.1002/anie.201000171

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      Burning bridges: The exponential distance dependence (β value) of singlet and triplet charge recombination (CR) pathways is determined for three donor-bridge-acceptor (DBA) molecules. p-Phenylethynylene and fluorenone bridges have similar β values, which differ significantly from those of p-phenylene bridges (see picture), thus implying that β for both singlet and triplet CR is system-dependent, not bridge-specific.

    12. Tandem Reactions

      Synthesis of Fluorene and Indenofluorene Compounds: Tandem Palladium-Catalyzed Suzuki Cross-Coupling and Cyclization (pages 2909–2912)

      Tao-Ping Liu, Chun-Hui Xing and Qiao-Sheng Hu

      Version of Record online: 19 MAR 2010 | DOI: 10.1002/anie.201000327

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      “Fluor” it: Palladium-catalyzed tandem reactions, in which C(sp3)[BOND]H bond activation is the key step (see scheme; DMA=dimethylacetamide), lead to substituted fluorenes and indenofluorenes through annulation in high yield and in one step. This method has potential for the preparation of other cyclic compounds, as well as substituted oligofluorenes and polyfluorenes.

    13. Photochromic Systems

      Significance of a Zwitterionic State for Fulgide Photochromism: Implications for the Design of Mimics (pages 2913–2916)

      Gaia Tomasello, Michael J. Bearpark, Michael A. Robb, Giorgio Orlandi and Marco Garavelli

      Version of Record online: 16 MAR 2010 | DOI: 10.1002/anie.200907250

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      Modeling and mimicry: An advanced computational model for the photocyclization of a furyl fulgide showed that a stable charge-transfer excited state, S1, and the corresponding conical intersection with the ground state (see picture) are responsible for the efficient photochromism observed in this system. This finding provides a rationale for the de novo design of related derivatives with similar (or even increased) efficiency.

    14. Nanoparticles

      A Seed-Based Diffusion Route to Monodisperse Intermetallic CuAu Nanocrystals (pages 2917–2921)

      Wei Chen, Rong Yu, Lingling Li, Annan Wang, Qing Peng and Yadong Li

      Version of Record online: 15 MAR 2010 | DOI: 10.1002/anie.200906835

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      A seedy route: Monodisperse CuAu and Cu3Au nanocrystals (NCs) were fabricated by a seed-based diffusion route using Au NCs as precursors. This method has advantages in controlling the size and monodispersity of the products. Moving a solid-state reaction into solution may help to achieve homogeneous diffusion and require less time and thermal energy.

    15. Tandem Reactions

      Asymmetric Tandem Wittig Rearrangement/Mannich Reactions (pages 2922–2924)

      Natalie C. Giampietro and John P. Wolfe

      Version of Record online: 15 MAR 2010 | DOI: 10.1002/anie.201000609

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      The choice is yours: A highly stereoselective synthesis of α-alkyl-α-hydroxy-β-amino esters is accomplished through a tandem Wittig-rearrangement/Mannich reaction sequence. Transformations of N-benzyl or N-Boc imines proceed with high selectivity for formation of syn-amino alcohol derivatives, whereas N-Boc-2-(phenylsulfonyl)amines generate anti-amino alcohol products. Auxiliary cleavage (transesterification or reduction) yields enantiomerically enriched products with up to 96 % ee.

      Corrected by:

      Corrigendum: Corrigendum: Asymmetric Tandem Wittig Rearrangement/Mannich Reactions

      Vol. 49, Issue 24, 4003, Version of Record online: 26 MAY 2010

    16. Electrocatalysis on Gold Clusters

      Aqueous CTAB-Assisted Electrodeposition of Gold Atomic Clusters and Their Oxygen Reduction Electrocatalytic Activity in Acid Solutions (pages 2925–2928)

      Chinnaiah Jeyabharathi, Shanmugam Senthil Kumar, Gobichettipalayam Venkataramani Manohar Kiruthika and Kanala Lakshmi Narasimha Phani

      Version of Record online: 9 FEB 2010 | DOI: 10.1002/anie.200905614

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      Gradual, yet a great leap: Electrosynthesized surfactant-stabilized gold atomic clusters (AuACs; Aun, 5≤n≤13) electrocatalyze the oxygen reduction reaction (ORR) in acid solution at low overpotentials. Depending on the surfactant concentration, the ORR mechanism gradually transits from a direct four-electron to a two-electron pathway (see picture; SHE=standard hydrogen electrode), which suggests the transformation of atomic clusters into nanoparticles.

    17. Amination Methods

      Nickel-Catalyzed Amination of Aryl Pivalates by the Cleavage of Aryl C[BOND]O Bonds (pages 2929–2932)

      Toshiaki Shimasaki, Mamoru Tobisu and Naoto Chatani

      Version of Record online: 12 MAR 2010 | DOI: 10.1002/anie.200907287

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      Catalytic amination: The title reaction demonstrates the use of aryl carboxylates as suitable electrophilic coupling substrates in catalytic amination reactions. N-heterocyclic carbene ligands and NaOtBu promote the amination of aryl pivalates through the cleavage of normally unreactive aryl carbon–oxygen bonds (see scheme; cod=cyclooctadiene).

    18. Catalytic C[BOND]F Activation

      Titanium-Catalyzed C–F Activation of Fluoroalkenes (pages 2933–2936)

      Moritz F. Kühnel and Dieter Lentz

      Version of Record online: 12 MAR 2010 | DOI: 10.1002/anie.200907162

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      Detox: Air-stable titanocene difluoride efficiently catalyzes the chemoselective hydrodefluorination of fluoroalkenes at room temperature leading to hydrofluoroalkenes in high yields (see scheme: Cp=cyclopentadienyl). This is a rare example of the catalyzed conversion of fluoroalkenes into less-fluorinated compounds, which have a lower climatic impact, and is a potential method for breaking down toxic perfluoroalkenes.

    19. Metallacycles

      Formation of a 1-Zircona-2,5-disilacyclopent-3-yne: Coordination of 1,4-Disilabutatriene to Zirconocene? (pages 2937–2940)

      Martin Lamač, Anke Spannenberg, Haijun Jiao, Sven Hansen, Wolfgang Baumann, Perdita Arndt and Uwe Rosenthal

      Version of Record online: 16 MAR 2010 | DOI: 10.1002/anie.201000021

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      Alkyne under stress: A novel metallacycle containing one Zr atom, two Si atoms, and a C[TRIPLE BOND]C bond has been prepared and its structure elucidated (Zr green, Si blue, C gray). According to X-ray data, spectral properties, and DFT calculations, the bonding situation in this compound is characterized as a 1-metalla-2,5-disilacyclopent-3-yne with a weak metal–triple-bond interaction.

    20. Chiral Metal Complexes

      NWHClI: A Small and Compact Chiral Molecule with Large Parity-Violation Effects in the Vibrational Spectrum (pages 2941–2943)

      Detlev Figgen, Anton Koers and Peter Schwerdtfeger

      Version of Record online: 23 MAR 2010 | DOI: 10.1002/anie.200906990

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      Small but mighty: An unprecedented large parity-violation energy difference of 0.7 Hz for the N–W stretching frequency of N[TRIPLE BOND]WHClI, which conveniently lies in the CO2 laser frequency range, is predicted from relativistic density functional theory. This result could lead to the first successful detection of such effects in chiral molecules.

  11. Preview

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

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