Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 10

March 3, 2014

Volume 53, Issue 10

Pages 2511–2775

  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. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Copolymerization of Metal Nanoparticles: A Route to Colloidal Plasmonic Copolymers (Angew. Chem. Int. Ed. 10/2014) (page 2511)

      Prof. Kun Liu, Ariella Lukach, Kouta Sugikawa, Siyon Chung, Dr. Jemma Vickery, Dr. Heloise Therien-Aubin, Prof. Bai Yang, Prof. Michael Rubinstein and Prof. Eugenia Kumacheva

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201401078

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      The self-assembly of colloidal analogues of molecular copolymers can greatly benefit fundamental studies of molecular copolymerization and nanotechnology. In their Communication on page 2648 ff., K. Liu, E. Kumacheva, et al. present microscopy and spectroscopy analyses to develop design rules and a kinetic model for the growth of colloidal random and block copolymers made from plasmonic nanorods with different lengths and compositions.

    2. You have free access to this content
      Inside Cover: Fourier Transform EPR Spectroscopy of Trityl Radicals for Multifunctional Assessment of Chemical Microenvironment (Angew. Chem. Int. Ed. 10/2014) (page 2512)

      Dr. Andrey A. Bobko, Dr. Ilirian Dhimitruka, Prof. Dr. Jay L. Zweier and Prof. Dr. Valery V. Khramtsov

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201401080

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      The long relaxation times of the monophosphonated trityl radical make possible its application in pulsed EPR spectroscopy. In their Communication on page 2735 ff., V. V. Khramtsov et al. use Fourier transform EPR spectroscopy in combination with the trityl probe to assess the physiologically relevant parameters of a chemical microenvironment. The spectra analysis enables quantitative and discriminative assessment of pH, pO2, and the concentrations of inorganic phosphate (Pi) and probe.

    3. You have free access to this content
      Inside Back Cover: Temperature-Responsive Microgel Films as Reversible Carbon Dioxide Absorbents in Wet Environment (Angew. Chem. Int. Ed. 10/2014) (page 2777)

      Mengchen Yue, Prof. Yu Hoshino, Yukinori Ohshiro, Kazushi Imamura and Prof. Yoshiko Miura

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201401095

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      Hydrogel films composed of temperature-responsive microgel particles (GPs) containing amine groups work as stimuli-responsive carbon dioxide absorbent, as reported by Y. Hoshino and co-workers in their Communication on page 2654 ff. The reversible CO2 absorption capacity of the GP films is proportional to the film thickness and is larger than that of a monolithic gel film. This discovery shows that the GP films can be used to sequester energy-efficiently CO2 from high-humidity exhaust gases.

    4. You have free access to this content
      Back Cover: Cationic Ir/Me-BIPAM-Catalyzed Asymmetric Intramolecular Direct Hydroarylation of α-Ketoamides (Angew. Chem. Int. Ed. 10/2014) (page 2778)

      Tomohiko Shirai, Prof. Dr. Hajime Ito and Prof. Dr. Yasunori Yamamoto

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201401083

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      Asymmetric intramolecular direct hydroarylation of α-ketoamides gives various optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities. As shown by Y. Yamamoto et al. in their Communication on page 2658 ff. this reaction is realized by the use of an asymmetric cationic iridium complex formed in situ, which provides enantioselective direct addition at the more hindered ortho C[BOND]H bond to a carbonyl group.

  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. Review
    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. Review
    12. Communications
    1. You have free access to this content
      Corrigendum: A Concise Synthesis of (−)-Aplyviolene Facilitated by a Strategic Tertiary Radical Conjugate Addition (page 2527)

      Dr. Martin J. Schnermann and Prof. Larry E. Overman

      Version of Record online: 25 FEB 2014 | DOI: 10.1002/anie.201308558

      This article corrects:

      A Concise Synthesis of (−)-Aplyviolene Facilitated by a Strategic Tertiary Radical Conjugate Addition1

      Vol. 51, Issue 38, 9576–9580, Version of Record online: 24 AUG 2012

  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. Review
    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. Review
    12. Communications
    1. Dirk M. Guldi (pages 2534–2535)

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/anie.201309697

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      “My favorite time of day is sunrise. I admire spontaneity …” This and more about Dirk M. Guldi can be found on page 2534.

  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. Review
    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. Review
    12. Communications
    1. A Tale of 7 Elements. By Eric Scerri. (page 2538)

      Andrea Kästner and Johannes Kästner

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201310155

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      Oxford University Press, 2013. 304 pp., hardcover, $ 19.95.—ISBN 978-0195391312

  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. Review
    12. Communications
    1. Energetic Materials

      Metal–Organic Frameworks as High Explosives: A New Concept for Energetic Materials (pages 2540–2542)

      Dr. Qinghua Zhang and Prof. Dr. Jean'ne M. Shreeve

      Version of Record online: 4 FEB 2014 | DOI: 10.1002/anie.201310014

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      Energetic MOFs with 1D, 2D, or 3D structures were synthesized through a self-assembly strategy by using energetic organic linkers to bridge non-toxic metal ions. This new concept for energetic MOFs opens opportunities for developing new-generation primary explosives in the field of energetic materials.

    2. CO2 Activation

      Creating Added Value with a Waste: Methylation of Amines with CO2 and H2 (pages 2543–2545)

      Dr. Anis Tlili, Xavier Frogneux, Enguerrand Blondiaux and Dr. Thibault Cantat

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310337

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      Unknown before 2013, a novel methodology utilizes CO2 as a carbon source for the methylation of amines, with water as the by-product. This strategy offers a sustainable route to methylamines by converting CO2 to value-added chemicals, using molecular hydrogen as a cheap and renewable reductant. The method may open novel applications for recycling CO2 to bulk and fine chemicals.

  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. Review
    12. Communications
    1. Organic Electronics

      α-Oligofurans: An Emerging Class of Conjugated Oligomers for Organic Electronics (pages 2546–2555)

      Dr. Ori Gidron and Prof. Dr. Michael Bendikov

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/anie.201308216

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      Long and short of it: A critical account of a new class of π-conjugated materials, long oligofurans, from the perspectives of their synthesis, molecular properties, chemical reactivity, and use in electronic devices is presented.

  10. 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. Review
    12. Communications
    1. Molecules and Music

      Toward a Symphony of Reactivity: Cascades Involving Catalysis and Sigmatropic Rearrangements (pages 2556–2591)

      Prof. Amanda C. Jones, Prof. Jeremy A. May, Prof. Richmond Sarpong and Prof. Brian M. Stoltz

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201302572

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      Unfinished Symphonies: The development of tandem processes has had a profound impact on organic synthesis. In this Review, catalyzed cascade transformations that involve sigmatropic rearrangements are discussed. To appeal to the musical sense of orchestration in chemical synthesis, we propose the descriptors duet, trio, quartet, etc. for defining transformations that involve more than one reaction in a cascade.

  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. Review
    12. Communications
    1. Lipid Analysis

      Pinpointing Double Bonds in Lipids by Paternò-Büchi Reactions and Mass Spectrometry (pages 2592–2596)

      Dr. Xiaoxiao Ma and Prof. Dr. Yu Xia

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201310699

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      Where is the double bond? For the first time, the Paternò–Büchi (P-B) reaction has been exploited for double-bond localization in lipids. The P-B reaction is facilitated by UV irradiation of a nanoelectrospray plume entraining lipids and acetone. Tandem mass spectrometry of the online reaction products by collision activation leads to the rupture of oxetane rings and the formation of diagnostic ions specific to the double-bond location (see picture).

    2. Structure-Based Drug Discovery

      Structure-Based Approach To Improve a Small-Molecule Inhibitor by the Use of a Competitive Peptide Ligand (pages 2597–2601)

      Dr. Katsuki Ono, Dr. Koh Takeuchi, Hiroshi Ueda, Yasuhiro Morita, Dr. Ryuji Tanimura, Prof. Ichio Shimada and Prof. Hideo Takahashi

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201310749

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      The best of both worlds: In a structure-based strategy to improve the affinity of a small-molecule inhibitor for its target protein, the interaction mode of a competitive peptide was constructively introduced. Thus, the discrimination of overlapping and non-overlapping peptide–compound pharmacophores by INPHARMA NMR spectroscopy enabled the design of a new compound (see structure) with improved affinity for the platelet receptor glycoprotein VI.

    3. Photoresponsive Assemblies

      Photocontrol Over Self-Assembled Nanostructures of π–π Stacked Dyes Supported by the Parallel Conformer of Diarylethene (pages 2602–2606)

      Prof. Dr. Shiki Yagai, Kazunori Iwai, Mitsuaki Yamauchi, Prof. Dr. Takashi Karatsu, Prof. Dr. Akihide Kitamura, Prof. Dr. Shinobu Uemura, Prof. Dr. Masakazu Morimoto, Dr. Hao Wang and Prof. Dr. Frank Würthner

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201310773

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      Leading light: Photoresponsive dye aggregates exhibiting remarkable morphological changes were constructed through complexation of the parallel conformer of a diarylethene receptor with dimeric stacks of perylene bisimide through multiple hydrogen bonds. The aggregates can be reversibly transformed between helical nanofibers and granular nanoaggregates upon exposure to visible and UV light, respectively.

    4. Vesicle Self-Assembly

      Frame-Guided Assembly of Vesicles with Programmed Geometry and Dimensions (pages 2607–2610)

      Yuanchen Dong, Dr. Yawei Sun, Dr. Liying Wang, Dianming Wang, Tao Zhou, Prof. Dr. Zhongqiang Yang, Zhong Chen, Prof. Dr. Qiangbin Wang, Prof. Dr. Qinghua Fan and Prof. Dr. Dongsheng Liu

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/anie.201310715

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      Frame-filling: Discontinuous, pre-positioned leading hydrophobic groups (LHGs) have been introduced to a frame, outlining the fringe of its designed structure. The formed frame will guide other amphiphilic molecules to fill in the gap between LHGs, finally leading to the formation of heterovesicles with designed shape and size.

    5. Hemoprotein Engineering

      Direct meso-Alkynylation of Metalloporphyrins Through Gold Catalysis for Hemoprotein Engineering (pages 2611–2614)

      Dr. Alexander Nierth and Prof. Michael A. Marletta

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201310145

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      Golden trick: Metalloporphyrins can be directly functionalized at the methine protons (meso positions) to yield asymmetric alkynylated derivatives by using gold catalysis and hypervalent iodine reagents. This single-step procedure was applied to b-type heme and the product was incorporated into a gas-sensor heme protein. The terminal alkyne allows fluorophore labeling through copper(I)-catalyzed azide–alkyne cycloaddition.

    6. Crystal Engineering

      Crystal Engineering of an nbo Topology Metal–Organic Framework for Chemical Fixation of CO2 under Ambient Conditions (pages 2615–2619)

      Wen-Yang Gao, Yao Chen, Youhong Niu, Kia Williams, Lindsay Cash, Pastor J. Perez, Lukasz Wojtas, Prof. Jianfeng Cai, Yu-Sheng Chen and Prof. Shengqian Ma

      Version of Record online: 4 FEB 2014 | DOI: 10.1002/anie.201309778

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      High catalytic activity for chemical fixation of CO2 into cyclic carbonates under ambient conditions has been demonstrated in the metal–organic framework (MOF) MMCF-2 (see picture; C gray, O red, N blue, Cu pale blue). This MOF features a high density of well-oriented Lewis acid active sites within the cuboctahedral cage.

    7. Biosensors

      Turning Tryptophanase into Odor-Generating Biosensors (pages 2620–2622)

      Yaqin Xu, Zhuyuan Zhang, Dr. M. Monsur Ali, Joanna Sauder, Xudong Deng, Karen Giang, Sergio D. Aguirre, Prof. Dr. Robert Pelton, Prof. Dr. Yingfu Li and Prof. Dr. Carlos D. M. Filipe

      Version of Record online: 4 FEB 2014 | DOI: 10.1002/anie.201309684

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      The nose knows: Tryptophanase (TPase), which converts S-methyl-L-cysteine into methyl mercaptan (smelly), was coupled to a molecular recognition element (such as an antibody) to create an odor-based biosensor. Biotinylated TPase could be combined with various biotin-labeled molecular recognition elements, thereby enabling a broad range of applications for this odor-based reporting system.

    8. Organic Chemistry

      Potential-Driven Chirality Manifestations and Impressive Enantioselectivity by Inherently Chiral Electroactive Organic Films (pages 2623–2627)

      Prof. Francesco Sannicolò, Serena Arnaboldi, Prof. Tiziana Benincori, Dr. Valentina Bonometti, Dr. Roberto Cirilli, Prof. Lothar Dunsch, Prof. Włodzimierz Kutner, Prof. Giovanna Longhi, Prof. Patrizia R. Mussini, Dr. Monica Panigati, Prof. Marco Pierini and Dr. Simona Rizzo

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201309585

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      A jolt upon recognition: Torsion in the electroactive backbone endows poly-heterocycle films with high chiroptical activity, which is reversibly tunable by the electric potential, and outstanding enantiorecognition capability with about 100 mV between two enantiomeric ferrocenyl amino probes, in any order, in alternating sequences, and as a racemate.

    9. Organocatalysis

      Catalytic Asymmetric Tamura Cycloadditions (pages 2628–2632)

      Francesco Manoni and Prof. Stephen J. Connon

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201309297

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      Squared away: The first strategy for bringing about enantioselective Tamura reactions is reported. In the presence of a squaramide-based catalyst, enolizable anhydrides react with alkylidene oxindoles to generate spirooxindole products with excellent enantio- and diastereocontrol. The methodology is of wide scope and leads to structurally diverse products.

    10. Stiboranyl Ligands

      Anion-Controlled Switching of an X Ligand into a Z Ligand: Coordination Non-innocence of a Stiboranyl Ligand (pages 2633–2637)

      Iou-Sheng Ke, James S. Jones and Prof. Dr. François P. Gabbaï

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201309132

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      Picture of (non)innocence: A chloride–fluoride exchange reaction leads to the metamorphosis of a stiboranyl X ligand into a stiborane Z ligand. This phenomenon, which illustrates the coordination non-innocence of the antimony ligand, results from the cleavage of the covalent Sb[BOND]Pt bond of 1 and formation of a longer and weaker Pt[RIGHTWARDS ARROW]Sb interaction in 2. This structural response is accompanied by a colorimetric one.

    11. Proton-Conducting Materials

      Two-in-One: Inherent Anhydrous and Water-Assisted High Proton Conduction in a 3D Metal–Organic Framework (pages 2638–2642)

      Sanjog S. Nagarkar, Sreekuttan M. Unni, Amitosh Sharma, Dr. Sreekumar Kurungot and Dr. Sujit K. Ghosh

      Version of Record online: 16 DEC 2013 | DOI: 10.1002/anie.201309077

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      Two-in-one: A three-dimensional proton-conducting metal–organic framework (MOF) with acid–base pairs in its coordination space has been developed. Unlike other MOFs, which conduct protons either under anhydrous or under humid conditions, this compound shows high proton conductivity under both conditions.

    12. Bioanalysis

      Real-Time Monitoring of Auxin Vesicular Exocytotic Efflux from Single Plant Protoplasts by Amperometry at Microelectrodes Decorated with Nanowires (pages 2643–2647)

      Jun-Tao Liu, Liang-Sheng Hu, Yan-Ling Liu, Dr. Rong-Sheng Chen, Zhi Cheng, Shi-Jing Chen, Prof. Christian Amatore, Prof. Wei-Hua Huang and Prof. Kai-Fu Huo

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201308972

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      Auxin(IAA) efflux has been shown by recent biochemical results to be mediated by a vesicular cycling mechanism, but up to now there was no means for direct detection of IAA release from single plant cells in real-time. A novel TiC@C/Pt-QANFA micro-electrochemical sensor has high sensitivity in detection of IAA, and allows real-time monitoring and quantification of the quantal release of auxin from single plant protoplast by exocytosis.

    13. Plasmonic Copolymers

      Copolymerization of Metal Nanoparticles: A Route to Colloidal Plasmonic Copolymers (pages 2648–2653)

      Prof. Kun Liu, Ariella Lukach, Kouta Sugikawa, Siyon Chung, Dr. Jemma Vickery, Dr. Heloise Therien-Aubin, Prof. Bai Yang, Prof. Michael Rubinstein and Prof. Eugenia Kumacheva

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309718

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      Golden chains (and some palladium too): Gold nanorods with different dimensions (see picture, red and blue rods) self-assemble into random and block colloidal copolymer structures, following the principles of molecular step-growth copolymerization. This approach was extended to the co-assembly of copolymers of gold and palladium nanorods.

    14. Green Chemistry

      Temperature-Responsive Microgel Films as Reversible Carbon Dioxide Absorbents in Wet Environment (pages 2654–2657)

      Mengchen Yue, Prof. Yu Hoshino, Yukinori Ohshiro, Kazushi Imamura and Prof. Yoshiko Miura

      Version of Record online: 23 JAN 2014 | DOI: 10.1002/anie.201309758

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      Carbon dioxide capture: Hydrogel films composed of temperature-responsive microgel particles (GP) containing amine groups reversibly absorbed carbon dioxide with a high capacity in response to the thermal stimuli (30–75 °C; see picture). A fast stimulus response rate of the GP films enabled the long-range and fast diffusion of bicarbonate ions into the films.

    15. Asymmetric C[BOND]H Functionalization

      Cationic Ir/Me-BIPAM-Catalyzed Asymmetric Intramolecular Direct Hydroarylation of α-Ketoamides (pages 2658–2661)

      Tomohiko Shirai, Prof. Dr. Hajime Ito and Prof. Dr. Yasunori Yamamoto

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/anie.201400147

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      Carbon's got a brand new bond: Asymmetric intramolecular direct hydroarylation of α-ketoamides gives various optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities. This is realized by the use of an asymmetric cationic iridium complex formed in situ (see Scheme).

    16. Proteins

      Tailoring Chimeric Ligands for Studying and Biasing ErbB Receptor Family Interactions (pages 2662–2666)

      Dr. Andrew T. Krueger, Dr. Carsten Kroll, Edgar Sanchez, Prof. Linda G. Griffith and Prof. Barbara Imperiali

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201307869

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      Signal tuning: A semisynthetic strategy for efficiently incorporating tunable functionality into chimeric recombinant proteins and application to a bivalent protein ligand tool for biasing signaling in the ErbB receptor family is described. Biasing away from an EGFR-HER2 dimerization with a bivalent EGF, reduced cell motility and intraligand spacing dependence, thus demonstrating the utility of this approach for potential structure–function studies.

    17. 2D-IR Spectroscopy

      Mixed IR/Vis Two-Dimensional Spectroscopy: Chemical Exchange beyond the Vibrational Lifetime and Sub-ensemble Selective Photochemistry (pages 2667–2672)

      Dr. Luuk J. G. W. van Wilderen, Dr. Andreas T. Messmer and Prof. Dr. Jens Bredenbeck

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201305950

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      The VIPER (vibrationally promoted electronic resonance) 2D-IR experiment selects a species within a mixture according to its IR spectrum and electronically excites it. The relaxation barrier for 2D-IR exchange spectroscopy can thus be broken and chemical exchange tracked over long timescales. The photochemistry of the IR-selected species such as distinct conformers can be studied in the presence of other species with virtually identical UV/Vis spectra.

    18. Micromotors

      You have full text access to this OnlineOpen article
      Stimuli-Responsive Microjets with Reconfigurable Shape (pages 2673–2677)

      Veronika Magdanz, Georgi Stoychev, Dr. Leonid Ionov, Dr. Samuel Sanchez and Prof. Dr. Oliver. G. Schmidt

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201308610

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      Micro jet boating: Flexible thermoresponsive polymer microjets can be fabricated. These self-propelled microjets can reversibly fold and unfold in an accurate manner by applying changes in temperature to the solution in which they are immersed. This effect allows them to start and stop multiple times by controlling the radius of curvature of the microtube.

    19. Cross-Coupling

      Ligand-Controlled α- and β-Arylation of Acyclic N-Boc Amines (pages 2678–2682)

      Anthony Millet, David Dailler, Dr. Paolo Larini and Prof. Dr. Olivier Baudoin

      Version of Record online: 6 FEB 2014 | DOI: 10.1002/anie.201310904

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      All manner of control: The arylation of α-zincated acyclic Boc-protected amines was selectively performed at the α- or β-position in a ligand-controlled manner. α-Arylation occurs by direct reductive elimination of the α-palladated intermediate whereas β-arylation involves palladium migration along the alkyl chain. Boc=tert-butoxycarbonyl.

    20. C[BOND]H Functionalization

      Rhodium(II)-Catalyzed Nondirected Oxidative Alkenylation of Arenes: Arene Loading at One Equivalent (pages 2683–2686)

      Dr. Harit U. Vora, Anthony P. Silvestri, Casper J. Engelin and Prof. Dr. Jin-Quan Yu

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201310539

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      Down to one: A C[BOND]H alkenylation of simple arenes without the need for an excess amount of the arene was possible with a bimetallic RhII catalyst (see scheme). A phosphine ligand as well as a combination of the oxidants Cu(TFA)2 and V2O5 proved essential for the efficient synthesis of monoalkenylated products with good selectivity, especially for di- and trisubstituted arene substrates.

    21. Polymers

      From Syndiotactic Homopolymers to Chemically Tunable Alternating Copolymers: Highly Active Yttrium Complexes for Stereoselective Ring-Opening Polymerization of β-Malolactonates (pages 2687–2691)

      Cédric G. Jaffredo, Dr. Yulia Chapurina, Dr. Sophie M. Guillaume and Prof. Dr. Jean-François Carpentier

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/anie.201310523

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      Alternating links: The first catalyst enabling the rapid, controlled, syndioselective polymerization of β-lactones with ester side-arms is described. With this catalyst, mixtures of β-lactones having opposite configurations are linked in an alternating fashion, thus affording a straightforward approach towards a new class of variously functionalized alternating copolymers.

    22. Natural Product Synthesis

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      Total Synthesis of the Antimitotic Marine Macrolide (−)-Leiodermatolide (pages 2692–2695)

      Prof. Dr. Ian Paterson, Kenneth K.-H. Ng, Simon Williams, David C. Millican and Dr. Stephen M. Dalby

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201310164

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      Supply to meet the demand: The tubulin-targeting mechanism of action of the marine macrolide leiodermatolide makes it a novel lead for anticancer drug discovery. With the aim of ensuring a sustainable supply and enabling structure–activity-relationship studies, a convergent synthetic route based on palladium-mediated fragment assembly and macrolactonization was developed (see scheme). Boron-mediated aldol reactions set six of the nine stereocenters.

    23. Synthetic Methods

      A Cobalt-Catalyzed Alkene Hydroboration with Pinacolborane (pages 2696–2700)

      Lei Zhang, Ziqing Zuo, Dr. Xuebing Leng and Prof. Dr. Zheng Huang

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/anie.201310096

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      A PNN pincer cobalt complex (see picture) has been developed for catalytic hydroboration of alkenes with pinacolborane. The system displays high activity and functional-group compatibility and the regio- and chemoselectivity of the hydroboration of α-olefins is excellent.

    24. Heterocycles | Hot Paper

      Rapid Synthesis of Fused N-Heterocycles by Transition-Metal-Free Electrophilic Amination of Arene C[BOND]H Bonds (pages 2701–2705)

      Dr. Hongyin Gao, Dr. Qing-Long Xu, Dr. Muhammed Yousufuddin, Prof. Daniel H. Ess and Prof. László Kürti

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201309973

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      Controlled fusion: A transition-metal-free, low-temperature, and regioselective intramolecular amination of aromatic C(sp2)[BOND]H bonds provides fused N-heterocycles. This reaction is operationally simple and scalable (1–10 mmol) and the scope of substrates is wide (see scheme). Density functional calculations indicate that a stepwise electrophilic aromatic cyclization mechanism may be operative.

    25. Organozinc Reagents

      Organozinc Pivalate Reagents: Segregation, Solubility, Stabilization, and Structural Insights (pages 2706–2710)

      Dr. Alberto Hernán-Gómez, Emma Herd, Prof. Eva Hevia, Dr. Alan R. Kennedy, Prof. Dr. Paul Knochel, Prof. Dr. Konrad Koszinowski, Sophia M. Manolikakes, Prof. Robert E. Mulvey and Christoph Schnegelsberg

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201309841

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      (un)Mixing cocktails: The secret ingredient in complicated multicomponent organozinc solution mixtures is magnesium pivalate, which enhances the air stability of Zn[BOND]C bonds by cleaning up OH or O2− antagonists and capturing H2O molecules, thus making these contaminants less accessible to carry out hydrolysis.

    26. Germanium(0) Compounds

      A Coordination Compound of Ge0 Stabilized by a Diiminopyridine Ligand (pages 2711–2715)

      Terry Chu, Lee Belding, Prof. Dr. Art van der Est, Prof. Dr. Travis Dudding, Dr. Ilia Korobkov and Dr. Georgii I. Nikonov

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/anie.201309421

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      Putting the e back into Ge: A cationic GeII complex was reduced to give a complex composed of a neutral germanium atom with a tridentate diiminopyridinate ligand. The Ge0 complex was found to have a singlet ground state and partial multiple-bond character between the Ge atom and the imine nitrogen atoms according to NMR, IR, and EPR spectroscopy, as well as X-ray analysis and DFT calculations.

    27. Depolymerization

      Zinc-Catalyzed Depolymerization of End-of-Life Polysiloxanes (pages 2716–2721)

      Dr. Stephan Enthaler

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201309299

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      Reclaiming resources: Straightforward zinc-catalyzed depolymerization of a range of polysiloxanes produced difluorodimethylsilanes and 1,3-difluoro-1,1,3,3-tetramethyldisiloxanes, which are appropriate starting materials for new polymers. In the presence of simple zinc salts, extraordinary catalytic activity and selectivity were feasible at low temperature (see scheme).

    28. Cross-coupling

      Rhodium-Catalyzed C[BOND]H Alkynylation of Arenes at Room Temperature (pages 2722–2726)

      Chao Feng and Prof. Dr. Teck-Peng Loh

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201309198

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      Hot rhod: A rhodium-catalyzed, electronically reversed Sonogashira reaction between unbiased arenes and the hypervalent iodine reagent 1 proceeds through C[BOND]H activation. This reaction displays excellent functional-group tolerance and high efficiency, and thus opens a new synthetic pathway to access functionalized alkynes. Cp*=C5Me5, DCE=1,2-dichloroethane, Piv=pivaloyl, TIPS=triisopropylsilyl.

    29. Iron Carbene Chemistry

      Coupling of an N-Heterocyclic Carbene on Iron with Alkynes to Form η5-Cyclopentadienyl-Diimine Ligands (pages 2727–2729)

      Dr. Tsubasa Hatanaka, Prof. Dr. Yasuhiro Ohki and Prof. Dr. Kazuyuki Tatsumi

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201309021

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      Iron sandwich with a side of diimines: A cyclometalated N-heterocyclic carbene ligand in a half-sandwich iron complex was found to couple with alkynes, leading to a unique type of ring opening of the carbene ligand and the formation of ferrocenyl–diimine complexes.

    30. Synthetic Methods

      Direct Synthesis of 1,4-Diols from Alkenes by Iron-Catalyzed Aerobic Hydration and C[BOND]H Hydroxylation (pages 2730–2734)

      Takuma Hashimoto, Daisuke Hirose and Dr. Tsuyoshi Taniguchi

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/anie.201308675

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      One more hydroxy group: A method for the synthesis of 1,4-diols from simple alkenes has been developed. This unusual transformation entails an iron-catalyzed aerobic hydration and is achieved with convenient reagents, such as molecular oxygen. The formation of an intermediary alkoxy radical, which undergoes a [1,5] hydrogen shift, is likely to be essential for C(sp3)[BOND]H hydroxylation. Pc=phthalocyanine.

    31. EPR Spectroscopy

      Fourier Transform EPR Spectroscopy of Trityl Radicals for Multifunctional Assessment of Chemical Microenvironment (pages 2735–2738)

      Dr. Andrey A. Bobko, Dr. Ilirian Dhimitruka, Prof. Dr. Jay L. Zweier and Prof. Dr. Valery V. Khramtsov

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/anie.201310841

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      Examination of tissue by EPR: Fourier transform EPR spectroscopy using a phosphonated trityl probe (p1TAM) makes possible the concurrent measurement of four parameters of the microenvironment related to the physiology of living tissue, namely pO2, pH, and the concentrations of inorganic phosphate (Pi) and the probe (see picture). The trityl radical possesses long relaxation times.

    32. Solid-Phase ATRP

      Solid-Phase Incorporation of an ATRP Initiator for Polymer–DNA Biohybrids (pages 2739–2744)

      Saadyah E. Averick, Sourav K. Dey, Debasish Grahacharya, Krzysztof Matyjaszewski and Subha R. Das

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201308686

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      Solid-phase polymer biohybrids: An atom-transfer radical polymerization (ATRP) initiator was incorporated onto DNA or biotin using solid-phase phosphoramidite chemistry, providing well-defined (co)polymers both in solution and on solid support. MOI=molecule of interest; AGET=activators generated by electron transfer.

    33. S[BOND]F Activation

      S[BOND]F and S[BOND]C Activation of SF6 and SF5 Derivatives at Rhodium: Conversion of SF6 into H2S (pages 2745–2749)

      Lada Zámostná, Prof. Dr. Thomas Braun and Dr. Beatrice Braun

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/anie.201308254

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      Activation of the stable greenhouse gas SF6: The rhodium hydrido complex [{Rh(μ-H)(dippp)}2] effected defluorination at the sulfur atom of SF6 and organic SF5 compounds under mild conditions. The reduction of SF6 in the presence of HSiEt3 led exclusively to the thiolato complex [Rh2(μ-H)(μ-SSiEt3)(dippp)2] and FSiEt3 (see Scheme). A cyclic process was developed for the conversion of SF6 into H2S.

    34. S-F Activation

      The Activation of Sulfur Hexafluoride at Highly Reduced Low-Coordinate Nickel Dinitrogen Complexes (pages 2750–2753)

      Dipl.-Chem. Patrick Holze, Dipl.-Chem. Bettina Horn, Prof. Dr. Christian Limberg, Dipl.-Chem. Corinna Matlachowski and Dr. Stefan Mebs

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201308270

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      SF6 taken into pieces: Reduced β-diketiminate nickel species are capable of converting SF6, which is used as an inert gaseous dielectric medium for high-voltage switches, into sulfide and fluoride compounds. The fluoride product complex features an unprecedented [NiF]+ unit, where the Ni atom is only three-coordinate. The low-coordinate sulfide product exhibits an almost linear [Ni(μ-S)Ni]2+ moiety.

    35. C[BOND]H Activation

      α-MsO/TsO/Cl Ketones as Oxidized Alkyne Equivalents: Redox-Neutral Rhodium(III)-Catalyzed C[BOND]H Activation for the Synthesis of N-Heterocycles (pages 2754–2758)

      Dr. Da-Gang Yu, Francisco de Azambuja and Prof. Dr. Frank Glorius

      Version of Record online: 2 FEB 2014 | DOI: 10.1002/anie.201310272

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      Who needs alkynes? α-Halo and pseudohalo ketones (as C(sp3)-based electrophiles) are utilized as oxidized alkyne equivalents in RhIII-catalyzed redox-neutral annulations to efficiently generate diverse N-heterocycles. Owing to the mild reaction conditions, a variety of functional groups are tolerated.

    36. Molecular Dynamics

      Force–Spectrum Relations for Molecular Optical Force Probes (pages 2759–2761)

      M. Sc. Tim Stauch and Prof. Dr. Andreas Dreuw

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201309794

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      Using the force: Molecules whose symmetry decreases on deformation are studied by state-of-the-art theoretical methods. A direct quantitative relationship between their spectroscopic properties and the mechanical force acting on them is established. This result allows for the computational design of unique molecular force probes.

    37. Supramolecular Chemistry

      Chemosensing Ensembles for Monitoring Biomembrane Transport in Real Time (pages 2762–2765)

      Garima Ghale, Adrienne G. Lanctôt, Hannah T. Kreissl, Dr. Maik H. Jacob, Dr. Helge Weingart, Prof. Dr. Mathias Winterhalter and Prof. Dr. Werner M. Nau

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/anie.201309583

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      Pass and release: Direct and real-time monitoring of analyte transport through the lipid bilayer is possible by the selective co-encapsulation of a macrocycle and a fluorescent dye inside liposomes. Once the analyte passes through the membrane, the dye is displaced from the macrocycle, and can be monitored by fluorescence. Tracking the translocation of an arginine-rich peptide across a bacterial membrane protein shows the applicability of the new method.

    38. Silylones

      Experimental Charge Density Study of a Silylone (pages 2766–2770)

      Benedikt Niepötter, Dr. Regine Herbst-Irmer, Dr. Daniel Kratzert, Dr. Prinson P. Samuel, Dr. Kartik Chandra Mondal, Prof. Dr. Herbert W. Roesky, Paul Jerabek, Prof. Dr. Gernot Frenking and Prof. Dr. Dietmar Stalke

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201308609

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      Two non-bonding VSCCs found in a silylone: An experimental and theoretical charge-density study confirms the interpretation of (cAAC)2Si as a silylone to be valid. The two separated VSCCs present in the non-bonding region of the central silicon are indicative for two lone pairs. The nitrogen–carbene-carbon bond seems to have a significant double bond character, indicating a singlet state for the carbene carbon atom.

    39. Metallostructures

      Preparation of an Organometallic Molecular Square by Self-Assembly of Phosphorus-Containing Building Blocks (pages 2771–2775)

      Dr. Jennifer Malberg, Dr. Michael Bodensteiner, M.Sc. Daniel Paul, Dr. Thomas Wiegand, Prof. Dr. Hellmut Eckert and Prof. Dr. Robert Wolf

      Version of Record online: 4 FEB 2014 | DOI: 10.1002/anie.201309493

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      A square of gold: [Au{Co(P2C2tBu2)2}]4 is formed by the self-assembly of gold(I) cations and anions comprising a cobalt center sandwiched by phosphorus-containing moieties. X-ray diffraction and NMR spectroscopy investigations confirm that the metal atoms form a C4 symmetrical arrangement. The results show the potential of phospha-organometallic sandwich complexes as building blocks in supramolecular assemblies.

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