Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

July 25, 2011

Volume 50, Issue 31

Pages 6931–7193

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. Highlights
    10. Reviews
    11. Communications
    12. Preview
    1. Cover Picture: A Nanosized Molybdenum Oxide Wheel with a Unique Electronic-Necklace Structure: STM Study with Submolecular Resolution (Angew. Chem. Int. Ed. 31/2011) (page 6931)

      Dr. Dingyong Zhong, Dr. Filipa Lourosa Sousa, Prof. Dr. Achim Müller, Prof. Dr. Lifeng Chi and Prof. Dr. Harald Fuchs

      Version of Record online: 14 JUL 2011 | DOI: 10.1002/anie.201104524

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      A nanosized metal oxide wheel of the molybdenum blue type of polyoxometalates, the discovery of which was considered as a step to new length scales, has been studied by STM. In their Communication on page 7018 ff., A. Müller, L. Chi, H. Fuchs, and co-workers report that the Mo154 cluster has a unique compartmentalized electronic structure, in which each compartment contains two delocalized electrons. This discovery allows a better understanding of these species.

  2. Inside Cover

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    5. Graphical Abstract
    6. Corrigendum
    7. News
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    9. Highlights
    10. Reviews
    11. Communications
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    1. Inside Cover: Synthesis and Structural Characterization of Crystalline Nonacenes (Angew. Chem. Int. Ed. 31/2011) (page 6932)

      Dr. Balaji Purushothaman, Matthew Bruzek, Dr. Sean R. Parkin, Prof. Anne-Frances Miller and Prof. John E. Anthony

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/anie.201104289

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      Nonacene crystals possess a bright metallic sheen and their solution absorption spectra fit well in the series of silylethyne-substituted acenes. As J. E. Anthony et al. report in their Communication on page 7013 ff., crystallographic analysis of functionalized nonacenes confirmed the nine-ringed structure and showed that π-stacked arrangements exist in the solid state. EPR analysis showed that the nonacenes possess radical character, and exposure of nonacene solutions to light caused decomposition to form a red-fluorescent compound.

  3. Back Cover

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    1. Back Cover: Halogen-Bond-Induced Activation of a Carbon–Heteroatom Bond (Angew. Chem. Int. Ed. 31/2011) (page 6932)

      M. Sc. Sebastian M. Walter, Dipl.-Chem. Florian Kniep, Dr. Eberhardt Herdtweck and Dr. Stefan M. Huber

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/anie.201104287

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      Strong halogen-bond donors can be used to activate carbon–halogen bonds, and in the extreme case heterolytic cleavage of the C[BOND]X bond results. In their Communication on page 7187 ff., S. M. Huber and co-workers report that activated benzhydryl bromide undergoes a Ritter-like reaction with acetonitrile to give N-benzhydryl acetamide.

  4. Graphical Abstract

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    5. Graphical Abstract
    6. Corrigendum
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    9. Highlights
    10. Reviews
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  5. Corrigendum

    1. Top of page
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    1. You have free access to this content
      Corrigendum: Backbone Dynamics of Cyclotide MCoTI-I Free and Complexed with Trypsin (pages 6948–6949)

      Shadakshara S. Puttamadappa, Dr. Krishnappa Jagadish, Dr. Alexander Shekhtman and Dr. Julio A. Camarero

      Version of Record online: 21 JUL 2011 | DOI: 10.1002/anie.201102607

      This article corrects:

      Backbone Dynamics of Cyclotide MCoTI-I Free and Complexed with Trypsin1

      Vol. 49, Issue 39, 7030–7034, Version of Record online: 16 AUG 2010

  6. News

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  7. Author Profile

    1. Top of page
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    1. Younan Xia (pages 6958–6959)

      Version of Record online: 4 JUL 2011 | DOI: 10.1002/anie.201103048

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      “When I was eighteen I wanted to be a mechanical engineer. The biggest challenge facing scientists is nonlinearity …” This and more about Younan Xia can be found on page 6958.

  8. Highlights

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    1. Organism Chemistry

      On the Road towards Chemically Modified Organisms Endowed with a Genetic Firewall (pages 6960–6962)

      Dr. Carlos G. Acevedo-Rocha and Prof. Dr. Nediljko Budisa

      Version of Record online: 24 JUN 2011 | DOI: 10.1002/anie.201103010

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      An automated system for the continuous cultivation of cells in suspension has been used to globally change the composition of the DNA genome of E. coli. Thymine was replaced almost completely by 5-chlorouracil through artificial evolution of cells, during which the bacterial genome accumulated hundreds of mutations under permanent conditions of proliferation and selection. The resulting 5-chlorouracil-adapted descendants had the ability to grow on 5-chlorouracil.

    2. Stereoselective Polymerization

      Duality in Catalyst Design: The Synergistic Coupling of Steric and Stereoelectronic Control over Polyolefin Microstructure (pages 6963–6965)

      Prof. Lawrence R. Sita

      Version of Record online: 24 JUN 2011 | DOI: 10.1002/anie.201101913

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      The full picture: In a new strategy for catalyst design, the coupling of steric and stereoelectronic differentiation to develop the salalen–titanium complex pictured resulted in one of the highest degrees of stereocontrol ever observed for the production of isotactic polypropene (iPP). Ad=adamantyl, Bn=benzyl.

  9. Reviews

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    1. Graphene

      Random Walk to Graphene (Nobel Lecture) (pages 6966–6985)

      Andre K. Geim

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/anie.201101174

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      There can be only one: In their Nobel Reviews, the laureates tell the story about the ever changing, exciting scientific pathways that eventually—for example, with the aid of simple adhesive tape—led them to the discovery of graphene. Graphene is a carbon monolayer with almost magical abilities, including exceptional strength, stability, and electronic properties, with massless Dirac fermions as charge carriers.

    2. Graphene: Materials in the Flatland (Nobel Lecture) (pages 6986–7002)

      Kostya S. Novoselov

      Version of Record online: 5 JUL 2011 | DOI: 10.1002/anie.201101502

      There can be only one: In their Nobel Reviews, the laureates tell the story about the ever-changing, exciting scientific pathways that eventually—for example, with the aid of simple adhesive tape—led them to the discovery of graphene. Graphene is a carbon monolayer with almost magical abilities, including exceptional rigidity, stability, and electronic properties, with massless Dirac fermions as charge carriers.

  10. Communications

    1. Top of page
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    5. Graphical Abstract
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    1. Triplet Naphthyl Cation

      Spectroscopic Evidence for a Triplet Ground State in the Naphthyl Cation (pages 7004–7007)

      Héctor Alvaro Galué and Prof. Jos Oomens

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201102333

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      Run to ground: Infrared spectroscopy of the isolated naphthyl carbocation, C10H7+ (prepared from C10H7Br, see scheme) provides evidence for a triplet electronic ground state (3A′′), in which a π electron is promoted to the vacant σ orbital. Previous computational studies have been ambiguous as to the relative stabilities of the singlet and triplet states; DFT calculations predict both states to be practically isoenergetic.

    2. Bioorganic Chemistry

      The Discovery of 5-Formylcytosine in Embryonic Stem Cell DNA (pages 7008–7012)

      M. Sc. Toni Pfaffeneder, M. Sc. Benjamin Hackner, Dr. Matthias Truß, Dipl.-Chem. Martin Münzel, Dr. Markus Müller, Dipl.-Biochem. Christian A. Deiml, Prof. Dr. Christian Hagemeier and Prof. Dr. Thomas Carell

      Version of Record online: 30 JUN 2011 | DOI: 10.1002/anie.201103899

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      Touching base: Sophisticated mass spectrometry has shown that 5-formylcytosine is a constituent of mammalian embryonic stem cell DNA. This base is likely produced from methylcytosine via hydroxymethylcytosine (see scheme), and it may serve as an intermediate in the long searched for pathway of active DNA demethylation.

    3. Oligoacenes

      Synthesis and Structural Characterization of Crystalline Nonacenes (pages 7013–7017)

      Dr. Balaji Purushothaman, Matthew Bruzek, Dr. Sean R. Parkin, Prof. Anne-Frances Miller and Prof. John E. Anthony

      Version of Record online: 29 JUN 2011 | DOI: 10.1002/anie.201102671

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      Nine in a line: A multifaceted approach, including a silylethylene functionalization strategy, to the synthesis of stable nonacene derivatives (see picture, F green, Si blue) allows an unprecedented level of characterization, including electrochemical, photophysical, and crystallographic studies. The nonacenes show a strong S0–S1 transition and no fluorescence in the visible region.

    4. Polyoxometalate Necklace

      A Nanosized Molybdenum Oxide Wheel with a Unique Electronic-Necklace Structure: STM Study with Submolecular Resolution (pages 7018–7021)

      Dr. Dingyong Zhong, Dr. Filipa Lourosa Sousa, Prof. Dr. Achim Müller, Prof. Dr. Lifeng Chi and Prof. Dr. Harald Fuchs

      Version of Record online: 29 JUN 2011 | DOI: 10.1002/anie.201102274

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      The electrons go in two by two: Scanning tunneling microscopy (STM)/spectroscopy (STS), shows the Mo154 giant wheel cluster to have a unique localization of states within each of the 14 identical compartments forming its necklace-type structure (see picture). Each compartment contains two delocalized electrons. These states make the system different from conventional quantum dots that have completely free electrons or excitonic states.

    5. Alkohol–Carbonyl Interconversion

      Controlled Alcohol–Carbonyl Interconversion by Nickel Catalysis (pages 7022–7026)

      Takehisa Maekawa, Hiromi Sekizawa and Prof. Dr. Kenichiro Itami

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201102092

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      All in one pot: A general synthetic platform allows the interconversion of alcohols and carbonyl compounds in a predictable and controlled fashion in one pot. Under the action of a Ni catalyst, PhCl, CsF, and arylboronates, several multistep alcohol–carbonyl interconversions have been achieved with good overall efficiency (see scheme). A one-pot nickel-catalyzed synthesis of flumecinol (a hepatic microsomal enzyme inducer) has also been demonstrated.

    6. Functional Nanoparticles

      Differentially Charged Hollow Core/Shell Lipid–Polymer–Lipid Hybrid Nanoparticles for Small Interfering RNA Delivery (pages 7027–7031)

      Dr. Jinjun Shi, Dr. Zeyu Xiao, Alexander R. Votruba, Dr. Cristian Vilos and Prof. Omid C. Farokhzad

      Version of Record online: 22 JUN 2011 | DOI: 10.1002/anie.201101554

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      Speedy delivery: Biodegradable and biocompatible polymers and lipids form hybrid core/shell nanoparticles (see picture, left) that show promising in vitro and in vivo results for delivering siRNA. The unique lipid–polymer–lipid nanostructure is elucidated by electron and fluorescence microscopy (right) and provides the delivery system with distinct functional features.

    7. Self-Assembly

      Spontaneous Generation of Highly Emissive RGB Organic Nanospheres (pages 7032–7036)

      Kuo-Pi Tseng, Dr. Fu-Chuan Fang, Dr. Jing-Jong Shyue, Prof. Ken-Tsung Wong, Guillaume Raffy, Prof. André Del Guerzo and Dr. Dario M. Bassani

      Version of Record online: 20 JUN 2011 | DOI: 10.1002/anie.201101945

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      Over the rainbow: Three highly luminescent compounds use hydrogen-bonding interactions to spontaneously generate hollow nanospheres when dropcast from anhydrous solvents (see picture). Together, they cover more than 75 % of the gamut of a conventional liquid crystalline display.

    8. Piezochromic Luminescence

      Layered Host–Guest Materials with Reversible Piezochromic Luminescence (pages 7037–7040)

      Dongpeng Yan, Prof. Jun Lu, Prof. Jing Ma, Shenghui Qin, Prof. Min Wei, Prof. David G. Evans and Prof. Xue Duan

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201102232

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      Under pressure: An anionic organic fluorophore (a stilbene derivative, BTZB) assembled into a layered double hydroxide host has reversible optical responses, including changes in absorption spectra, luminescence color, and fluorescence lifetime, on changing the external pressure (see picture). These changes are not observed for pristine BTZB.

    9. Conformation Analysis

      The Conformation of ATP within the Na,K-ATPase Nucleotide Site: A Statistically Constrained Analysis of REDOR Solid-State NMR Data (pages 7041–7044)

      Dr. David A. Middleton, Dr. Eleri Hughes and Prof. Dr. Mikael Esmann

      Version of Record online: 10 JUN 2011 | DOI: 10.1002/anie.201100736

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      Simplification through statistics: The conformation of adenosine triphosphate (ATP) bound to the high-affinity nucleotide site of Na,K-ATPase in its native membrane (see picture) can be determined by REDOR solid-state NMR measurements. The structural analysis of ligands may be improved dramatically by considering their conformational preferences based on the statistical analysis of a limited number of 31P–13C distances.

    10. Nanoparticles

      Rapid One-Step Low-Temperature Synthesis of Nanocrystalline γ-Al2O3 (pages 7045–7047)

      Dr. Nina Lock, Dr. Mogens Christensen, Kirsten M. Ø. Jensen and Prof. Dr. Bo B. Iversen

      Version of Record online: 21 JUN 2011 | DOI: 10.1002/anie.201100668

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      Alumina in flow: Information obtained from in situ synchrotron powder X-ray diffraction (PXRD) measurements was used to develop the first large-scale, rapid, one-step synthesis of γ-Al2O3. The data suggest a reaction mechanism that does not involve crystalline intermediates, and γ-Al2O3 was prepared at low temperature in a continuous-flow reactor using aluminum isopropoxide in 2-propanol/water without subsequent calcination.

    11. Amyloid Toxicity

      You have full text access to this OnlineOpen article
      Disulfide Bonds Reduce the Toxicity of the Amyloid Fibrils Formed by an Extracellular Protein (pages 7048–7051)

      Dr. Maria F. Mossuto, Dr. Benedetta Bolognesi, Bernat Guixer, Dr. Anne Dhulesia, Federico Agostini, Dr. Janet R. Kumita, Dr. Gian G. Tartaglia, Dr. Mireille Dumoulin, Prof. Christopher M. Dobson and Dr. Xavier Salvatella

      Version of Record online: 10 JUN 2011 | DOI: 10.1002/anie.201100986

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      In a stable condition: Disulfide bonds stabilize folded proteins primarily by decreasing the entropic cost of folding. Such cross-links also reduce toxic aggregation by favoring the formation of highly structured amyloid fibrils (see picture). It is suggested that disulfide bonds in extracellular proteins were selected by evolutionary pressures because they decrease the propensity to form toxic aggregates.

    12. Sticky Oligonucleotides

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      Membrane Anchored Immunostimulatory Oligonucleotides for In Vivo Cell Modification and Localized Immunotherapy (pages 7052–7055)

      Dr. Haipeng Liu, Brandon Kwong and Prof. Darrell J. Irvine

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201101266

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      Amphiphilic oligonucleotides synthesized by covalent conjugation between a hydrophobic diacyllipid tail and chemically stabilized RNA or DNA oligonucleotides can directly label tumor cells on injection into solid tumors. In a murine melanoma tumor model, cell membrane-anchored CpG ODNs with a nuclease-resistant phophorothioate backbone (row a) exhibited significantly enhanced immunostimulatory activity compared to soluble CpG (row b).

    13. Gold Nanoclusters

      Insulin-Directed Synthesis of Fluorescent Gold Nanoclusters: Preservation of Insulin Bioactivity and Versatility in Cell Imaging (pages 7056–7060)

      Chien-Liang Liu, Hung-Tsung Wu, Yi-Hsuan Hsiao, Dr. Chih-Wei Lai, Chun-Wei Shih, Yung-Kang Peng, Dr. Kuo-Chun Tang, Hsing-Wei Chang, Yun-Chen Chien, Prof. Jong-Kai Hsiao, Prof. Juei-Tang Cheng and Prof. Pi-Tai Chou

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201100299

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      Go for gold: As-prepared insulin–Au nanoclusters (NCs) show intense red fluorescence, excellent biocompatibility, and preservation of natural insulin bioactivity in lowering the blood-glucose level. Their versatility in applications is demonstrated by fluorescence imaging, X-ray computed tomography, and insulin–inhibitor interactions (see picture; IDE=insulin-degrading enzyme).

    14. Single-Crystal Transformations

      Dimerization of a Metal Complex through Thermally Induced Single-Crystal-to-Single-Crystal Transformation or Mechanochemical Reaction (pages 7061–7064)

      Dr. Jie Sun, Fangna Dai, Dr. Wenbing Yuan, Dr. Wenhua Bi, Xiaoliang Zhao, Wenming Sun and Prof. Dr. Daofeng Sun

      Version of Record online: 22 JUN 2011 | DOI: 10.1002/anie.201101277

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      Come together: Monomers of copper carboxylate complex 1 (see picture, Cu blue-green, N blue, O red, S yellow, C gray) can dimerize to 2 when previously H-bonded carboxylate groups coordinate to copper. This dimerization can be induced by thermal single-crystal-to-single-crystal transformation or by mechanochemical reaction.

    15. Graphene Conjugates

      Graphene Oxide–Peptide Conjugate as an Intracellular Protease Sensor for Caspase-3 Activation Imaging in Live Cells (pages 7065–7069)

      Dr. Haibo Wang, Dr. Qing Zhang, Prof. Dr. Xia Chu, Dr. Tingting Chen, Dr. Jia Ge and Prof. Ruqin Yu

      Version of Record online: 16 JUN 2011 | DOI: 10.1002/anie.201101351

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      All systems GO! An intracellular protease sensor is based on the covalent conjugate of graphene oxide and peptide substrates with fluorophore labels. The conjugate can be delivered into live cells and provides specific, high-contrast imaging of caspase-3 activation (see picture; orange=cell penetration peptide, blue/black=caspase-3 peptide probe).

    16. Polymersome Morphologies

      Controlled Shape Transformation of Polymersome Stomatocytes (pages 7070–7073)

      Silvie A. Meeuwissen, Prof. Dr. Kyoung Taek Kim, Yingchao Chen, Prof. Dr. Darrin J. Pochan and Prof. Dr. Jan C. M. van Hest

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201102167

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      Shape up your polymersome: Polymeric vesicles composed of block-copolymers with a glassy hydrophobic segment are no longer merely destined to take on the morphology obtained right after self-assembly. Gradual introduction of plasticizing solvents creates a permeable vesicular membrane, which together with osmotic pressure differences leads to shape transformation (see scheme).

    17. Self-Assembly

      Spatially Oriented and Reversible Surface Assembly of Single-Walled Carbon Nanotubes: A Strategy Based on π–π Interactions (pages 7074–7078)

      Prof. Tommaso Ferri, Dr. Daniele Frasca, Prof. Olimpia Arias de Fuentes, Prof. Roberto Santucci and Dr. Marco Frasconi

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201102406

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      Nanotubes released: π–π stacking interactions between single-walled carbon nanotubes (SWCNTs) and a monolayer of aromatic rings anchored on a gold surface result in reversible surface assembly of the SWCNTs. Protonation of a pyridine-based self-assembled monolayer reduces the pyridine–SWCNT interaction and thus releases the SWNCTs (see picture).

    18. Enantioselective Catalysis

      NHC-Cu-Catalyzed Enantioselective Hydroboration of Acyclic and Exocyclic 1,1-Disubstituted Aryl Alkenes (pages 7079–7082)

      Dr. Rosa Corberán, Nicholas W. Mszar and Prof. Amir H. Hoveyda

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201102398

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      Tough nut to crack: Chiral bidentate N-heterocyclic carbene copper complexes were designed that promote enantioselective hydroborations of one of the most difficult substrate classes: acyclic and exocyclic 1,1-disubstituted alkenes undergo reaction with >98 % site selectivity, in up to >98 % yield and e.r=96.5:3.5 (see scheme, B2(pin)2 = bis(pinacolato)diboron).

    19. Sustainable Chemistry

      Caprolactam from Renewable Resources: Catalytic Conversion of 5-Hydroxymethylfurfural into Caprolactone (pages 7083–7087)

      Teddy Buntara, Dr. Sebastien Noel, Dr. Pim Huat Phua, Dr. Ignacio Melián-Cabrera, Prof. Dr. Johannes G. de Vries and Prof. Dr. Hero J. Heeres

      Version of Record online: 22 JUN 2011 | DOI: 10.1002/anie.201102156

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      Renewable nylon: 5-Hydroxymethylfurfural (HMF), which can be obtained from renewable resources such as D-fructose, was converted into caprolactone with very good overall selectivity in only three steps. The new route involves two hydrogenation steps to obtain 1,6-hexanediol, which was oxidatively cyclized to caprolactone, and then converted into caprolactam.

    20. Photocatalysts

      A Highly Active Titanium Dioxide Based Visible-Light Photocatalyst with Nonmetal Doping and Plasmonic Metal Decoration (pages 7088–7092)

      Qiao Zhang, Diana Q. Lima, Dr. Ilkeun Lee, Prof. Francisco Zaera, Dr. Miaofang Chi and Prof. Yadong Yin

      Version of Record online: 24 JUN 2011 | DOI: 10.1002/anie.201101969

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      Nicely decorated: A sandwich-structured photocatalyst shows an excellent performance in degradation reactions of a number of organic compounds under UV, visible light, and direct sunlight (see picture). The catalyst was synthesized by a combination of nonmetal doping and plasmonic metal decoration of TiO2 nanocrystals, which improves visible-light activity and enhances light harvesting and charge separation, respectively.

    21. Natural Product Synthesis

      Biomimetic Synthesis of 5,6-dihydro-glaucogenin C: Construction of the Disecopregnane Skeleton by Iron(II)-Promoted Fragmentation of an α-Alkoxy Hydroperoxide (pages 7093–7096)

      Jinghan Gui, Dr. Dahai Wang and Prof. Dr. Weisheng Tian

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201101893

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      A skeleton key: A biomimetic synthesis of the title natural product was completed in 19 steps and 6.4 % overall yield. Iron(II)-promoted fragmentation of α-alkoxy hydroperoxide and subsequent trapping of the resulting tertiary carbon radical by iodide enabled the highly efficient construction of the challenging 13,14:14,15-disecopregnane skeleton (see scheme; TBDPS=tert-butyldiphenylsilyl).

    22. Synthetic Methods

      Mutual Activation: Suzuki–Miyaura Coupling through Direct Cleavage of the sp2 C[BOND]O Bond of Naphtholate (pages 7097–7100)

      Da-Gang Yu and Prof. Zhang-Jie Shi

      Version of Record online: 24 JUN 2011 | DOI: 10.1002/anie.201101461

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      Working together: A new approach of mutual activation between naphtholates and aryl boronic acid derivatives by the formation of borates to facilitate the Suzuki–Miyaura coupling through direct cleavage of the sp2 C[BOND]O bond by nickel catalysis is described (see scheme; R′: annulated ring system). Various naphtholates and aryl boronic acid derivatives could be directly coupled in good yields.

    23. Natural Products

      Chemical and Chemoenzymatic Syntheses of Bacillithiol: A Unique Low-Molecular-Weight Thiol amongst Low G + C Gram-Positive Bacteria (pages 7101–7104)

      Dr. Sunil V. Sharma, Dr. Vishnu K. Jothivasan, Gerald L. Newton, Heather Upton, Judy I. Wakabayashi, Melissa G. Kane, Dr. Alexandra A. Roberts, Dr. Mamta Rawat, Dr. James J. La Clair and Dr. Chris J. Hamilton

      Version of Record online: 12 JUL 2011 | DOI: 10.1002/anie.201100196

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      The full monty: The recently discovered thiol cofactor bacillithiol (BSH), its biosynthetic precursors, and its symmetrical disulfide are prepared in two ways. The fosfomycin resistance protein (FosB) is shown to be a BSH-utilizing enzyme. It displays bacillithiol-S-transferase activity with a strong preference for BSH over L-cysteine as its thiol substrate.

    24. Enforced Ring-Opening

      Force-Transformed Free-Energy Surfaces and Trajectory-Shooting Simulations Reveal the Mechano-Stereochemistry of Cyclopropane Ring-Opening Reactions (pages 7105–7108)

      Dr. Przemyslaw Dopieralski, Dr. Jordi Ribas-Arino and Prof. Dominik Marx

      Version of Record online: 21 JUN 2011 | DOI: 10.1002/anie.201100399

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      A force to be reckoned with: The force-transformed free-energy surfaces obtained by means of sophisticated ab-initio metadynamics simulations on force-transformed potential-energy surfaces have rationalized the intriguing experimental data on the ring opening of dichlorocyclopropane (see scheme) induced by a mechanical force (F).

    25. Chemically Modified Organisms

      Chemical Evolution of a Bacterium’s Genome (pages 7109–7114)

      Dr. Philippe Marlière, Julien Patrouix, Dr. Volker Döring, Prof. Dr. Piet Herdewijn, Sabine Tricot, Dr. Stéphane Cruveiller, Dr. Madeleine Bouzon and Prof. Dr. Rupert Mutzel

      Version of Record online: 27 JUN 2011 | DOI: 10.1002/anie.201100535

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      Automated selection was used to evolve an Escherichia coli strain unable to synthesize thymine nucleotides into a chemically modified organism whose DNA genome is composed of adenine, cytosine, guanine, and an artificial base, the thymine analogue 5-chlorouracil. Evolving cells were initially observed as irregular filaments and progressively recovered the appearance of short rods typical of wild-type E. coli (see picture).

    26. Heteronanostructures

      Matchstick-Shaped Ag2S–ZnS Heteronanostructures Preserving both UV/Blue and Near-Infrared Photoluminescence (pages 7115–7118)

      Dr. Shuling Shen, Yejun Zhang, Long Peng, Dr. Yaping Du and Prof. Dr. Qiangbin Wang

      Version of Record online: 21 JUN 2011 | DOI: 10.1002/anie.201101084

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      Heterostructured semiconductor matchsticks with Ag2S heads and ZnS stems (see TEM image) were synthesized by thermal co-decomposition of Ag(DDTC) and Zn(DDTC)2 (DDTC=diethyldithiocarbamate). The heteronanostructures show both UV/blue (λex=280 nm) and near-infrared (λex=785 nm) photoluminescence.

    27. C[BOND]O Bond Formation

      C(sp3)[BOND]O Bond-Forming Reductive Elimination of Ethers from Bisphosphine-Ligated Benzylpalladium(II) Aryloxide Complexes (pages 7119–7123)

      Seth L. Marquard and Prof. Dr. John F. Hartwig

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201101088

      Thumbnail image of graphical abstract

      On the contrary: Isolated benzylpalladium aryloxide complexes undergo C(sp3)[BOND]O bond-forming reductive elimination by a stepwise ionic mechanism (see scheme) distinct from the accepted concerted pathway for reductive elimination of aromatic ethers from arylpalladium(II) species. The mechanism is proposed to result from dissociation of the aryloxide ligand followed by nucleophilic attack on the benzylic carbon atom.

    28. Antitumor Agents

      Thermoresponsive Chlorambucil Derivatives for Tumour Targeting (pages 7124–7127)

      Catherine M. Clavel, Dr. Olivier Zava, Dr. Frédéric Schmitt, Blanka Halamoda Kenzaoui, Dr. Alexey A. Nazarov, Dr. Lucienne Juillerat-Jeanneret and Prof. Paul J. Dyson

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201101133

      Thumbnail image of graphical abstract

      Putting the heat on: Drugs that are essentially inactive at 37 °C and are active under mild hyperthermia can be synthesized by modification of chlorambucil with thermoresponsive groups (see picture; C gray, Cl green, F yellow, H white, N blue, O red). This modification should allow this cytotoxic agent to be used in a more targeted fashion, and consequently, with reduced side-effects.

    29. Spin Transitions

      Spin Transition and Exchange Interaction: Janus Visions of Supramolecular Spin Coupling between Face-to-Face Verdazyl Radicals (pages 7128–7131)

      Dr. Lucie Norel, Dr. Jean-Baptiste Rota, Lise-Marie Chamoreau, Dr. Guillaume Pilet, Prof. Dr. Vincent Robert and Prof. Dr. Cyrille Train

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201101190

      Thumbnail image of graphical abstract

      Look both ways: Coordination bonding of verdazyl radicals to diamagnetic metal ions dramatically modifies the crystal packing of the electronic spin bearers. The face-to-face positioning of two radicals leads to a magnetic behavior that is more relevant to a S=0 to S=1 spin-transition phenomenon than to the usual exchange-interaction view.

    30. Electrocatalysis

      Boron-Doped Carbon Nanotubes as Metal-Free Electrocatalysts for the Oxygen Reduction Reaction (pages 7132–7135)

      Dr. Lijun Yang, Dr. Shujuan Jiang, Yu Zhao, Lei Zhu, Sheng Chen, Prof. Xizhang Wang, Prof. Qiang Wu, Prof. Jing Ma, Prof. Yanwen Ma and Prof. Zheng Hu

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201101287

      Thumbnail image of graphical abstract

      A metal-free electrocatalyst has been developed by doping carbon nanotubes with electron-deficient boron. The good performance in the oxygen reduction reaction originates from the enhanced O2 chemisorption and effective utilization of π electrons in the conjugated carbon from the boron doping, as revealed by DFT calculations.

    31. Transition-Metal Catalysis

      Dual Ti–Ru Catalysis in the Direct Radical Haloalkylation of N-Acyl Oxazolidinones (pages 7136–7139)

      Dr. Zhenhua Gu, Aaron T. Herrmann and Prof. Dr. Armen Zakarian

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201101364

      Thumbnail image of graphical abstract

      Waste not, want not: A mechanistic study of the ruthenium-catalyzed haloalkylation of titanium enolates led to the development of a process that is catalytic in both metals: titanium and ruthenium (see scheme; Bn=benzyl, PMP=1,2,2,6,6-pentamethylpiperidine). Catalytic turnover was observed in the formation of the titanium enolates from N-acyl oxazolidinones, and insight was gained into the inhibitory effect of the amine base.

    32. C[BOND]H Activation

      Copper-Catalyzed Dehydrogenative Cross-Coupling Reactions of N-para-Tolylamides through Successive C[BOND]H Activation: Synthesis of 4H-3,1-Benzoxazines (pages 7140–7143)

      Tao Xiong, Yan Li, Prof. Dr. Xihe Bi, Yunhe Lv and Prof. Dr. Qian Zhang

      Version of Record online: 10 JUN 2011 | DOI: 10.1002/anie.201101391

      Thumbnail image of graphical abstract

      A novel annulation reaction of readily available tolylamides was catalyzed by Cu(OTf)2 in the presence of Selectfluor and water through successive intermolecular C[BOND]H activated dehydrogenative cross-coupling reactions of benzylic methyl C(sp3)[BOND]H and aromatic C(sp2)[BOND]H bonds, and subsequent intramolecular C[BOND]O bond formation (see scheme).

    33. Propeller Structures

      Enantioseparation and Electronic Properties of a Propeller-Shaped Triarylborane (pages 7144–7147)

      Dr. Hiroshi Ito, Takanori Abe and Dr. Kazuhiko Saigo

      Version of Record online: 21 JUN 2011 | DOI: 10.1002/anie.201101406

      Thumbnail image of graphical abstract

      Flip out! Bulky substituents induce a high barrier to interconversion of the helically chiral enantiomers of the title triarylborane (see picture) and thus allow the separation of the enantiomers by chiral chromatography. The electronic properties of the central boron atom play a significant role in the flipping dynamics of the propeller structure, and racemization can be greatly accelerated by UV-light irradiation.

    34. Enzymology

      Oxygen-Independent Decarbonylation of Aldehydes by Cyanobacterial Aldehyde Decarbonylase: A New Reaction of Diiron Enzymes (pages 7148–7152)

      Debasis Das, Dr. Bekir E. Eser, Prof. Jaehong Han, Aaron Sciore and Prof. E. Neil G. Marsh

      Version of Record online: 10 JUN 2011 | DOI: 10.1002/anie.201101552

      Thumbnail image of graphical abstract

      Just add water: Structurally, cyanobacterial aldehyde decarbonylases are members of the non-heme diiron oxygenase family of enzymes. However, the enzyme catalyzes the hydrolysis of aliphatic aldehydes to alkanes and formate (see scheme), in an oxygen-independent reaction. This unusual and chemically difficult reaction most likely involves free radical intermediates.

    35. Fluorine Chemistry

      Synthesis of gem-Difluorinated Cyclopropanes and Cyclopropenes: Trifluoromethyltrimethylsilane as a Difluorocarbene Source (pages 7153–7157)

      Fei Wang, Tao Luo, Prof. Dr. Jinbo Hu, Dr. Ying Wang, Hema S. Krishnan, Dr. Parag V. Jog, Dr. Somesh K. Ganesh, Prof. Dr. G. K. Surya Prakash and Prof. Dr. George A. Olah

      Version of Record online: 16 JUN 2011 | DOI: 10.1002/anie.201101691

      Thumbnail image of graphical abstract

      Highly versatile: The Ruppert–Prakash reagent (Me3SiCF3) can be an efficient source of difluorocarbene. By varying the nonmetallic initiator that is used (F at lower temperatures and I at higher temperatures), a range of structurally diverse alkenes and alkynes can be converted into the corresponding gem-difluorinated cyclopropanes and cyclopropenes in good yields (see scheme).

    36. Boron Chemistry

      Transition-Metal-Free Diboration Reaction by Activation of Diboron Compounds with Simple Lewis Bases (pages 7158–7161)

      Amadeu Bonet, Cristina Pubill-Ulldemolins, Dr. Carles Bo, Dr. Henrik Gulyás and Dr. Elena Fernández

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201101941

      Thumbnail image of graphical abstract

      Changing behavior: A nucleophilic sp2 carbene-type boryl moiety, formed upon interaction of tetraalkoxydiboranes and a Lewis base, can attack non-activated C[DOUBLE BOND]C bonds. Computational studies identify the interaction as the overlap between the strongly polarized B[BOND]B σ bond (HOMO) and the antibonding π* orbital (LUMO) of the C[DOUBLE BOND]C bond. Conceptually, the normally electrophilic boron becomes nucleophilic and forces the olefin to act as an electrophile.

    37. [2+2+2] Cycloaddition

      A Simple and Highly Efficient Iron Catalyst for a [2+2+2] Cycloaddition to Form Pyridines (pages 7162–7166)

      Chunxiang Wang, Dr. Xincheng Li, Fan Wu and Prof. Dr. Boshun Wan

      Version of Record online: 22 JUN 2011 | DOI: 10.1002/anie.201102001

      Thumbnail image of graphical abstract

      Joined by iron: The iron catalyst for the formation of pyridines at room temperature (see scheme), which was generated in situ from an inorganic iron salt and a diphosphine ligand, exhibited high reactivity and regioselectivity.

    38. Domino Reactions

      Direct and Highly Diastereoselective Synthesis of Azaspirocycles by a Dysprosium(III) Triflate Catalyzed Aza-Piancatelli Rearrangement (pages 7167–7170)

      Leoni I. Palmer and Prof. Javier Read de Alaniz

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201102102

      Thumbnail image of graphical abstract

      Ring the changes: The first example of an intramolecular aza-Piancatelli rearrangement is reported. Dysprosium(III) trifluoromethanesulfonate efficiently catalyzes the synthesis of functionalized azaspirocycles in a trans-selective manner by a 4π electrocyclization of elaborated furylcarbinols (see scheme; Tf=trifluoromethanesulfonyl).

    39. Photochemistry

      Visible-Light-Induced Oxidation/[3+2] Cycloaddition/Oxidative Aromatization Sequence: A Photocatalytic Strategy To Construct Pyrrolo[2,1-a]isoquinolines (pages 7171–7175)

      You-Quan Zou, Liang-Qiu Lu, Liang Fu, Ning-Jie Chang, Jian Rong, Dr. Jia-Rong Chen and Prof. Dr. Wen-Jing Xiao

      Version of Record online: 22 JUN 2011 | DOI: 10.1002/anie.201102306

      Thumbnail image of graphical abstract

      A ray of sunshine: The title reaction sequence using ethyl 2-(3,4-dihydroisoquinolin-2(1H)-yl)acetates with a series of electron-deficient alkenes and alkynes provides rapid and efficient access to pyrrolo[2,1-a]isoquinolines (see scheme; bpy=2,2′-bipyridine, EWG=electron-withdrawing group). The reaction offers a strategically new protocol for the direct and efficient construction of the core structure of naturally occurring lamellarin alkaloids.

    40. Natural Products

      A Synthetic Route to the Saxitoxin Skeleton: Synthesis of Decarbamoyl α-Saxitoxinol, an Analogue of Saxitoxin Produced by the Cyanobacterium Lyngbya wollei (pages 7176–7178)

      Dr. Yusuke Sawayama and Prof. Toshio Nishikawa

      Version of Record online: 17 JUN 2011 | DOI: 10.1002/anie.201102494

      Thumbnail image of graphical abstract

      Pick your poison: Salient features of a concise synthetic route for the saxitoxin skeleton are a bromonium-ion-initiated cascade cyclization of readily prepared 1 to give tricyclic intermediate 2 and the transformation of the gem-dibromomethylene group into an enol acetate unit. This new route enabled the preparation of 3, a naturally occurring analogue of saxitoxin. Cbz=benzyloxycarbonyl, Ms=methanesulfonyl, Py=pyridine.

    41. Boron Ligands

      Unexpected Bonding Mode of the Diboran(4)yl Ligand: Combining the Boryl Motif with a Dative Pt[BOND]B Interaction (pages 7179–7182)

      Prof. Dr. Holger Braunschweig, Dipl.-Chem. Alexander Damme and Dr. Thomas Kupfer

      Version of Record online: 16 JUN 2011 | DOI: 10.1002/anie.201102593

      Thumbnail image of graphical abstract

      Catching the anchor: Although diboranes(4) commonly react by way of B[BOND]B bond activation, reaction of B2Mes2Br2 with [Pt(PEt3)3] led to the selective oxidative addition of one B[BOND]Br bond; the resulting diboran(4)yl complex shows an unexpected dative Pt[BOND]B bonding interaction to the second boron center of the diboran(4)yl ligand. Oxidative addition of one B[BOND]Br bond in B2(NMe2)2Br2 to [Pt(PiPr3)2] enabled the isolation of a diboran(4)yl species without any dative Pt[BOND]B interaction.

    42. Frustrated Lewis pairs

      Reaction of Frustrated Lewis Pairs with Conjugated Ynones-Selective Hydrogenation of the Carbon–Carbon Triple Bond (pages 7183–7186)

      Dr. Bao-Hua Xu, Dr. Gerald Kehr, Dr. Roland Fröhlich, Birgit Wibbeling, Birgitta Schirmer, Prof. Dr. Stefan Grimme and Prof. Dr. Gerhard Erker

      Version of Record online: 16 JUN 2011 | DOI: 10.1002/anie.201101051

      Thumbnail image of graphical abstract

      Frustrated, but not frustrating: Frustrated Lewis pairs (FLPs) can undergo selective 1,4-addition reactions with conjugated ynones (see scheme). Upon FLP dihydrogen activation selective hydrogenation of the carbon–carbon triple bond can be achieved, in one case even catalytically.

      Corrected by:

      Addition: Addition: Reaction of Frustrated Lewis Pairs with Conjugated Ynones-Selective Hydrogenation of the Carbon–Carbon Triple Bond

      Vol. 51, Issue 41, 10213, Version of Record online: 1 OCT 2012

    43. Halogen Bonds

      Halogen-Bond-Induced Activation of a Carbon–Heteroatom Bond (pages 7187–7191)

      M. Sc. Sebastian M. Walter, Dipl.-Chem. Florian Kniep, Dr. Eberhardt Herdtweck and Dr. Stefan M. Huber

      Version of Record online: 29 JUN 2011 | DOI: 10.1002/anie.201101672

      Thumbnail image of graphical abstract

      I⋅⋅⋅Br-idging: Benzhydryl bromide can be activated by novel halogen-bond donors and subsequently undergoes a Ritter-like reaction with acetonitrile (see scheme). Comparative experiments with non-iodinated reference compounds and tests with added acids indicate that halogen bonds are very likely the basis for this effect. The activation seems to be applicable to other substrates as well.

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