Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 2

January 7, 2013

Volume 52, Issue 2

Pages 469–769

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    1. You have free access to this content
      Cover Picture: Observation of the Fe[BOND]CN and Fe[BOND]CO Vibrations in the Active Site of [NiFe] Hydrogenase by Nuclear Resonance Vibrational Spectroscopy (Angew. Chem. Int. Ed. 2/2013) (page 469)

      Dr. Saeed Kamali, Dr. Hongxin Wang, Dr. Devrani Mitra, Dr. Hideaki Ogata, Prof. Wolfgang Lubitz, Brian C. Manor, Prof. Thomas B. Rauchfuss, Dr. Deborah Byrne, Dr. Violaine Bonnefoy, Prof. Francis E. Jenney Jr., Prof. Michael W. W. Adams, Dr. Yoshitaka Yoda, Dr. Ercan Alp, Dr. Jiyong Zhao and Prof. Stephen P. Cramer

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201208498

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      The active site of [NiFe] hydrogenase is an excellent catalyst for hydrogen conversion with an intriguing ability to recover from exposure to dioxygen. In their Communication on page 724 ff., W. Lubitz, S. P. Cramer, and co-workers use the synchrotron technique of nuclear resonance vibrational spectroscopy to identify normal modes associated with active-site Fe[BOND]CN and Fe[BOND]CO motion.

    2. You have free access to this content
      Inside Cover: Dendritic Fluoroalcohols as Catalysts for Alkene Epoxidation with Hydrogen Peroxide (Angew. Chem. Int. Ed. 2/2013) (page 470)

      Prof. Dr. Albrecht Berkessel, Jan Krämer, Dr. Florian Mummy, Dr. Jörg-M. Neudörfl and Prof. Dr. Rainer Haag

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201209130

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      Electrophilic activation of H2O2 by fluoroalcohols relies on multiple and cooperative hydrogen bonding, and was thus far restricted to the use of these compounds as the solvent, which is costly. In their Communication on page 739 ff., A. Berkessel, R. Haag et al. report that polyglycerol-based dendritic polymers with fluoroalcohol end groups act as catalysts in the epoxidation of olefins with H2O2 through enforced cooperativity of the end groups in the multifunctional dendritic architecture, irrespective of the bulk medium (graphics: Adrian von der Höh).

    3. You have free access to this content
      Inside Back Cover: Direct Prediction of NMR Residual Dipolar Couplings from the Primary Sequence of Unfolded Proteins (Angew. Chem. Int. Ed. 2/2013) (page 771)

      Dr. Jie-rong Huang, Valéry Ozenne, Dr. Malene Ringkjøbing Jensen and Dr. Martin Blackledge

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/anie.201209487

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      NMR spectroscopy is a powerful method for studying disordered proteins, providing atomic resolution and ensemble-averaged information. In their Communication on page 687 ff., M. Blackledge et al. show that by analyzing local and long-range effects, residual dipolar couplings can be determined up to six orders of magnitude faster than by existing techniques.

    4. You have free access to this content
      Back Cover: Highly Branched Concave Au/Pd Bimetallic Nanocrystals with Superior Electrocatalytic Activity and Highly Efficient SERS Enhancement (Angew. Chem. Int. Ed. 2/2013) (page 772)

      Lin-Fei Zhang, Dr. Sheng-Liang Zhong and Prof. Dr. An-Wu Xu

      Version of Record online: 28 DEC 2012 | DOI: 10.1002/anie.201209489

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      The synthesis of highly branched concave Au/Pd bimetallic nanocrystals by seed-mediated growth at room temperature is described by A. W. Xu et al. in their Communication on page 645 ff. These star-shaped nanostructures have high-index facets on their surfaces, exhibit much better catalytic activity for the oxidation of ethanol than spherical Au/Pd catalysts, and show highly efficient SERS enhancement.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    1. You have free access to this content
      Corrigendum: Enantioselective Synthesis of Cyclopropanes That Contain Fluorinated Tertiary Stereogenic Carbon Centers: A Chiral α-Fluoro Carbanion Strategy (page 488)

      Xiao Shen, Dr. Wei Zhang, Lei Zhang, Tao Luo, Xiaolong Wan, Dr. Yucheng Gu and Prof. Dr. Jinbo Hu

      Version of Record online: 28 DEC 2012 | DOI: 10.1002/anie.201208981

  4. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    1. Frank Caruso (page 496)

      Version of Record online: 28 AUG 2012 | DOI: 10.1002/anie.201205933

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      “My favorite food is Thai (red) curry. The most exciting thing about my research is working with bright, dynamic, and motivated researchers …” This and more about Frank Caruso can be found on page 496.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    1. Michael Polanyi and His Generation. Origins of the Social Construction of Science. By Mary Jo Nye. (pages 498–500)

      Bretislav Friedrich

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/anie.201207330

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      The University of Chicago Press, Chicago, 2011. 405 pp., hardcover, $ 45.00.—ISBN 978-0226610634

  8. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    1. Dynamic Kinetic Resolution

      Non-Enzymatic Dynamic Kinetic Resolution of Secondary Aryl Alcohols: Planar Chiral Ferrocene and Ruthenium Catalysts in Cooperation (pages 502–504)

      Dr. Alba E. Díaz-Álvarez, Laura Mesas-Sánchez and Dr. Peter Dinér

      Version of Record online: 6 DEC 2012 | DOI: 10.1002/anie.201207648

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      “Ruth” helps iron! A novel method for the non-enzymatic dynamic kinetic resolution (DKR) of secondary aryl alcohols by the use of the planar chiral ferrocene derivative (+)-1 in combination with the ruthenium racemization catalyst 2 yields acetylated alcohols in high enantioselectivity and yield. This development opens opportunities for new developments in the field of non-enzymatic dynamic kinetic resolution.

    2. Glycoproteins

      Total Synthesis of Erythropoietin through the Development and Exploitation of Enabling Synthetic Technologies (pages 505–507)

      Dr. Richard J. Payne

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201207906

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      A convergent and operationally simple method for the preparation of N-linked glycopeptides (see picture) was highlighted in the preparation of three glycopeptide fragments of erythropoietin. These fragments were assembled by ligation chemistry in the first total synthesis of erythropoietin bearing four glycans. This methodology should find far-reaching applications in the synthesis of a whole range of glycoproteins for biological study.

  9. Minireview

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    1. Receptor Ligands

      Molecular Alliance—From Orthosteric and Allosteric Ligands to Dualsteric/Bitopic Agonists at G Protein Coupled Receptors (pages 508–516)

      Prof. Dr. Klaus Mohr, Dr. Jens Schmitz, Ramona Schrage, Priv.-Doz. Christian Tränkle and Prof. Dr. Ulrike Holzgrabe

      Version of Record online: 6 DEC 2012 | DOI: 10.1002/anie.201205315

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      Balance of power: The simultaneous binding of a ligand to two binding sites of a receptor can leads to high selectivity as an agonist and/or antagonist and may induce pathway-specific signaling. This concept offers access to GPCR modulators with an unprecedented receptor-subtype and signaling selectivity profile and, as a consequence, to drugs with fewer side effects (GPCR=G protein coupled receptor).

  10. Reviews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    1. ACDC

      Asymmetric Counteranion-Directed Catalysis: Concept, Definition, and Applications (pages 518–533)

      Manuel Mahlau and Prof. Dr. Benjamin List

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201205343

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      Opposites attract: This simple realization is the basis for asymmetric counteranion-directed catalysis (ACDC). All reactions proceeding via cationic intermediates are accompanied by a counteranion. Inducing high enantioselectivities in these reactions merely by ion pairing with an enantiomerically pure counteranion has been achieved for the first time during recent years.

    2. Asymmetric Catalysis

      Asymmetric Ion-Pairing Catalysis (pages 534–561)

      Dr. Katrien Brak and Prof. Eric N. Jacobsen

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201205449

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      Framing the field, this review provides an overview of four ion-pairing strategies that have emerged for asymmetric catalysis of transformations proceeding through charged intermediates or reagents (see picture). Particular emphasis is placed on the mechanistic features that enable high asymmetric induction in these systems.

  11. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    1. Protein Models

      Discovery of a Novel Aggregation Domain in the Huntingtin Protein: Implications for the Mechanisms of Htt Aggregation and Toxicity (pages 562–567)

      Dr. Zhe-Ming Wang and Prof. Dr. Hilal A. Lashuel

      Version of Record online: 12 NOV 2012 | DOI: 10.1002/anie.201206561

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      Aggravating aggregation: An N-terminal domain that is in close proximity to the polyQ domain in the huntingtin protein, htt105–138, is shown to be highly aggregation prone (see scheme). Potential cross-talk between this domain and the polyQ region may play a central role in regulating the aggregation and toxicity of Htt-N-terminal fragments.

    2. Silicon Chemistry

      A Generic One-Pot Route to Acyclic Two-Coordinate Silylenes from Silicon(IV) Precursors: Synthesis and Structural Characterization of a Silylsilylene (pages 568–571)

      Dr. Andrey V. Protchenko, Dr. Andrew D. Schwarz, Matthew P. Blake, Prof. Cameron Jones, Prof. Nikolas Kaltsoyannis, Prof. Philip Mountford and Prof. Simon Aldridge

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201208554

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      Si in sight: A one-pot, single-step synthesis of an acyclic silylsilylene, Si{Si(SiMe3)3}{N(SiMe3)Dipp} (Dipp=2,6-iPr2C6H3), from a silicon(IV) starting material is reported, together with evidence for a mechanism involving alkali metal silylenoid intermediates.

    3. Synthetic Methods

      “On Water”: Efficient Iron-Catalyzed Cycloaddition of Aziridines with Heterocumulenes (pages 572–575)

      Mani Sengoden and Prof. Tharmalingam Punniyamurthy

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201207746

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      In suspension: The reaction of aziridines with heterocumulenes in the presence of Fe(NO3)3⋅9 H2O in aqueous suspension provides access to functionalized five-membered heterocycles in good to high yields. This protocol has a wide substrate scope, is simple, and uses a nontoxic and cheap catalyst.

    4. Biotechnology

      Microgel-Stabilized Smart Emulsions for Biocatalysis (pages 576–579)

      Dipl.-Chem. Susanne Wiese, Prof. Dr. Antje C. Spiess and Prof. Dr. Walter Richtering

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201206931

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      Emulsions stabilized by stimuli-responsive microgels were used to perform enzyme catalysis. Many substrates are poorly water-soluble, while enzymes naturally require aqueous environments, thus resulting in a two-phase aqueous–organic system. Smart microgels allow an enzyme-catalyzed reaction to be performed in an emulsion that can be broken under controlled conditions to separate the reaction product and to recycle the enzyme (E) and the microgel.

    5. C[BOND]H Activation

      Rhodium or Ruthenium-Catalyzed Oxidative C[BOND]H/C[BOND]H Cross-Coupling: Direct Access to Extended π-Conjugated Systems (pages 580–584)

      Jiaxing Dong, Zhen Long, Dr. Feijie Song, Ningjie Wu, Qiang Guo, Prof. Dr. Jingbo Lan and Prof. Dr. Jingsong You

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201207196

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      Doubling up: A chemo- and regioselective oxidative cross-coupling between various N-heteroarene-containing arenes and heteroarenes has been carried out by rhodium- or ruthenium-catalyzed twofold C[BOND]H activation, to deliver an array of highly functionalized π-conjugated systems.

    6. Carbocycles

      Catalytic [4+2] Cyclization of α,β-Unsaturated Acyl Chlorides with 3-Alkylenyloxindoles: Highly Diastereo- and Enantioselective Synthesis of Spirocarbocyclic Oxindoles (pages 585–588)

      Dr. Li-Tao Shen, Wen-Qiang Jia and Prof. Dr. Song Ye

      Version of Record online: 13 NOV 2012 | DOI: 10.1002/anie.201207405

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      Cinchona alkaloids were used as Lewis base catalysts in the title reaction. The [4+2] cyclization of α,β-unsaturated acyl chlorides with electron-deficient alkenes derived from oxindole gave the corresponding spirocarbocyclic oxindoles.

    7. Radicals

      Reversible σ-Dimerizations of Persistent Organic Radical Cations (pages 589–592)

      Xiaoyu Chen, Dr. Xingyong Wang, Zhaoyi Zhou, Prof. Yizhi Li, Yunxia Sui, Prof. Jing Ma, Prof. Xinping Wang and Prof. Philip P. Power

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201207412

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      A class of well-defined reversible σ-dimerizations of 9,10-dialkoxyanthracene radical cations are presented. Yellow crystals of the σ-dimerized dication dissociate to purple solutions of monomeric radical cations in solution (see scheme). The identity and stability of radical cations were unequivocally confirmed, providing evidence for reversible σ-dimerizations of persistent radical cations of aromatic systems.

    8. Asymmetric Synthesis

      Asymmetric Hydrogenation of α,α′-Disubstituted Cycloketones through Dynamic Kinetic Resolution: An Efficient Construction of Chiral Diols with Three Contiguous Stereocenters (pages 593–596)

      Chong Liu, Prof. Jian-Hua Xie, Ya-Li Li, Ji-Qiang Chen and Prof. Qi-Lin Zhou

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201207561

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      Chiral diols with three contiguous stereocenters were synthesized by a highly enantioselective ruthenium-catalyzed asymmetric hydrogenation of racemic α,α′-disubstituted cycloketones involving dynamic kinetic resolution. This new catalytic asymmetric method provides a concise route to the alkaloid (+)-γ-lycorane.

    9. Heterocycles

      Selective Ruthenium-Catalyzed Three-Component Synthesis of Pyrroles (pages 597–601)

      Prof. Dr. Min Zhang, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201206082

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      It's a snap: A novel catalytic three-component coupling reaction using simple and easily available substrates leads to a wide range of substituted pyrroles with high regioselectively (see scheme; Xantphos=9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene).

    10. Solar cells

      Highly Efficient p-Type Dye-Sensitized Solar Cells based on Tris(1,2-diaminoethane)Cobalt(II)/(III) Electrolytes (pages 602–605)

      Satvasheel Powar, Torben Daeneke, Michelle T. Ma, Dongchuan Fu, Dr. Noel W. Duffy, Dr. Günther Götz, Martin Weidelener, Dr. Amaresh Mishra, Prof. Peter Bäuerle, Prof. Leone Spiccia and Prof. Udo Bach

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201206219

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      Co-produced: Using [Co(en)3]2+/3+ based-electrolytes in p-type dye-sensitized solar cells (p-DSCs) gives record energy conversion efficiencies of 1.3 % and open-circuit voltages up to 709 mV under simulated sun light. The increase in photovoltage is due to the more negative redox potential of [Co(en)3]2+/3+ compared to established mediators.

    11. Synthetic Methods

      Effect of Multinuclear Copper/Aluminum Complexes in Highly Asymmetric Conjugate Addition of Trimethylaluminum to Acyclic Enones (pages 606–610)

      Prof. Dr. Kohei Endo, Daisuke Hamada, Sayuri Yakeishi and Prof. Dr. Takanori Shibata

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201206297

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      Al and friends: Asymmetric conjugate addition of Me3Al to β,β-disubstituted α,β-unsaturated ketones in the presence copper and L1 leads to a highly efficient construction of an all-carbon-substituted chiral quaternary center. This result is the first example of an asymmetric conjugate addition of Me3Al to acyclic enones to give a chiral quaternary carbon center with excellent yield and enantioselectivity under mild reaction conditions.

    12. Amino Acids

      5(4H)-Oxazolones as Intermediates in the Carbodiimide- and Cyanamide-Promoted Peptide Activations in Aqueous Solution (pages 611–614)

      Dr. Grégoire Danger, Arthur Michaut, Manon Bucchi, Dr. Laurent Boiteau, Justine Canal, Dr. Raphaël Plasson and Dr. Robert Pascal

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201207730

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      The early days: Although considered a species to be avoided in peptide chemistry, the intermediacy of 5(4H)-oxazolones is demonstrated to be essential for the formation of peptides through cyanamide and carbodiimide activation in aqueous solution (see scheme).

    13. Cross-Coupling

      Mild and General Conditions for Negishi Cross-Coupling Enabled by the Use of Palladacycle Precatalysts (pages 615–619)

      Yang Yang, Nathan J. Oldenhuis and Prof. Dr. Stephen L. Buchwald

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201207750

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      A wide range of biaryls were synthesized by palladium-catalyzed Negishi cross-couplings at ambient temperature or with low catalyst loading. This protocol features the use of a recently reported aminobiphenyl palladacycle precatalyst to generate the catalytically active XPhosPd0 species. Significantly, a wide range of challenging heterocyclic and polyfluorinated aromatic substrates can be employed to give products in excellent yields.

    14. Natural Products

      Stereoselective Total Syntheses of (−)-Flueggine A and (+)-Virosaine B (pages 620–624)

      Dr. Hao Wei, Chuang Qiao, Gang Liu, Prof. Dr. Zhen Yang and Prof. Dr. Chuang-chuang Li

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201208261

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      Convergent approach: The total syntheses of (−)-flueggine A and (+)-virosaine B (see scheme) have been accomplished in a concise and convergent manner. Key steps in these approaches were relay ring-closing metathesis reactions for rapid construction of the key intermediates, and 1,3-dipolar cycloaddition reactions for the formation of the natural products.

    15. Cascade Reactions

      Cascade Approach to Stereoselective Polycyclic Ether Formation: Epoxides as Trapping Agents in the Transposition of Allylic Alcohols (pages 625–628)

      Youwei Xie and Prof. Paul E. Floreancig

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201208132

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      Complexity from simplicity: Polycyclic ethers are synthesized by cascade reactions involving the use of epoxides as electrophilic traps in the transposition of allylic alcohols. Stereogenic centers are created by functionalizing prochiral sites under thermodynamic control, and remote stereoinduction can be achieved through the use of ketones as conduits.

    16. Annulation

      Rhodium(III)-Catalyzed Alkenyl C[BOND]H Bond Functionalization: Convergent Synthesis of Furans and Pyrroles (pages 629–633)

      Yajing Lian, Tatjana Huber, Kevin D. Hesp, Prof. Dr. Robert G. Bergman and Prof. Dr. Jonathan A. Ellman

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201207995

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      Ring in the new: A new annulation for the efficient synthesis of substituted furans and pyrroles is reported. The RhIII-catalyzed reaction of O-methyl α,β-unsaturated oximes with aldehydes and N-tosyl imines affords secondary alcohol and amine intermediates, respectively. Cyclization and aromatization occurs under the reaction conditions to provide access to biologically relevant furans and pyrroles in good yields. Cp*=C5Me5, DCE=1,2-dichloroethane, THF=tetrahydrofuran.

    17. Surface-Enhanced Spectroscopy

      Gold Nanoparticle Capping Layers: Structure, Dynamics, and Surface Enhancement Measured Using 2D-IR Spectroscopy (pages 634–638)

      Paul M. Donaldson and Peter Hamm

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201204973

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      Surface analysis: Two-dimensional infrared spectroscopy (2D-IR) was used to probe amide and carboxylate functional groups in the vicinity of gold nanoparticles and their aggregates. The data presented shows that the unique ability of 2D-IR spectroscopy to characterize broadening mechanisms and cross peaks offers new insights into gold nanoparticle capping layer structure and dynamics (see picture).

    18. Cyclodextrin Functionalization

      An “Against the Rules” Double Bank Shot with Diisobutylaluminum Hydride To Allow Triple Functionalization of α-Cyclodextrin (pages 639–644)

      Dr. Elena Zaborova, Maxime Guitet, Dr. Giuseppe Prencipe, Prof. Yves Blériot, Dr. Mickaël Ménand and Prof. Matthieu Sollogoub

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201204974

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      Frustration leads to overreaction: When diametrically opposed regioselective debenzylation is frustrated, an unexpected double debenzylation reaction affords original tetrafunctionalized cyclodextrins in a controlled and efficient manner. A rationale of the reaction is proposed based on a kinetic study.

    19. Bimetallic Nanocrystals

      Highly Branched Concave Au/Pd Bimetallic Nanocrystals with Superior Electrocatalytic Activity and Highly Efficient SERS Enhancement (pages 645–649)

      Lin-Fei Zhang, Dr. Sheng-Liang Zhong and Prof. Dr. An-Wu Xu

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201205279

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      Superstar: Branched concave Au/Pd bimetallic nanocrystals (see picture) were synthesized in high yield by seed-mediated co-reduction of Au and Pd metal precursors in an aqueous solution at room temperature. The branches are concave and have high-index facets on their surfaces. These nanocrystals show superior electrocatalytic activity for the oxidation of ethanol and highly efficient SERS enhancement.

    20. Fluorescent Dyes

      A Common Diaryl Ether Intermediate for the Gram-Scale Synthesis of Oxazine and Xanthene Fluorophores (pages 650–654)

      Andrew V. Anzalone, Tracy Y. Wang, Zhixing Chen and Prof. Virginia W. Cornish

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201205369

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      Common ground: Copper-catalyzed coupling reactions can be used for the high-yielding preparation of widely used oxazine and xanthene fluorophores from a common diaryl ether intermediate on a gram-scale (see scheme). This general approach may facilitate the future development of novel fluorophores and probes with unique properties.

    21. Host–Guest Chemistry

      Reversible Photochemically Gated Transformation of a Hemicarcerand to a Carcerand (pages 655–659)

      Hao Wang, Fang Liu, Dr. Roger C. Helgeson and Prof. Dr. Kendall N. Houk

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201205376

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      Guests in a gated community: Introduction of two anthracene groups into a linker in a hemicarcerand creates a new type of photochemically controlled gated hemicarcerand. The reversible opening and closing of the “gate” of the host is controlled photochemically. The encapsulation and release of the guest molecules such as 1,4-dimethoxybenzene is controlled by irradiation with light of different wavelengths.

    22. Alkali-Resistant Catalysts

      A “Smart” Hollandite DeNOx Catalyst: Self-Protection against Alkali Poisoning (pages 660–664)

      Zhiwei Huang, Dr. Xiao Gu, Dr. Wen Wen, Pingping Hu, Prof. Michiel Makkee, Dr. He Lin, Prof. Freek Kapteijn and Prof. Xingfu Tang

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201205808

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      Banish the villains to their own realm: Biomass has gained widespread attention as a renewable energy source. However, commercial catalysts used in power plants (co-)fuelled by biomass are deactivated by the alkali-rich flue gas (see graph, black line). In contrast, one of two types of active sites in a promising alkali-resistant hollandite catalyst traps alkali-metal ions to free up the catalytically active sites for the reduction of NO by NH3.

    23. Protein Dynamics

      Protein Surface and Core Dynamics Show Concerted Hydration-Dependent Activation (pages 665–668)

      Dr. Kathleen Wood, Dr. François-Xavier Gallat, Dr. Renee Otten, Auke J. van Heel, Mathilde Lethier, Dr. Lambert van Eijck, Martine Moulin, Dr. Michael Haertlein, Dr. Martin Weik and Prof. Dr. Frans A. A. Mulder

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201205898

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      By specifically labeling leucine/valine methyl groups and lysine side chains “inside” and “outside” dynamics of proteins on the nanosecond timescale are compared using neutron scattering (see picture). Surprisingly, both groups display similar dynamics as a function of temperature, and the buried hydrophobic core is sensitive to hydration and undergoes a dynamical transition.

    24. Dendrimers

      Photoswitchable Conductivity in a Rigidly Dendronized Salt (pages 669–673)

      Dr. Thi-Thanh-Tam Nguyen, Dr. David Türp, Dr. Manfred Wagner and Prof. Dr. Klaus Müllen

      Version of Record online: 27 NOV 2012 | DOI: 10.1002/anie.201206010

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      Light switch: A dendronized salt exhibiting photoswitchable conductivity was designed and synthesized. The salt consists of tetrabutylammonium cations and large, rigidly dendronized borate anions, each bearing eight photoresponsive azobenzene moieties. The conductivity of solutions of this salt can be reversibly switched by irradiation, owing to light-induced changes in the overall size of the dendronized anion and the density of its polyphenylene shell.

    25. Gels

      Broad-Spectrum Antimicrobial and Biofilm-Disrupting Hydrogels: Stereocomplex-Driven Supramolecular Assemblies (pages 674–678)

      Yan Li, Dr. Kazuki Fukushima, Dr. Daniel J. Coady, Dr. Amanda C. Engler, Dr. Shaoqiong Liu, Yuan Huang, Dr. John S. Cho, Dr. Yi Guo, Dr. Lloyd S. Miller, Dr. Jeremy P. K. Tan, Dr. Pui Lai Rachel Ee, Dr. Weimin Fan, Prof. Yi Yan Yang and Dr. James L. Hedrick

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201206053

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      Fighting the resistance: Biodegradable and injectable/moldable hydrogels with hierarchical nanostructures (see picture) were made with broad-spectrum antimicrobial activities and biofilm-disruption capability. They demonstrate no cytotoxicity in vitro, and show excellent skin biocompatibility in animals. These hydrogels have great potential for clinical use in prevention and treatment of various multidrug-resistant infections.

    26. Core–Shell Structures

      Bright and Stable Alloy Core/Multishell Quantum Dots (pages 679–682)

      Dr. Shinae Jun and Dr. Eunjoo Jang

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201206333

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      Color conversion: A quantum dot (QD) structure consisting of an alloy core (CdSe//ZnS) and multishells (CdSZnS) was prepared (see picture). The photoluminescence of the QDs could be tuned especially in the green-light region by controlling the thickness of the inner CdS shell. The alloy core/multishell (AC/MS) QDs showed a quantum efficiency of 100 % and a narrow spectrum width.

    27. G-Quadruplex Folding

      Decrease in RNA Folding Cooperativity by Deliberate Population of Intermediates in RNA G-Quadruplexes (pages 683–686)

      Chun Kit Kwok, Madeline E. Sherlock and Prof. Dr. Philip C. Bevilacqua

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201206475

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      Keeping a broad (RNA) perspective: Conventional biochemical detection systems only have a 100-fold linear response range. The range of potassium concentrations detected by an RNA G-quadruplex sequence can be broadened by intentionally populating multiple intermediate folding states (see scheme). The folding of the RNA G-quadruplexes was monitored by both circular dichroism and intrinsic fluorescence spectroscopy.

    28. Dipolar Couplings of Proteins

      Direct Prediction of NMR Residual Dipolar Couplings from the Primary Sequence of Unfolded Proteins (pages 687–690)

      Dr. Jie-rong Huang, Valéry Ozenne, Dr. Malene Ringkjøbing Jensen and Dr. Martin Blackledge

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201206585

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      Conformational analysis: An approach to the prediction of RDCs from disordered protein chains, integrating the effect of nearest neighbors and the alignment characteristics of the statistical coil, is reported. NMR residual dipolar couplings (RDC) are sensitive probes of conformational sampling in unfolded proteins (see picture).

    29. Posttranslational Modifications

      Simultaneous Measurement of SUMOylation using SNAP/CLIP-Tag-Mediated Translation at the Single-Molecule Level (pages 691–694)

      Dr. Yong Yang and Prof. Dr. Chun-yang Zhang

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201206695

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      Two opposing SUMO wrestlers: Simultaneous measurement of multiple SUMOylations was achieved at the single-molecule level by integrating SNAP/CLIP-tag-mediated translation with single-molecule detection (see scheme; SUMO=small ubiquitin-like modifier). This method gives exceptional sensitivity, and is capable of measuring the SUMOylation of different proteins under various physiological conditions.

    30. Intracellular Release

      Light-Addressable Capsules as Caged Compound Matrix for Controlled Triggering of Cytosolic Reactions (pages 695–699)

      Markus Ochs, Dr. Susana Carregal-Romero, Dr. Joanna Rejman, Prof. Kevin Braeckmans, Prof. Stefaan C. De Smedt and Prof. Wolfgang J. Parak

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201206696

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      Release me: Polyelectrolyte capsules with different cargo in their cavities and plasmonic and magnetic nanoparticles in their walls were synthesized. Enzymatic reactions were triggered inside cells by light-mediated opening of two individual capsules containing either an enzyme or its substrate, by using photothermal heating. Furthermore, this technique allows controlled release of mRNA from capsules, thereby resulting in synthesis of green fluorescent protein (GFP).

    31. Water Oxidation

      Copper(II) Catalysis of Water Oxidation (pages 700–703)

      Dr. Zuofeng Chen and Prof. Thomas J. Meyer

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201207215

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      Copper leads to a breakup: Simple CuII salts are shown to be highly reactive as water oxidation electrocatalysts in neutral to weakly basic aqueous buffer solutions of CO2/HCO3/CO32− or HPO42−/PO43−. Coordination to the buffer anions under these conditions prevents the precipitation of Cu(OH)2, CuCO3, or Cu3(PO4)2 and appears to stabilize higher oxidation states of copper.

    32. Sequence-Dependent Assembly

      Sequence-Dependent Assembly to Control Molecular Interface Properties (pages 704–709)

      Graham de Ruiter, Dr. Michal Lahav, Hodaya Keisar and Prof. Milko E. van der Boom

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201207467

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      Variation's what you need: Variation of the assembly sequence in which layers of two isostructural metal complexes are built up leads to molecular materials with electrochemical properties that depend on the assembly sequence. These properties vary from reversible electron transfer to unidirectional current flows and even charge trapping. The sequence-dependent assembly strategy has implications for various disciplines that involve self-assembly.

    33. Metal–Organic Frameworks

      A Luminescent Metal–Organic Framework as a Turn-On Sensor for DMF Vapor (pages 710–713)

      Yu Li, Shanshan Zhang and Prof. Datong Song

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201207610

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      A real turn-on: A luminescent lanthanide metal–organic framework shows strong and fast turn-on responses to N,N-dimethylformamide (DMF) vapor. The selective turn-on effect is triggered mainly by DMF–ligand interactions, along with the removal of quencher, water, from the metal coordination sphere.

    34. Self-Assembly

      Nonlinear Amplification of a Supramolecular Complex at a Multivalent Interface (pages 714–719)

      Dr. Shu-Han Hsu, Dr. M. Deniz Yilmaz, Prof. Dr. David N. Reinhoudt, Prof. Dr. Aldrik H. Velders and Prof. Dr. Jurriaan Huskens

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201207647

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      Competition with a monovalent cyclodextrin host (blue cones) in solution drives the multivalent binding of a Eu3+ complex and a sensitizer molecule to cyclodextrin monolayers through a nonlinear self-assembly process. Adamantyl groups (light-blue spheres) are attached to the EDTA ligand (black) and the antenna molecule (orange), which has a carboxylate group for coordination to the Eu3+ ion (yellow or red in free or complexed form, respectively).

    35. Supramolecular Chemistry

      A Self-Assembled Multiporphyrin Cage Complex through Three Different Zinc(II) Center Formation under Well-Balanced Aqueous Conditions (pages 720–723)

      Takashi Nakamura, Dr. Hitoshi Ube, Dr. Motoo Shiro and Prof. Dr. Mitsuhiko Shionoya

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201208040

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      Construction of a self-assembled cage complex through three different ZnII centers is achieved using a Zn porphyrin ligand with four 2,2′-bipyridin-5-yl (bpy) groups. The multiporphyrin cage encapsulates guest molecules unsymmetrically by π–π interactions. Well-balanced aqueous conditions, which allow the formation of both tris(bpy) and hydrated bis(bpy) ZnII units, result in the unsymmetrical yet well-defined supramolecular structure.

    36. Hydrogenases

      Observation of the Fe[BOND]CN and Fe[BOND]CO Vibrations in the Active Site of [NiFe] Hydrogenase by Nuclear Resonance Vibrational Spectroscopy (pages 724–728)

      Dr. Saeed Kamali, Dr. Hongxin Wang, Dr. Devrani Mitra, Dr. Hideaki Ogata, Prof. Wolfgang Lubitz, Brian C. Manor, Prof. Thomas B. Rauchfuss, Dr. Deborah Byrne, Dr. Violaine Bonnefoy, Prof. Francis E. Jenney Jr., Prof. Michael W. W. Adams, Dr. Yoshitaka Yoda, Dr. Ercan Alp, Dr. Jiyong Zhao and Prof. Stephen P. Cramer

      Version of Record online: 8 NOV 2012 | DOI: 10.1002/anie.201204616

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      Nuclear inelastic scattering of 57Fe labeled [NiFe] hydrogenase is shown to give information on different states of the enzyme. It was thus possible to detect and assign Fe[BOND]CO and Fe[BOND]CN bending and stretching vibrations of the active site outside the spectral range of the Fe[BOND]S cluster normal modes.

    37. Reversible Coupling of :CO and :BR

      Reversible Intramolecular Coupling of the Terminal Borylene and a Carbonyl Ligand of [Cp(CO)2Mn[DOUBLE BOND]B[BOND]tBu] (pages 729–733)

      Prof. Dr. Holger Braunschweig, Dr. Krzysztof Radacki, Dr. Rong Shang and Dr. Christopher W. Tate

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201207017

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      Cyclic complex 2 with bridging carbonyl ligands was synthesized from a facile and reversible intermolecular carbonyl–borylene ligand coupling reaction at room temperature. Complex 2 exhibits an unprecedented coordination mode for boron–metal complexes, which is also reflected in its remarkable 11B NMR chemical shift of −57.2 ppm. Findings from spectroscopic, X-ray, and computational studies are presented, along with a proposed mechanism.

    38. Layered ammines

      The Layered Structure of [Na(NH3)4][Indenide] Containing a Square-Planar Na(NH3)4+ Cation (pages 734–738)

      Reent Michel, Tobias Nack, Roman Neufeld, Dr. Johannes M. Dieterich, Prof. Dr. Ricardo A. Mata and Prof. Dr. Dietmar Stalke

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201207082

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      It's hip to be a square! The ammines [Li(NH3)4][Ind] and [Na(NH3)4][Ind] both contain a cation coordinated by four ammonia molecules. Whereas the first shows the anticipated tetrahedral coordination, in the second the metal coordination is unexpectedly square-planar. The solvent-separated ion pair forms a rippled layer structure of alternating planar Na(NH3)4+ cations and indenyl carbanions that is attributed to NH3⋅⋅⋅π hydrogen bonds.

    39. Dendritic Oxidation Catalysts

      Dendritic Fluoroalcohols as Catalysts for Alkene Epoxidation with Hydrogen Peroxide (pages 739–743)

      Prof. Dr. Albrecht Berkessel, Jan Krämer, Dr. Florian Mummy, Dr. Jörg-M. Neudörfl and Prof. Dr. Rainer Haag

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201206003

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      Cooperativity is the key for mild catalytic epoxidation: The immobilization of fluoroalcohols on dendritic polyglycerol (by “click chemistry”) provides organocatalysts that can form multiple hydrogen bonds. The epoxidation of alkenes with aqueous hydrogen peroxide proceeds efficiently in the presence of dendritic fluoroalcohol catalysts. The supported catalysts can be separated by membrane filtration and reused.

    40. Computational Chemistry

      Model and Mechanism: N-Hydroxylation of Primary Aromatic Amines by Cytochrome P450 (pages 744–748)

      Li Ji and Prof. Dr. Gerrit Schüürmann

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201204116

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      Only one path applies: To date, five different mechanisms have been suggested for the P450-catalyzed N-hydroxylation of primary aromatic amines. Computational analysis employing density functional theory demonstrates that only the H-atom-transfer pathway, that is H abstraction from an amine N followed by a radical rebound step, on a low-spin route can contribute to the aromatic hydroxylamine formation.

    41. Artificial Membranes

      In Vitro Expressed GPCR Inserted in Polymersome Membranes for Ligand-Binding Studies (pages 749–753)

      Sylvia May, Mirjam Andreasson-Ochsner, Zhikang Fu, Ying Xiu Low , Dr. Darren Tan, Dr. Hans-Peter M. de Hoog, Dr. Sandra Ritz, Dr. Madhavan Nallani and Prof. Dr. Eva-Kathrin Sinner

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201204645

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      The dopamine receptor D2 (DRD2), a G-protein coupled receptor is expressed into PBd22-PEO13 and PMOXA20-PDMS54-PMOXA20 block copolymer vesicles (see scheme). The conformational integrity of the receptor is confirmed by antibody- and ligand-binding assays. Replacement of bound dopamine is demonstrated on surface-immobilized polymersomes, thus making this a promising platform for drug screening.

    42. Graphane

      On the Way to Graphane—Pronounced Fluorescence of Polyhydrogenated Graphene (pages 754–757)

      Ricarda A. Schäfer, Jan M. Englert, Peter Wehrfritz, Walter Bauer, Frank Hauke, Thomas Seyller and Andreas Hirsch

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201206799

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      Chemistry meets graphane: A Birch-type reaction using frozen water as a gentle proton source causes the exfoliation of graphite and formation of hydrogenated graphene with electronically decoupled π-nanodomains. This highly functionalized graphene displays pronounced fluorescence.

    43. Gold Complexes

      Gold(III)- versus Gold(I)-Induced Cyclization: Synthesis of Six-Membered Mesoionic Carbene and Acyclic (Aryl)(Heteroaryl) Carbene Complexes (pages 758–761)

      Gaël Ung, Dr. Michele Soleilhavoup and Prof. Guy Bertrand

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201207961

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      The golden state: Selective 5-exo- and 6-endo-cyclizations of an alkynyl benzothioamide have been achieved. The selectivity is controlled by the oxidation state of the gold precursor (+I or +III), yielding two new types of carbene ligand: an (aryl)(heteroaryl)carbene and a six-membered mesoionic carbene (see scheme). Mes=2,4,6-trimethylphenyl.

    44. Click Polymer Ligation

      Light-Induced Modular Ligation of Conventional RAFT Polymers (pages 762–766)

      Kim K. Oehlenschlaeger, Jan O. Mueller, Niklas B. Heine, Mathias Glassner, Dr. Nathalie K. Guimard, Dr. Guillaume Delaittre, Dr. Friedrich G. Schmidt and Prof. Dr. Christopher Barner-Kowollik

      Version of Record online: 22 OCT 2012 | DOI: 10.1002/anie.201206905

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      Making light work of RAFT conjugation: A non-activated RAFT agent at the end of RAFT polymers can readily be coupled with ortho-quinodimethanes (photoenols) in a photo-triggered Diels–Alder reaction under mild conditions without catalyst (see scheme). The method is universal and opens the door for the conjugation of a large number of RAFT-prepared polymers with photoenol-functionalized (macro)molecules. (RAFT=reversible addition-fragmentation chain transfer.)

    45. Highest Oxidation States

      The Elusive Halides VCl5, MoCl6, and ReCl6 (pages 767–769)

      Dr. Farhad Tamadon and Prof. Dr. Konrad Seppelt

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201207552

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      Vanadium pentachloride and molybdenum and rhenium hexachloride are all thermally unstable but can be prepared by metathesis from the corresponding fluorides with BCl3 at low temperatures. MoCl6 is structurally related to β-WCl6, and ReCl6 to α-WCl6. VCl5 is a dimer in the solid state (see structure; V red, Cl green).

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