Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 7

February 10, 2014

Volume 53, Issue 7

Pages 1711–2001

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: A Mass Spectrometric Approach for Probing the Stability of Bioorganic Radicals (Angew. Chem. Int. Ed. 7/2014) (page 1711)

      Lei Tan, Hanfeng Hu, Prof. Joseph S. Francisco and Prof. Yu Xia

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201400198

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      Radical stability can be assessed by a new mass spectrometric approach proposed by L. Tan and co-workers in their Communication on page 1887 ff. The stability of carbon-centered bioorganic radicals is evaluated by a method based on the gas-phase dissociation of sulfinyl radical ions. The degree of CH2SO loss is found to be correlated with the stability of the as-formed radical species, which can be molecularly tuned by the electronic effect of the neighboring groups.

    2. You have free access to this content
      Inside Cover: Total Synthesis of (±)-Aspidophylline A (Angew. Chem. Int. Ed. 7/2014) (page 1712)

      Dr. Weiwu Ren, Dr. Qian Wang and Prof. Dr. Jieping Zhu

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201400427

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      The total synthesis of the monoterpene alkaloid aspidophylline A is described by J. Zhu and et. al. in their Communication on page 1818 ff. The concise synthetic strategy features rapid access to the pentacyclic skeleton of aspidophylline A by using intramolecular Michael additions as key steps. The strategy could potentially provide a feasible route to other congeners of the akuammiline family of alkaloids.

    3. You have free access to this content
      Inside Back Cover: Bandgap Engineering through Controlled Oxidation of Polythiophenes (Angew. Chem. Int. Ed. 7/2014) (page 2003)

      Dr. Sujun Wei, Dr. Jianlong Xia, Emma J. Dell, Yivan Jiang, Rui Song, Dr. Hyunbok Lee, Philip Rodenbough, Prof. Alejandro L. Briseno and Prof. Luis M. Campos

      Version of Record online: 23 JAN 2014 | DOI: 10.1002/anie.201400272

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      Hypofluorous acid is a potent and selective oxidizing agent that can react with thiophene-containing polymers to change their optoelectronic properties. As L. M. Campos and co-workers report in their Communication on page 1832 ff., the thiophene units are converted into nonaromatic thiophene-1,1-dioxides, thereby resulting in materials with increased electron affinity and a smaller optical bandgap. The image depicts the fast chemical transformation of the conjugated polymers.

    4. You have free access to this content
      Back Cover: Biomimetic RNA-Silencing Nanocomplexes: Overcoming Multidrug Resistance in Cancer Cells (Angew. Chem. Int. Ed. 7/2014) (page 2004)

      Dr. Zhongliang Wang, Dr. Zhe Wang, Dr. Dingbin Liu, Dr. Xuefeng Yan, Prof. Fu Wang, Prof. Gang Niu, Prof. Min Yang and Prof. Xiaoyuan Chen

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201400197

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      Synthetic RISC-mimic nanocomplexes for sequence-specific gene silencing are demonstrated by X. Chen, M. Yang, et al. in their Communication on page 1997 ff. Owing to unusual cooperative interaction among the components, the nanocomplexes, which were designed to target multidrug resistance, are able to successfully restore the sensitivity of OVCAR8/ADR cells to Pgp-transportable cytotoxic agents, and also exhibit resistance to enzymatic degradation, excellent target selectivity, and specific self-delivery.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Guinness Molecules: Identifying Lowest-Energy Structures (pages 1714–1715)

      Prof. Dr. Martin A. Suhm

      Version of Record online: 29 NOV 2013 | DOI: 10.1002/anie.201309063

      “ Which is the most stable molecular structure of the sum formula C6H12O6? Nobody really knows yet, but for sure it is not glucose. The winners—and there is just one for every reasonable sum formula—might be termed ‘Guinness molecules ’ Read more in the Editorial by Martin Suhm.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Ashraf Brik (page 1738)

      Version of Record online: 9 OCT 2013 | DOI: 10.1002/anie.201308262

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      “The worst advice I have ever been given was not to study chemistry. My favorite song is any song by Fairuz …” This and more about Ashraf Brik can be found on page 1738.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. More Dead Ends and Detours. En Route to Successful Total Synthesis. By Miguel A. Sierra, Maria C. de la Torre, and Fernando P. Cossío. (page 1740)

      Steve McKerrall and Phil Baran

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/anie.201309008

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      Wiley-VCH, Weinheim, 2013. 288 pp., softcover, € 59.00.—ISBN 978-3527329762

  8. Highlight

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. RNA Modification

      Structural Basis for Regulation of Ribosomal RNA 2′-O-Methylation (pages 1742–1744)

      Dr. Martin Hengesbach and Prof. Dr. Harald Schwalbe

      Version of Record online: 2 JAN 2014 | DOI: 10.1002/anie.201309604

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      Methods that interrogate different, yet overlapping structural-size ranges were integrated to gain high-resolution information on the Pyrococcus furiosus box C/D ribonucleoprotein complex. The new structure shows how 2′-O-methylation of RNA substrates through four active methyltransferases occurs in a strictly sequential manner.

  9. Minireview

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Functional Materials

      Integrated Antimicrobial and Nonfouling Zwitterionic Polymers (pages 1746–1754)

      Luo Mi and Prof. Shaoyi Jiang

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201304060

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      Fighting germs: Molecular design leads to zwitterionic nonfouling polymers with surface bactericidal and bulk antimicrobial functionalities (sketched in the picture). This functional versatility makes zwitterionic polymers a promising alternative and improvement to the conventional poly(ethylene glycol) (PEG) nonfouling materials.

  10. Review

    1. Top of page
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    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Nanoparticles

      Anisotropic Gold Nanoparticles: Synthesis, Properties, Applications, and Toxicity (pages 1756–1789)

      Na Li, Dr. Pengxiang Zhao and Prof. Didier Astruc

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201300441

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      Function follows form: Anisotropic gold nanoparticles (AuNPs) have attracted the interest of scientists for over a century. Research in this field has considerably accelerated since 2000 with the synthesis of numerous 1D, 2D, and 3D shapes as well as hollow AuNP structures. The synthetic modes, variety of shapes, applications, and toxicity issues of this fast-growing class of nanomaterials are reviewed here.

  11. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Iron Catalysis

      The Electronic Ground State of [Fe(CO)3(NO)]: A Spectroscopic and Theoretical Study (pages 1790–1794)

      M.Sc. Johannes E. M. N. Klein, Dr. Burkhard Miehlich, Dr. Michael S. Holzwarth, Prof. Dr. Matthias Bauer, Dipl.-Chem. Magdalena Milek, Dr. Marat M. Khusniyarov, Dr. Gerald Knizia, Prof. Dr. Hans-Joachim Werner and Prof. Dr. Bernd Plietker

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201309767

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      Even more complex: Spectroscopic and quantum chemical investigations show that the complex ferrate [Fe(CO)3(NO)] cannot be considered to be a Fe−II species, but rather is predominantly an Fe0 species, in which the metal is covalent bound to NO by two π bonds. A metal[BOND]N σ bond is not observed.

    2. Natural Products

      Structure Elucidation and Total Synthesis of Kulkenon (pages 1795–1798)

      Dipl.-Chem. Gerrit Symkenberg and Prof. Dr. Markus Kalesse

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201309386

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      Similar but not identical: The related natural products sulfangolid and kulkenon exhibit different configurations, which only became apparent by synthesizing the proposed structure and comparison with the authentic data. A combination of NOE experiments and computational conformational search identified the correct structure of kulkenon.

    3. Zinc-Catalyzed Borylation

      Zinc-Catalyzed Borylation of Primary, Secondary and Tertiary Alkyl Halides with Alkoxy Diboron Reagents at Room Temperature (pages 1799–1803)

      Dr. Shubhankar Kumar Bose, Dr. Katharina Fucke, Prof. Dr. Lei Liu, Prof. Dr. Patrick G. Steel and Prof. Dr. Todd B. Marder

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201308855

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      Coupling a la carte: A catalytic system based on a ZnII N-heterocyclic carbene precursor has been developed for the cross-coupling reaction of alkyl halides with diboron reagents (see scheme). This is a novel use of a Group 12 catalyst for C[BOND]X borylation. IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene.

    4. Homoleptic Iron Complexes

      TMEDA in Iron-Catalyzed Kumada Coupling: Amine Adduct versus Homoleptic “ate” Complex Formation (pages 1804–1808)

      Prof. Dr. Robin B. Bedford, Dr. Peter B. Brenner, Dr. Emma Carter, Paul M. Cogswell, Dr. Mairi F. Haddow, Prof. Dr. Jeremy N. Harvey, Prof. Dr. Damien M. Murphy, Joshua Nunn and Dr. Christopher H. Woodall

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201308395

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      Casting iron in catalytic roles: Chelating diamine ligands such as TMEDA are routinely used in iron-catalyzed cross-coupling reactions of aryl Grignard reagents. However, it was found that under catalytically relevant conditions, there is little evidence for their coordination to iron centers; homoleptic anionic organoiron species are produced instead.

    5. C–H Functionalization

      Pd/C as a Catalyst for Completely Regioselective C[BOND]H Functionalization of Thiophenes under Mild Conditions (pages 1809–1813)

      Dan-Tam D. Tang, Dr. Karl D. Collins, Johannes B. Ernst and Prof. Dr. Frank Glorius

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309305

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      I+ can do better! Pd/C can be used without ligands or additives to catalyze the completely C3-selective arylation of diversely substituted thiophenes and benzo[b]thiophenes under mild reaction conditions. The physical nature of the catalytic species was investigated and the mechanism was studied. Relative rate data generated in a “robustness screen” were used to design a complex substrate that undergoes highly chemoselective sequential functionalization.

    6. Natural Products Synthesis

      Total Synthesis of the Monoterpenoid Indole Alkaloid (±)-Aspidophylline A (pages 1814–1817)

      Mingxing Teng, Dr. Weiwei Zi and Prof. Dr. Dawei Ma

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201310928

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      Nice and concise: In a 15-step total synthesis of (±)-aspidophylline A (see structure), an intramolecular oxidative coupling was used to create the tetracyclic furoindoline motif, and a [Ni(cod)2]-mediated cyclization was used to install the bridging piperidine ring. The simultaneous installation of two rings of the pentacyclic natural product by oxidative coupling was key to the efficiency of the synthesis.

    7. Total Synthesis of (±)-Aspidophylline A (pages 1818–1821)

      Dr. Weiwu Ren, Dr. Qian Wang and Prof. Dr. Jieping Zhu

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/anie.201310929

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      Simplicity in complexity: In an efficient total synthesis of aspidophylline A, rapid access was gained to a fully functionalized dihydrocarbazole by the desymmetrization of a 2,2-disubstituted cyclohexane-1,3-dione (see scheme). A further key step was the intramolecular azidoalkoxylation of an enecarbamate to construct the fused furoindoline system and install an azido group. The final ring was formed by an intramolecular Michael addition.

    8. Chemoselective Coupling

      Site-Differentiated Polyboron Arenes Prepared by Direct C[BOND]H Borylation and Their Highly Selective Suzuki–Miyaura Cross-Coupling Reactions (pages 1822–1826)

      Liang Xu, Siyi Ding and Prof. Dr. Pengfei Li

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309546

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      Assembly line: The title reaction was developed for the synthesis of differentiated di- and polyboron-substituted (hetero)arenes from readily available (hetero)aryl N-methyliminodiacetic acid boronates. Subsequent chemoselective and consecutive Suzuki–Miyaura cross-coupling reactions allowed rapid, efficient, and flexible synthesis of multifunctionalized poly(hetero)arenes from simple building blocks.

    9. Synthetic Methods

      S-((Phenylsulfonyl)difluoromethyl)thiophenium Salts: Carbon-Selective Electrophilic Difluoromethylation of β-Ketoesters, β-Diketones, and Dicyanoalkylidenes (pages 1827–1831)

      Xin Wang, Guokai Liu, Dr. Xiu-Hua Xu, Naoyuki Shibata, Etsuko Tokunaga and Prof. Dr. Norio Shibata

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309875

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      S and F join forces: The title salts were designed and prepared by a triflic acid catalyzed intramolecular cyclization of ortho-ethynyl aryldifluoromethyl sulfanes. The salts 1 were efficient as electrophilic difluoromethylating reagents for introducing a CF2H group to sp3-hybridized carbon nucleophiles. Enantioselective electrophilic difluoromethylation was also investigated. DBU=1,8-diazabicyclo[5.4.0]undec-7-ene, Tf=trifluoromethanesulfonyl.

    10. Polymer Chemistry

      Bandgap Engineering through Controlled Oxidation of Polythiophenes (pages 1832–1836)

      Dr. Sujun Wei, Dr. Jianlong Xia, Emma J. Dell, Yivan Jiang, Rui Song, Dr. Hyunbok Lee, Philip Rodenbough, Prof. Alejandro L. Briseno and Prof. Luis M. Campos

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309398

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      Rusted root: Rozen's reagent (HOF⋅CH3CN) can convert polythiophenes to polythiophene-1,1-dioxides. The oxidation of thiophene-containing polymers, including telechelic polythiophenes, can be controlled with this potent, yet orthogonal reagent under mild conditions. By modulating the backbone of well-defined polymers, rather than varying the monomers, this approach provides an efficient means to tune their electronic properties.

    11. Natural Product Synthesis

      Collective Synthesis of Cladiellins Based on the Gold-Catalyzed Cascade Reaction of 1,7-Diynes (pages 1837–1840)

      Guozong Yue, Yun Zhang, Lichao Fang, Prof. Dr. Chuang-chuang Li, Prof. Dr. Tuoping Luo and Prof. Dr. Zhen Yang

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309449

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      Clad(iellins) in gold: A gold-catalyzed tandem reaction of 1,7-diynes was previously developed to construct the 6-5-bicyclic ring systems that are present in a number of natural products. This reaction was applied to realize the total synthesis of nine members of the cladiellin family. This modular and efficient approach, which is enantio- and stereoselective, could also be used for the construction of other cladiellins and their analogues.

    12. Biphenylenes

      Dihydrobiphenylenes through Ruthenium-Catalyzed [2+2+2] Cycloadditions of ortho-Alkenylarylacetylenes with Alkynes (pages 1841–1844)

      Dr. Silvia García-Rubín, Dr. Carlos González-Rodríguez, Dr. Cristina García-Yebra, Dr. Jesús A. Varela, Prof. Miguel A. Esteruelas and Prof. Carlos Saá

      Version of Record online: 17 JAN 2014 | DOI: 10.1002/anie.201309496

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      A new synthetic route to dihydrobiphenylenes involves a mild RuII-catalyzed [2+2+2] dimerization of ortho-alkenylarylacetylenes or its more versatile variant, the Ru-catalyzed [2+2+2] cycloaddition of ortho-ethynylstyrenes with alkynes. The mechanistic aspects of this [2+2+2] cycloaddition are also discussed.

    13. Bioanalysis

      Mismatches Improve the Performance of Strand-Displacement Nucleic Acid Circuits (pages 1845–1848)

      Yu Sherry Jiang, Dr. Sanchita Bhadra, Bingling Li and Andrew D. Ellington

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/anie.201307418

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      Catalytic hairpin assembly (CHA) is a useful amplification method for the detection of nucleic acids. CHA circuits, however, have been shown to execute non-specifically even in the absence of catalyst, which can make quantitation of lower input concentrations difficult. By introducing two mismatched bases into a specific domain on the circuit, the signal-to-background ratio can be improved from less than 10:1 to over 100:1.

    14. Integrated Devices

      Fiber-Based Flexible All-Solid-State Asymmetric Supercapacitors for Integrated Photodetecting System (pages 1849–1853)

      Xianfu Wang, Bin Liu, Rong Liu, Qiufan Wang, Xiaojuan Hou, Prof. Di Chen, Prof. Rongming Wang and Prof. Guozhen Shen

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201307581

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      All on a single fiber: Fiber-shaped all-solid-state asymmetric supercapacitors were prepared on Ni or Ti fibers. Furthermore, the combination of a supercapacitor and a photodetector based on graphene on carbon fibers as light-sensitive material gave a flexible integrated system on a single fiber to simultaneously realize energy storage and photodetection.

    15. Renewable Chemicals

      Hydrodeoxygenation of the Angelica Lactone Dimer, a Cellulose-Based Feedstock: Simple, High-Yield Synthesis of Branched C7–C10 Gasoline-like Hydrocarbons (pages 1854–1857)

      Prof. Mark Mascal, Dr. Saikat Dutta and Dr. Inaki Gandarias

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201308143

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      Fuel for thought: Biomass-derived levulinic acid can be converted in three simple steps via the angelica lactone dimer into branched, gasoline-range hydrocarbons in high yield by using a combination of oxophilic metal and noble metal catalysts (see scheme).

    16. Mizoroki–Heck Chemistry

      Nickel-Catalyzed Mizoroki–Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products (pages 1858–1861)

      Sarah Z. Tasker, Dr. Alicia C. Gutierrez and Prof. Timothy F. Jamison

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/anie.201308391

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      Branching out: A Ni-catalyzed Heck reaction for the preparation of 1,1-disubstituted alkenes is presented. High selectivity for the branched products is achieved with electronically unbiased aliphatic terminal olefins. Regioselectivities remain consistently high (≥19:1) throughout. TESOTf=triethylsilyl trifluoromethanesulfonate.

    17. Asymmetric Synthesis

      Catalytic Asymmetric 1,2-Addition of α-Isothiocyanato Phosphonates: Synthesis of Chiral β-Hydroxy- or β-Amino-Substituted α-Amino Phosphonic Acid Derivatives (pages 1862–1866)

      Yi-Ming Cao, Fang-Fang Shen, Fu-Ting Zhang, Jin-Long Zhang and Prof. Dr. Rui Wang

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201308514

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      Correct chirality critical: Organocatalytic asymmetric Adol-type and Mannich-type reactions of α-isothiocyanato phosphonate have been realized. Michael addition was also applicable under the same catalytic conditions. This versatile approach provides a new route for the synthesis of diverse highly optically active functionalized α-amino phosphonic acid derivatives.

    18. Synthetic Methods

      Copper-Catalyzed α-Amination of Phosphonates and Phosphine Oxides: A Direct Approach to α-Amino Phosphonic Acids and Derivatives (pages 1867–1871)

      Stacey L. McDonald and Prof. Dr. Qiu Wang

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201308890

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      A direct approach to important α-amino phosphonic acids and derivatives, by using copper-catalyzed electrophilic amination of α-phosphonate zincates using O-acylhydroxylamines, is described. This amination is the first example of C[BOND]N bond formation which directly introduces acyclic and cyclic amines to the α-position of phosphonates in one step. The reaction proceeds at room temperature with as little as 0.5 mol % of the catalyst.

    19. Polymerization Mechanisms

      Polymerization of Ethylene by Silica-Supported Dinuclear CrIII Sites through an Initiation Step Involving C[BOND]H Bond Activation (pages 1872–1876)

      Matthew P. Conley, Murielle F. Delley, Georges Siddiqi, Giuseppe Lapadula, Sébastien Norsic, Vincent Monteil, Olga V. Safonova and Christophe Copéret

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201308983

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      Three is better than two: CrIII silicates, in contrast to the CrII analogues, were found to be efficient ethylene-polymerization catalysts that initiate the reaction without a cocatalyst through the heterolytic splitting of an ethylene C[BOND]H bond across a Cr[BOND]O bond (see picture). This study provides clues about the active sites and initiation mechanism of the industrial Phillips catalyst.

    20. Click Chemistry

      Iridium-Catalyzed Intermolecular Azide–Alkyne Cycloaddition of Internal Thioalkynes under Mild Conditions (pages 1877–1880)

      Shengtao Ding, Prof. Guochen Jia and Prof. Jianwei Sun

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309855

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      Sometimes it just clicks: An iridium-catalyzed azide–alkyne cycloaddition reaction (IrAAC) of electron-rich internal alkynes is described. This reaction represents the first efficient intermolecular AAC of thioalkynes. It exhibits remarkable features, such as high efficiency and regioselectivity, mild reaction conditions, easy operation, and excellent compatibility with air and a broad spectrum of organic and aqueous solvents.

    21. Synthetic Methods

      Copper-Catalyzed Intermolecular Trifluoromethylazidation of Alkenes: Convenient Access to CF3-Containing Alkyl Azides (pages 1881–1886)

      Fei Wang, Xiaoxu Qi, Zhaoli Liang, Dr. Pinhong Chen and Prof. Dr. Guosheng Liu

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201309991

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      The title reaction proceeds with a CF3+ reagent under mild reaction conditions. This transformation presents a broad substrate scope and good functional-group tolerance. A variety of CF3-containing organoazides are directly synthesized from a wide range of olefins, including activated and unactivated alkenes. The resulting products are easily transformed into the corresponding amine derivatives.

    22. Radicals

      A Mass Spectrometric Approach for Probing the Stability of Bioorganic Radicals (pages 1887–1890)

      Lei Tan, Hanfeng Hu, Prof. Joseph S. Francisco and Prof. Yu Xia

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201310480

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      The dissociation of sulfinyl radical ions in the gas phase leads to a mass spectrometric approach to probe the stability of glycyl radical. CID=collision-induced dissociation, BDE=bond dissociation energy, RSE=radical stabilization energy.

    23. C[BOND]C Activation

      Rhodium(I)-Catalyzed Decarbonylative Spirocyclization through C[BOND]C Bond Cleavage of Benzocyclobutenones: An Efficient Approach to Functionalized Spirocycles (pages 1891–1895)

      Dr. Tao Xu, Nikolas A. Savage and Prof. Dr. Guangbin Dong

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201310149

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      All-carbon spirocenters were formed by a decarbonylative coupling of trisubstituted cyclic olefins and benzocyclobutenones through C[BOND]C activation. The metal–ligand combination of [{Rh(CO)2Cl}2] and P(C6F5)3 catalyzed this transformation most efficiently; a range of spirocyclic rings was thus synthesized in good to excellent yields.

    24. Reactive Intermediates

      Asymmetric Hydrogenation with Iridium C,N and N,P Ligand Complexes: Characterization of Dihydride Intermediates with a Coordinated Alkene (pages 1896–1900)

      Dr. Stefan Gruber and Prof. Dr. Andreas Pfaltz

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309515

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      Previously elusive iridium dihydride alkene complexes (see scheme) have been identified and characterized by NMR spectroscopy in solution. Reactivity studies indicated that these complexes are catalytically competent intermediates. Additional H2 is required to convert the catalyst-bound alkene into the hydrogenation product, supporting an IrIII/IrV cycle via an [IrIII(H)2(alkene)(H2)(L)]+ intermediate.

    25. Structure Elucidation

      Mechanism of the Asymmetric Hydrogenation of Exocyclic α,β-Unsaturated Carbonyl Compounds with an Iridium/BiphPhox Catalyst: NMR and DFT Studies (pages 1901–1905)

      Yuanyuan Liu, Prof. Ilya D. Gridnev and Prof. Wanbin Zhang

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309677

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      H in a fix: The title studies show an equilibrium of dinuclear iridium hydrides at low temperature after hydrogenation of the precatalyst. Computations of the conceivable R and S pathways allowed elucidation of the mechanism for enantioselection, thus affording computed optical yields which are consistent with the experimental values. The structure S1 features hydrogen bonding between the catalyst and the carbonyl group of the substrate.

    26. Asymmetric Synthesis

      Turning Regioselectivity into Stereoselectivity: Efficient Dual Resolution of P-Stereogenic Phosphine Oxides through Bifurcation of the Reaction Pathway of a Common Intermediate (pages 1906–1909)

      Dr. Kirill Nikitin, Dr. Kamalraj V. Rajendran, Dr. Helge Müller-Bunz and Prof. Dr. Declan G. Gilheany

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309556

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      Railroad switch: Both enantiomers of n-alkylphenyl-o-tolylphosphine oxide have been prepared from a single intermediate, which functions as a stereochemical railroad switch. Arbuzov-type collapse of the (RP)-alkoxyphosphonium chloride proceeds through C[BOND]O bond fission with retention of configuration at the phosphorus center, whereas alkaline hydrolysis leads to the SP enantiomer through P[BOND]O bond cleavage.

    27. Multicomponent Catalysis

      A Multicomponent Ni-, Zr-, and Cu-Catalyzed Strategy for Enantioselective Synthesis of Alkenyl-Substituted Quaternary Carbons (pages 1910–1914)

      Kevin P. McGrath and Prof. Amir H. Hoveyda

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309456

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      One-two-three punch: Ni-catalyzed alkyne hydroalumination, Zr-catalyzed alkyne carbometalation/acylation, and Cu-catalyzed enantioselective conjugate addition are combined for accessing acyclic organic molecules that contain an alkene-substituted quaternary carbon stereogenic center. The entire process takes less than four hours and affords products in up to 77 % overall yield and 99:1 enantiomeric ratio.

    28. Nitrogen Heterocycles

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      Ligand Bite Angle-Dependent Palladium-Catalyzed Cyclization of Propargylic Carbonates to 2-Alkynyl Azacycles or Cyclic Dienamides (pages 1915–1920)

      David S. B. Daniels, Alison S. Jones, Dr. Amber L. Thompson, Dr. Robert S. Paton and Dr. Edward A. Anderson

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309162

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      Chomp! The bite angle of bidentate phosphine ligands determined the course of the palladium-catalyzed cyclization of propargylic carbonates with sulfonamide nucleophiles. A small bite angle favored attack on the central C atom of the allenylpalladium intermediate, whereas alkynyl azacycles were formed from attack on the terminal C atom using ligands with a large bite angle.

    29. Noncovalent Interactions

      Intramolecular Interactions of a Phenyl/Perfluorophenyl Pair in the Formation of Supramolecular Nanofibers and Hydrogels (pages 1921–1927)

      Shu-Min Hsu, Yu-Chun Lin, Jui-Wen Chang, Yu-Hao Liu and Prof. Dr. Hsin-Chieh Lin

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201307500

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      Intramolecular binding: The incorporation of a phenyl/perfluorophenyl pair into the structure of a peptide hydrogelator leads to the formation of the supramolecular nanofibers. The quadrupole–dipole–quadrupole (q-d-q) interactions between the aromatic rings facilitate self-assembly. This work illustrates the importance of the structure–hydrogelation relationship and provides new insights into the design of self-assembled nanobiomaterials.

    30. Protein Modification

      One-Pot Semisynthesis of Exon 1 of the Huntingtin Protein: New Tools for Elucidating the Role of Posttranslational Modifications in the Pathogenesis of Huntington’s Disease (pages 1928–1933)

      Annalisa Ansaloni, Dr. Zhe-Ming Wang, Dr. Jae Sun Jeong, Francesco Simone Ruggeri, Prof. Dr. Giovanni Dietler and Prof. Dr. Hilal A. Lashuel

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201307510

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      Tailor-made: A one-pot semisynthetic strategy that enables the site-specific introduction of posttranslational modifications within the N terminus of exon 1 of the Huntingtin protein (Httex1) is reported. This approach was applied to generate untagged wild-type and T3-phosphorylated Httex1. Httex1 with polyQ repeats below the pathogenic threshold (Httex1-23Q) was shown to aggregate in vitro and phosphorylation at T3 slows aggregation.

    31. Polyoxotitanium Cages

      Dipole-Induced Band-Gap Reduction in an Inorganic Cage (pages 1934–1938)

      Yaokang Lv, Dr. Jun Cheng, Dr. Alexander Steiner, Prof. Lihua Gan and Prof. Dominic S. Wright

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201307721

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      Mind the gap: Band-structure calculations on a series of nano- and sub-nano sized cobalt(II)-polyoxotitanium cages reveal that the molecular dipole moment can have an unexpected effect on the band gap (see scheme; CB=conduction band, VB=valence band). This ability to decrease the band gap provides a strategy for the formation of low-band-gap cages.

    32. Reaction Mechanisms

      The Pauson–Khand Mechanism Revisited: Origin of CO in the Final Product (pages 1939–1942)

      Dr. Denis Lesage, Prof. Anne Milet, Dr. Antony Memboeuf, Jérôme Blu, Dr. Andrew E. Greene, Prof. Jean-Claude Tabet and Dr. Yves Gimbert

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201307745

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      The CO–Co connection: The existence of a commonly accepted Magnus intermediate in the Pauson–Khand reaction has been disproven through mass spectrometry experiments with 13CO. In such experiments the expected labeled cyclopentenone was not detected. Alternative reaction pathways are advanced from theoretical studies.

    33. Biosynthetic Pathways

      Biosynthesis of Streptolidine Involved Two Unexpected Intermediates Produced by a Dihydroxylase and a Cyclase through Unusual Mechanisms (pages 1943–1948)

      Dr. Chin-Yuan Chang, Syue-Yi Lyu, Dr. Yu-Chen Liu, Ning-Shian Hsu, Dr. Chih-Chung Wu, Dr. Cheng-Fong Tang, Kuan-Hung Lin, Dr. Jin-Yuan Ho, Dr. Chang-Jer Wu, Dr. Ming-Daw Tsai and Dr. Tsung-Lin Li

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201307989

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      Green label: In streptolidine biosynthesis, OrfP catalyzes the FeII-dependent double hydroxylation of L-Arg to form 1, which is undergoes a PLP-dependent cyclization reaction catalyzed by OrfR to form 2. The longstanding question of the streptolidine biosynthesis was solved by the incorporation of [13C6]-2 (green dots are 13C) into streptothricin by a feeding experiment.

    34. DNA Metalloinsertors

      Thread Insertion of a Bis(dipyridophenazine) Diruthenium Complex into the DNA Double Helix by the Extrusion of AT Base Pairs and Cross-Linking of DNA Duplexes (pages 1949–1952)

      D. Roeland Boer, Lisha Wu, Per Lincoln and Miquel Coll

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201308070

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      Pinned together by molecular rivets: The crystal structure of the complex between double-stranded DNA and the binuclear complex [μ-(11,11′-bidppz)(1,10-phenanthroline)4 Ru2]4+ (1, shown in blue; bidppz=bis(dipyridophenazine)), showed that one half of the bidppz ligand inserts into a DNA duplex, and the other half stacks onto the blunt end of a nearby DNA duplex. Two molecules of 1 with the same binding mode effectively cross-link two DNA duplexes.

    35. Molecular Switches

      An Electrochemically and Thermally Switchable Donor–Acceptor [c2]Daisy Chain Rotaxane (pages 1953–1958)

      Carson J. Bruns, Dr. Jianing Li, Dr. Marco Frasconi, Dr. Severin T. Schneebeli, Dr. Julien Iehl, Dr. Henri-Pierre Jacquot de Rouville, Prof. Samuel I. Stupp, Prof. Gregory A. Voth and Prof. J. Fraser Stoddart

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201308498

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      Flexing molecular muscles: A bistable [c2]daisy chain rotaxane, based on π-associated donor–acceptor interactions between naphthalene diimide and dioxynaphthalene recognition units, is obtained using click chemistry. A combination of experimental data and molecular dynamics simulations demonstrates that the daisy chain's extensile and contractile motions can be controlled, either by redox chemistry (a thermodynamically driven process), or by temperature (an entropy-driven process).

    36. Hydroamination

      Inorganic-Base-Mediated Hydroamination of Alkenyl Oximes for the Synthesis of Cyclic Nitrones (pages 1959–1962)

      Dr. Xingao Peng, Benny Meng Kiat Tong, Prof. Hajime Hirao and Prof. Shunsuke Chiba

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201308617

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      Basic ring building: A method for the synthesis of cyclic nitrones by using alkenyl oximes was developed based on hydroamination mediated by an inorganic base. DFT calculations for the reaction pathway suggested that this hydroamination could proceed through nucleophilic amination of the unactivated alkene by the oxime nitrogen atom, with the transition state stabilized by ionic interaction with a metal cation such as K+.

    37. Antitumor Agents

      The Prodrug Platin-A: Simultaneous Release of Cisplatin and Aspirin (pages 1963–1967)

      Dr. Rakesh K. Pathak, Sean Marrache, Joshua H. Choi, Trenton B. Berding and Prof. Dr. Shanta Dhar

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/anie.201308899

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      The prodrug Platin-A was designed to release cisplatin and aspirin to ameliorate the side effects of cisplatin. Platin-A exhibits anticancer and anti-inflammatory properties which are better than those for the combined use of cisplatin and aspirin. These findings highlight the advantages of combining anti-inflammatory treatment with chemotherapy when both the drugs are delivered as a single prodrug.

    38. Olefin Metathesis

      Broadly Applicable Z- and Diastereoselective Ring-Opening/Cross-Metathesis Catalyzed by a Dithiolate Ru Complex (pages 1968–1972)

      Ming Joo Koh, R. Kashif M. Khan, Dr. Sebastian Torker and Prof. Amir H. Hoveyda

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309430

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      Finally, the full range: For the first time, Ru-catalyzed olefin metathesis transformations with heteroaryl-substituted alkenes, 1,3-dienes, enol ethers, and allylic and homoallylic alcohols can be performed efficiently and often with >98 % Z selectivity. Hydrogen bonding with the dithiolate ligand likely facilitates ring-opening/cross-metathesis reactions of allylic alcohols.

    39. Photochemistry

      Copper Nanoparticles on Graphene Support: An Efficient Photocatalyst for Coupling of Nitroaromatics in Visible Light (pages 1973–1977)

      Dr. Xiaoning Guo, Caihong Hao, Prof. Guoqiang Jin, Prof. Dr. Huai-Yong Zhu and Prof. Dr. Xiang-Yun Guo

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309482

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      Green, light-assisted catalysis: Graphene-supported copper nanoparticles are used as photocatalysts. The photocatalysts can controllably reduce nitroaromatics to corresponding azoxy and azo compounds (see picture) under visible-light irradiation.

    40. Asymmetric Catalysis

      SpinPhox/Iridium(I)-Catalyzed Asymmetric Hydrogenation of Cyclic α-Alkylidene Carbonyl Compounds (pages 1978–1982)

      Xu Liu, Dr. Zhaobin Han, Dr. Zheng Wang and Prof. Dr. Kuiling Ding

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201309521

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      Take it for a spin: SpinPhox/IrI complexes are highly efficient and versatile in the enantioselective hydrogenation of a broad spectrum of exocyclic α,β-unsaturated carbonyl compounds, especially the challenging α-alkylidene lactam substrates with six- or seven-membered rings. The synthetic utility of the present protocol is demonstrated in the asymmetric synthesis of biologically important loxoprofen and ε-aminocaproic acid derivatives.

    41. Spin Crossover

      Synergistic Spin Transition between Spin Crossover and Spin-Peierls-like Singlet Formation in the Halogen-Bonded Molecular Hybrid System: [Fe(Iqsal)2][Ni(dmit)2]⋅CH3CN⋅H2O (pages 1983–1986)

      Kappei Fukuroi, Prof. Dr. Kazuyuki Takahashi, Prof. Dr. Tomoyuki Mochida, Dr. Takahiro Sakurai, Prof. Dr. Hitoshi Ohta, Dr. Takashi Yamamoto, Prof. Dr. Yasuaki Einaga and Prof. Dr. Hatsumi Mori

      Version of Record online: 21 JAN 2014 | DOI: 10.1002/anie.201309865

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      Something to get crossover: An FeIII complex with iodine-substituted ligands involving a paramagnetic nickel dithiolene anion shows a synergy between a spin-crossover transition and a spin-Peierls-like singlet formation. The halogen-bond interactions between the iodine and the sulfur atoms stabilized the paramagnetic state of π-spins and played a significant role in the synergistic magnetic transition between d- and π-spins.

    42. Aromaticity

      Synthesis of Triangular Tripalladium Cations as Noble-Metal Analogues of the Cyclopropenyl Cation (pages 1987–1991)

      Dr. Sébastien Blanchard, Prof. Louis Fensterbank, Geoffrey Gontard, Dr. Emmanuel Lacôte, Dr. Giovanni Maestri and Prof. Max Malacria

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/anie.201310204

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      Pd trifecta: C3-symmetric cationic triangular palladium clusters [{(SAr′)(PAr3)Pd}3]+ were prepared by activation of the C[BOND]S bond of isothioureas. These complexes are the first noble-metal analogues of the π-aromatic cyclopropenyl cation [C3H3]+.

    43. Metallaligands

      Formation, Expansion, and Interconversion of Metallarings in a Sulfur-Bridged AuICoIII Coordination System (pages 1992–1996)

      Katsuya Oji, Dr. Asako Igashira-Kamiyama, Dr. Nobuto Yoshinari and Prof. Takumi Konno

      Version of Record online: 8 JAN 2014 | DOI: 10.1002/anie.201309986

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      The eight-membered AuI2CoIII2 metallaring in [Au2Co2(D-nmp)4] (D-nmp=N-methyl-D-penicillaminate) was synthesized from [Co(D-nmp)2] and a gold(I) precursor. By treatment with [Au2(dppe)2]2+ (dppe=1,2-bis(diphenylphosphino)ethane), this metallaring could be rationally expanded to the eighteen-membered AuI4CoIII2 metallaring in [Au4Co2(dppe)2(D-nmp)4]2+ , which also accommodates a tetrahedral anion inside the ring.

    44. Biomimetics

      Biomimetic RNA-Silencing Nanocomplexes: Overcoming Multidrug Resistance in Cancer Cells (pages 1997–2001)

      Dr. Zhongliang Wang, Dr. Zhe Wang, Dr. Dingbin Liu, Dr. Xuefeng Yan, Prof. Fu Wang, Prof. Gang Niu, Prof. Min Yang and Prof. Xiaoyuan Chen

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201309985

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      RISC management: Synthetic RISC-mimic nanocomplexes have been developed for sequence-specific gene silencing. The nanocomplexes, which were designed to target multidrug resistance, were shown to effectively suppress Pgp expression and thus restore drug sensitivity in OVCAR8/ADR cells to Pgp-transportable cytotoxic agents.

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