Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 14

March 27, 2015

Volume 54, Issue 14

Pages 4127–4400

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Cover Picture: Photoinduced Postsynthetic Polymerization of a Metal–Organic Framework toward a Flexible Stand-Alone Membrane (Angew. Chem. Int. Ed. 14/2015) (page 4127)

      Yuanyuan Zhang, Dr. Xiao Feng, Haiwei Li, Yifa Chen, Jingshu Zhao, Shan Wang, Lu Wang and Prof. Dr. Bo Wang

      Article first published online: 4 MAR 2015 | DOI: 10.1002/anie.201501643

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      The processability of metal–organic frameworks presents a major challenge in their further application. In their Communication on page 4259 ff., X. Feng, Bo Wang, and co-workers introduce a photoinduced postsynthetic polymerization (PSP) strategy to covalently link crystals of metal–organic frameworks (MOFs) by polymer chains. The PSP approach is a facile and mild method to prepare flexible and stand-alone MOF-based membranes.

    2. Inside Cover: Efficient Access to Titanaaziridines by C[BOND]H Activation of N-Methylanilines at Ambient Temperature (Angew. Chem. Int. Ed. 14/2015) (page 4128)

      Manfred Manßen, Dr. Nicolai Lauterbach, Jaika Dörfler, Dr. Marc Schmidtmann, Wolfgang Saak, Prof. Dr. Sven Doye and Prof. Dr. Rüdiger Beckhaus

      Article first published online: 16 MAR 2015 | DOI: 10.1002/anie.201501994

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      Killing two birds with one stoneIn the presence of a bis(η51-pentafulvene) titanium complex, N-methylanilines undergo two bond activation reactions to directly give titanaaziridines. Based on this transformation, S. Doye, R. Beckhaus, et al. report in their Communication on page 4383 ff. the isolation and investigation of all key intermediates of the titanium-catalyzed hydroaminoalkylation of alkenes. The results represent the first experimental proof of the suggested reaction mechanism of this industrially promising reaction.

    3. Inside Back Cover: Bioinspired Therapeutic Dendrimers as Efficient Peptide Drugs Based on Supramolecular Interactions for Tumor Inhibition (Angew. Chem. Int. Ed. 14/2015) (page 4401)

      Xiao Zhang, Zhijun Zhang, Dr. Xianghui Xu, Yunkun Li, Yachao Li, Yeting Jian and Prof. Zhongwei Gu

      Article first published online: 16 MAR 2015 | DOI: 10.1002/anie.201501882

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      Bioinspired therapeutic dendrimers are the first dendritic peptide drugs that can be used for efficient tumor therapy. In their Communication on page 4289 ff., X. Xu, Z. Gu, et al. describe the significant supramolecular interactions between the therapeutic dendrimers and nucleic acids via the tryptophan residues. Furthermore, it is shown that the therapeutic dendrimers are efficient antitumor agents both in vitro and in vivo.

    4. Back Cover: Polymeric Micelle Assembly with Inorganic Nanosheets for Construction of Mesoporous Architectures with Crystallized Walls (Angew. Chem. Int. Ed. 14/2015) (page 4402)

      Dr. Bishnu Prasad Bastakoti, Yunqi Li, Dr. Masataka Imura, Prof. Nobuyoshi Miyamoto, Prof. Teruyuki Nakato, Prof. Takayoshi Sasaki and Prof. Yusuke Yamauchi

      Article first published online: 9 MAR 2015 | DOI: 10.1002/anie.201501642

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      Mesoporous architectures were synthesized through assembly of polymeric micelles with crystalline inorganic nanosheets. In their Communication on page 4222 ff., Y. Yamauchi et al. show that the electrostatic interactions between negatively charged nanosheeets and positively charged polymeric micelles lead to the formation of composite micelles. Removal of the micelles by calcination results in mesoporous oxides with the original crystalline structure.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Frontispiece: A Separation-Integrated Cascade Reaction to Overcome Thermodynamic Limitations in Rare-Sugar Synthesis

      Nina Wagner, Andreas Bosshart, Jurek Failmezger, Dr. Matthias Bechtold and Prof. Sven Panke

      Article first published online: 24 MAR 2015 | DOI: 10.1002/anie.201581461

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      Biocatalysis S. Panke et al. describe in their Communication on page 4182 ff. how integration of continuous chromatography into a multienzyme cascade reaction allows thermodynamic constraints to be overcome to form pure D-psicose from sucrose in high yield.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Varinder K. Aggarwal (pages 4150–4151)

      Article first published online: 10 NOV 2014 | DOI: 10.1002/anie.201409950

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      “My favorite author (fiction) is V. S. Naipaul (A House for Mr. Biswas). I would have liked to have discovered the zipper—brilliant, flexible, versatile, and essential. Simple, yet intricate …” This and more about Varinder K. Aggarwal can be found on page 4150.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Understanding Organometallic Reaction Mechanisms and Catalysis: Computational and Experimental Tools. Edited by Valentin P. Ananikov (page 4154)

      Peter H. M. Budzelaar

      Article first published online: 12 MAR 2015 | DOI: 10.1002/anie.201501206

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      Wiley-VCH, Weinheim 2014. 400 pp., hardcover, €138.—ISBN 978-3527335626

  8. Highlight

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

      A New Class of Enzymes Discovered: A Non-Heme Oxidase Produces Medium-Chain 1-Alkenes (pages 4156–4158)

      Jun.-Prof. Dr. Robert Kourist

      Article first published online: 16 FEB 2015 | DOI: 10.1002/anie.201500466

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      The recently discovered non-heme oxidase UndA catalyzes the conversion of lauric acid into 1-undecene. For the discovery, an impressive number of 6000 bacterial clones bearing a genome library of Pseudomonas fluorescens had to be screened by gas chromatography. The discovery of UndA is a breakthrough, as it paves the way towards the biotechnological production of medium-chain 1-alkenes from renewable materials.

  9. Review

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

      Bioactive Glasses—Structure and Properties (pages 4160–4181)

      Jun.-Prof. Dr. Delia S. Brauer

      Article first published online: 12 MAR 2015 | DOI: 10.1002/anie.201405310

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      Boning up: Bioactive glasses are successfully used for bone regeneration, as they bond to bone, degrade over time, release ions, and stimulate bone healing. This Review discusses how the glass structure controls their properties, and shows how a structure-based design may pave the way towards new bioactive glass implants for bone regeneration.

  10. Communications

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

      A Separation-Integrated Cascade Reaction to Overcome Thermodynamic Limitations in Rare-Sugar Synthesis (pages 4182–4186)

      Nina Wagner, Andreas Bosshart, Jurek Failmezger, Dr. Matthias Bechtold and Prof. Sven Panke

      Article first published online: 16 FEB 2015 | DOI: 10.1002/anie.201411279

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      Bed of sugars: A multienzyme cascade reaction was integrated with continuous chromatography, realized as simulated moving-bed chromatography to overcome an intrinsic yield limitation. Efficient production in a three-step cascade reaction yielded pure D-psicose from sucrose with high yields and high enzyme efficiency.

    2. Supramolecular Chemistry

      You have full text access to this OnlineOpen article
      Reversible Control of Nanoparticle Functionalization and Physicochemical Properties by Dynamic Covalent Exchange (pages 4187–4191)

      Flavio della Sala and Dr. Euan R. Kay

      Article first published online: 14 JAN 2015 | DOI: 10.1002/anie.201409602

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      Ligand swap shop: Dynamic covalent hydrazone exchange within a homogeneous monolayer bound to the surface of gold nanoparticles is tracked in real time. The introduction of appropriately functionalized aldehyde exchange units allows reversible tuning of nanoparticle solvophilicity and presents a generalizable covalent approach to postsynthetic modification of nanoparticle functionalization and properties.

    3. Dynamic Combinatorial Chemistry

      Localized Template-Driven Functionalization of Nanoparticles by Dynamic Combinatorial Chemistry (pages 4192–4197)

      Piotr Nowak, Dr. Vittorio Saggiomo, Dr. Fatemeh Salehian, Mathieu Colomb-Delsuc, Dr. Yang Han and Prof. Dr. Sijbren Otto

      Article first published online: 6 FEB 2015 | DOI: 10.1002/anie.201409667

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      On target: By combining imine-based dynamic combinatorial chemistry and DNA templates, amines capable of interacting with the target were grafted on aldehyde-functionalized nanoparticles only if and where the nanoparticles (NPs) interacted with the templates. The method opens up new opportunities for synthesizing multivalent, nanoparticle-based receptors for biomacromolecules.

    4. Oxidative Cross-Coupling

      Significant Enhancement in the Efficiency and Selectivity of Iron-Catalyzed Oxidative Cross-Coupling of Phenols by Fluoroalcohols (pages 4198–4202)

      Eden Gaster, Yulia Vainer, Almog Regev, Dr. Sachin Narute, Dr. Kavitha Sudheendran, Aviya Werbeloff, Hadas Shalit and Dr. Doron Pappo

      Article first published online: 5 FEB 2015 | DOI: 10.1002/anie.201409694

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      Not just a solvent: The use of fluorinated solvents leads to a significant rate acceleration and enhancement of the chemoselectivity of the iron-catalyzed oxidative coupling of phenols. This method was used for the synthesis of 2′′′-dehydroxycalodenin B.

    5. Nanostructures

      Metal Redox Processes for the Controlled Synthesis of Metal Alloy Nanoparticles (pages 4203–4207)

      Alec Kirkeminde, Stan Spurlin, Laura Draxler-Sixta, Jamie Cooper and Prof. Shenqiang Ren

      Article first published online: 4 FEB 2015 | DOI: 10.1002/anie.201411460

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      A metal redox method makes use of spontaneous oxidation–reduction processes to grow a variety of nanocrystalline alloys from zerovalent metal precursors and salts of a suitable second metal in an oxidized state. The compositional stoichiometry of the final nanoparticles can be controlled by adjusting the temperature of the alloying reactions.

    6. Biomimetic Catalysis

      A TEMPO-Free Copper-Catalyzed Aerobic Oxidation of Alcohols (pages 4208–4211)

      Boran Xu, Prof. Jean-Philip Lumb and Prof. Bruce A. Arndtsen

      Article first published online: 10 FEB 2015 | DOI: 10.1002/anie.201411483

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      That's (non)radical: The employment of a tyrosinase-based biomimetic catalyst led to the efficient oxidation of various alcohols (including secondary aliphatic ones) at ambient temperature, without the use of a radical co-oxidant. The unique catalyst system provides complementary selectivity to previously described Cu-based systems. DMAP=dimethylaminopyridine.

    7. N-Heterocyclic Carbenes

      Generating and Trapping Metalla-N-Heterocyclic Carbenes (pages 4212–4216)

      Prof. Javier Ruiz, Lucía García, Dr. Marilín Vivanco, Ángela Berros and Dr. Juan Francisco Van der Maelen

      Article first published online: 5 FEB 2015 | DOI: 10.1002/anie.201411647

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      Caught in a trap: Metalla-imidazolium salts have been prepared and are used in the generation of highly nucleophilic singlet metalla-N-heterocyclic carbenes (MNHCs). MNHCs were trapped by addition of transition-metal fragments, such as CuCl. [Mn]=[Mn(bipy)(CO)2]; LiHDMS=lithium hexamethyldisilazide.

    8. Structure–Property Relationships

      Tailored Synthesis of a Nonlinear Optical Phosphate with a Short Absorption Edge (pages 4217–4221)

      Dr. Sangen Zhao, Pifu Gong, Dr. Siyang Luo, Dr. Lei Bai, Prof. Zheshuai Lin, Yuanyuan Tang, Yuelan Zhou, Prof. Maochun Hong and Prof. Junhua Luo

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201411772

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      Next generation: A deep-UV nonlinear optical material Ba5P6O20 based on flexible [P3O10]5− building units has been synthesized. Ba5P6O20 inherits the structural features of Ba3P3O10Cl, one of the first deep-UV NLO phosphates, but exhibits a markedly shortened absorption edge of λ=167 nm.

    9. Mesoporous Materials | Hot Paper

      Polymeric Micelle Assembly with Inorganic Nanosheets for Construction of Mesoporous Architectures with Crystallized Walls (pages 4222–4225)

      Dr. Bishnu Prasad Bastakoti, Yunqi Li, Dr. Masataka Imura, Prof. Nobuyoshi Miyamoto, Prof. Teruyuki Nakato, Prof. Takayoshi Sasaki and Prof. Yusuke Yamauchi

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201410942

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      Mesoporous architectures were obtained through evaporation-induced assembly of polymeric micelles with crystalline nanosheets. The electrostatic interactions between negatively charged nanosheets and positively charged polymeric micelles make possible the formation of composite micelles. Removal of the micelles by calcination results in mesoporous oxides with the original crystalline structure.

    10. Biocatalysis

      Directed Evolution of RebH for Site-Selective Halogenation of Large Biologically Active Molecules (pages 4226–4230)

      James T. Payne, Dr. Catherine B. Poor and Prof. Jared C. Lewis

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201411901

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      Halogenase variants capable of site-selective halogenation of large biologically active compounds (e.g., 24) were obtained through directed evolution. The substrate scope of the halogenase RebH is limited primarily to compounds similar in size to tryptophan (1). RebH was engineered to accept a range of large indoles and carbazoles, including tryptoline (2), yohimbine (4), and carvedilol, with levels of conversion sufficient for preparative-scale reactions.

    11. Charge Transport

      Multichannel Conductance of Folded Single-Molecule Wires Aided by Through-Space Conjugation (pages 4231–4235)

      Long Chen, Ya-Hao Wang, Bairong He, Han Nie, Dr. Rongrong Hu, Prof. Fei Huang, Prof. Anjun Qin, Dr. Xiao-Shun Zhou, Prof. Zujin Zhao and Prof. Ben Zhong Tang

      Article first published online: 18 FEB 2015 | DOI: 10.1002/anie.201411909

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      Single-molecule junctions with simultaneous through-bond and trough-space conducting channels are achieved based on the folded molecules that contain a pair of π–π stacked biphenyls. They were investigated by the scanning tunneling microscope based break-junction technique and theoretical calculations.

    12. Oxa-Michael Additions

      A Metal–Ligand Cooperative Pathway for Intermolecular Oxa-Michael Additions to Unsaturated Nitriles (pages 4236–4240)

      Sébastien Perdriau, Douwe S. Zijlstra, Prof. Dr. Hero J. Heeres, Prof. Dr. Johannes G. de Vries and Dr. Edwin Otten

      Article first published online: 6 FEB 2015 | DOI: 10.1002/anie.201412110

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      It all adds up: A novel pathway for oxa-Michael addition to challenging β-substituted unsaturated nitrile substrates is described based on a dearomatized ruthenium PNN pincer catalyst (see picture). Metal–ligand cooperative activation of the nitrile is key to the observed reactivity.

    13. Synthetic Methods

      Access to Nitriles from Aldehydes Mediated by an Oxoammonium Salt (pages 4241–4245)

      Christopher B. Kelly, Kyle M. Lambert, Michael A. Mercadante, John M. Ovian, Prof. William F. Bailey and Prof. Nicholas E. Leadbeater

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201412256

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      A serendipitous find: The scalable and high yielding title reaction is mediated by 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate and hexamethyldisilazane (HMDS). The reaction likely involves reversible silyl-imine formation between HMDS and an aldehyde, and subsequent oxidation and desilylation. The spent oxidant can be easily recycled.

    14. Photoredox Catalysis

      Efficient Cu-catalyzed Atom Transfer Radical Addition Reactions of Fluoroalkylsulfonyl Chlorides with Electron-deficient Alkenes Induced by Visible Light (pages 4246–4249)

      Dr. Xiao-Jun Tang and Prof. Dr. William R. Dolbier Jr.

      Article first published online: 18 FEB 2015 | DOI: 10.1002/anie.201412199

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      Fluorinated radicals are generated under Cu catalysis from RfSO2Cl. They are used for atom transfer radical addition reactions with electron-deficient alkenes such as α,β-unsaturated ketones, amides, esters, carboxylic acids, sulfone, and phosphonate. ISET=inner single electron transfer.

    15. Nanowires | Very Important Paper

      Flow-Enabled Self-Assembly of Large-Scale Aligned Nanowires (pages 4250–4254)

      Bo Li, Chuchu Zhang, Beibei Jiang, Dr. Wei Han and Prof. Zhiqun Lin

      Article first published online: 16 FEB 2015 | DOI: 10.1002/anie.201412388

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      Metallic nanowires are obtained by using highly oriented DNA nanowires as templates. A swelling-induced transfer printing technique is employed to transfer the ultralong DNA nanowires onto a desirable substrate; metallic nanowires are then generated by exposing the DNA nanowires preloaded with metal salts to an oxygen plasma.

    16. Yttrium–Arsenic Complexes

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      Yttrium Complexes of Arsine, Arsenide, and Arsinidene Ligands (pages 4255–4258)

      Dr. Thomas Pugh, Dr. Andrew Kerridge and Dr. Richard A. Layfield

      Article first published online: 5 FEB 2015 | DOI: 10.1002/anie.201500173

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      As to why: Deprotonation of the yttrium–arsine complex [Cp′3YAs(H)2Mes] (Cp′=η5-C5H4Me, Mes=mesityl) yields the μ-arsenide complex [{Cp′2Y[μ-As(H)Mes]}3]. Deprotonation of the arsenide complex by nBuLi produces [Li(thf)4]2[{Cp′2Y(μ-AsMes)}3Li], which contains the first example of an arsinidene ligand in rare-earth metal chemistry. The structures and bonding characteristic of each complex are described.

    17. Metal–Organic Frameworks | Hot Paper

      Photoinduced Postsynthetic Polymerization of a Metal–Organic Framework toward a Flexible Stand-Alone Membrane (pages 4259–4263)

      Yuanyuan Zhang, Dr. Xiao Feng, Haiwei Li, Yifa Chen, Jingshu Zhao, Shan Wang, Lu Wang and Prof. Dr. Bo Wang

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201500207

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      Link-up: A UV-light-induced postsynthetic polymerization (PSP) was employed to covalently link crystals of metal–organic frameworks (MOFs) by flexible polymer chains. The obtained MOF-based membranes are homogeneously structured and show very good separation capacities for the removal of CrVI ions from water.

    18. Asymmetric Catalysis

      Ferrocene-Based Planar Chiral Imidazopyridinium Salts for Catalysis (pages 4264–4268)

      Dr. Christopher T. Check, Dr. Ki Po Jang, C. Benjamin Schwamb, Alexander S. Wong, Michael H. Wang and Prof. Dr. Karl A. Scheidt

      Article first published online: 23 JAN 2015 | DOI: 10.1002/anie.201410118

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      Planar chiral azolium salts that incorporate a sterically demanding iron sandwich complex are synthesized. These new N-heterocyclic carbenes can be employed both as organocatalysts and as ligands for transition-metal catalysis, which demonstrates their unprecedented versatility and potential broad utility in asymmetric catalysis.

    19. Sulfur Atom Transfer

      Metal-Catalyzed “On-Demand” Production of Carbonyl Sulfide from Carbon Monoxide and Elemental Sulfur (pages 4269–4273)

      Wesley S. Farrell, Peter Y. Zavalij and Prof. Lawrence R. Sita

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201410353

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      BeCOS: Carbonyl sulfide (COS) is conveniently generated in situ in high yield and chemical purity directly from CO and S8 in solution and under near-ambient conditions upon photolysis of the precatalyst [Cp*Mo{N(iPr)C(Ph)N(iPr)}(CO)2]. The tolerance of this catalytic process to protic substrates supports the facile synthesis of more complex organic products through the “on-demand” production of COS.

    20. Host–Guest Systems

      Sensing Remote Chirality: Stereochemical Determination of β-, γ-, and δ-Chiral Carboxylic Acids (pages 4274–4278)

      Prof. Dr. Marina Tanasova, Dr. Mercy Anyika and Prof. Dr. Babak Borhan

      Article first published online: 12 FEB 2015 | DOI: 10.1002/anie.201410371

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      Binding of bis(porphyrin) tweezers to β-, γ-, or δ-chiral carboxylic amides yields chiral helical complexes which generate a bisignate Cotton Effect (ECCD) to enable the unambiguous determination of the chirality for remote stereocenters. The sign of the observed ECCD curve can be related to the absolute stereochemistry of the bound chiral substrate in a predictable manner.

    21. Imaging Agents | Hot Paper

      Spatially Resolved Quantification of Gadolinium(III)-Based Magnetic Resonance Agents in Tissue by MALDI Imaging Mass Spectrometry after In Vivo MRI (pages 4279–4283)

      Dr. Michaela Aichler, Katharina Huber, Dr. Franz Schilling, Dr. Fabian Lohöfer, Dr. Katja Kosanke, Dr. Reinhard Meier, Prof.Dr. Ernst J. Rummeny, Prof. Dr. Axel Walch and Dr. Moritz Wildgruber

      Article first published online: 16 FEB 2015 | DOI: 10.1002/anie.201410555

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      Contrast agents: As a consequence of nonlinear correlation between the contrast agent concentration in tissue and the MRI signal obtained in vivo, quantification of certain biological or pathophysiological processes by MRI remains a challenge. MALDI imaging is a valuable tool for corroborating the in vivo imaging MRI signals. This method enabled in situ quantification of the contrast agent directly in tissue with high spatial resolution.

    22. Biocatalysis

      You have full text access to this OnlineOpen article
      Combinatorial Library Based Engineering of Candida antarctica Lipase A for Enantioselective Transacylation of sec-Alcohols in Organic Solvent (pages 4284–4288)

      Ylva Wikmark, Dr. Maria Svedendahl Humble and Prof. Jan-E. Bäckvall

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201410675

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      Try the library: A method is reported for screening lipase libraries for the enantioselective transacylation of sec-alcohols in organic solvents. This could be useful for creating enantioselective lipase variants for synthetic applications such as the dynamic kinetic resolution of alcohols and amines. The method could also be applied to other His6-tagged enzymes and other reactions.

    23. Peptide Drugs

      Bioinspired Therapeutic Dendrimers as Efficient Peptide Drugs Based on Supramolecular Interactions for Tumor Inhibition (pages 4289–4294)

      Xiao Zhang, Zhijun Zhang, Dr. Xianghui Xu, Yunkun Li, Yachao Li, Yeting Jian and Prof. Zhongwei Gu

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201500683

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      Tryptophan-rich peptide dendrimers (TRPDs) with a precise molecular structure were developed as a new type of dendritic peptide drug for efficient tumor therapy. The significant supramolecular interactions between the therapeutic dendrimers and DNA were extensively studied, and experimental results indicate that TRPDs are efficient antitumor agents both in vitro and in vivo.

    24. Medium-Ring Compounds

      Structure and Reactivity of an Isolable Seven-Membered-Ring trans-Alkene (pages 4295–4298)

      Brisa Hurlocker, Dr. Chunhua Hu and Prof. K. A. Woerpel

      Article first published online: 5 FEB 2015 | DOI: 10.1002/anie.201410752

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      Feeling the strain: A seven-membered-ring trans-alkene was isolated in 72 % yield from a one-flask, two-step reaction. X-ray crystallographic analysis shows that the double bond is twisted out of coplanarity by 54°, and the C atoms are pyramidalized by 31° from the ideal trigonal-planar geometry. Hyperconjugative interactions with the C[BOND]Si bond and the proximity of the O atom to the double bond are consistent with the observed reactivity.

    25. Li–O2 Batteries

      Three Dimensionally Ordered Mesoporous Carbon as a Stable, High-Performance Li–O2 Battery Cathode (pages 4299–4303)

      Jin Xie, Xiahui Yao, Qingmei Cheng, Ian P. Madden, Paul Dornath, Chun-Chih Chang, Prof. Dr. Wei Fan and Prof. Dr. Dunwei Wang

      Article first published online: 10 FEB 2015 | DOI: 10.1002/anie.201410786

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      Concealed: To address the issue of carbon-support instability in Li–O2 batteries, a layer of FeOx grown on the carbon surface by atomic layer deposition (ALD) is used to physically separate a three dimensionally ordered mesoporous carbon support from the electrolyte. When the FeOx surface is decorated with ALD-grown Pd nanoparticles, the cyclability of the cathode is significantly enhanced.

    26. Photonic Patterns

      Photonic Patterns Printed in Chiral Nematic Mesoporous Resins (pages 4304–4308)

      Dr. Mostofa K. Khan, Anas Bsoul, Prof. Konrad Walus, Dr. Wadood Y. Hamad and Prof. Mark J. MacLachlan

      Article first published online: 12 FEB 2015 | DOI: 10.1002/anie.201410411

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      Printing photonic patterns made easy: Using chemical “inks”, latent photonic patterns were written onto chiral nematic mesoporous-resin films. The patterns are invisible in the dry films, but emerge upon swelling. Inkjet printing of the resin films afforded high-resolution photonic patterns that can be revealed upon swelling and erased by drying, making them suitable for anti-counterfeiting applications.

    27. Surface Chirality

      Remote Chiral Communication in Coadsorber-Induced Enantioselective 2D Supramolecular Assembly at a Liquid/Solid Interface (pages 4309–4314)

      Dr. Ting Chen, Shu-Ying Li, Prof. Dong Wang, Prof. Man Yao and Prof. Li-Jun Wan

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201410927

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      Getting the message across: The transmission of stereochemical information through a long flexible spacer of up to five methylene groups and noncovalent hydrogen bonds was observed in 2D supramolecular assembly at a liquid/solid interface. The confinement effect during 2D crystallization and specific noncovalent interactions between the chiral coadsorber and the achiral building blocks play an important role in efficient chiral communication.

    28. RNA Detection

      Highly Sensitive and Robust Linear Probe for Detection of mRNA in Cells (pages 4315–4319)

      Prof. Dr. Hiroyuki Asanuma, Mariko Akahane, Rie Niwa, Dr. Hiromu Kashida and Dr. Yukiko Kamiya

      Article first published online: 17 FEB 2015 | DOI: 10.1002/anie.201411000

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      A linear probe robustly detects mRNA in cells with high sensitivity. The probe was modified with base surrogates prepared from D-threoninol, with anthraquinone moieties near the 5′- and 3′-termini, and with perylene moieties. In cells, a probe designed to target DsRed resulted in distinct blue fluorescence only in cells transfected with plasmid encoding DsRed.

    29. Perfluoroalkylation

      Heterogeneous Platinum-Catalyzed C[BOND]H Perfluoroalkylation of Arenes and Heteroarenes (pages 4320–4324)

      Dr. Lin He, Dr. Kishore Natte, Dr. Jabor Rabeah, Dr. Christoph Taeschler, Dr. Helfried Neumann, Prof. Dr. Angelika Brückner and Prof. Dr. Matthias Beller

      Article first published online: 10 FEB 2015 | DOI: 10.1002/anie.201411066

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      Platinum level: The efficient and versatile title reaction is based on the radical reactivity of perfluoroalkyl halides. The ready availability of the starting materials, the excellent substrate tolerance, and the reusability of catalyst make this protocol attractive for the economic synthesis of perfluoroalkyl-group-substituted aromatic compounds.

    30. Electrochemistry | Very Important Paper

      Strong Lithium Polysulfide Chemisorption on Electroactive Sites of Nitrogen-Doped Carbon Composites For High-Performance Lithium–Sulfur Battery Cathodes (pages 4325–4329)

      Dr. Jiangxuan Song, Mikhail L. Gordin, Dr. Terrence Xu, Shuru Chen, Zhaoxin Yu, Dr. Hiesang Sohn, Dr. Jun Lu, Dr. Yang Ren, Dr. Yuhua Duan and Prof. Donghai Wang

      Article first published online: 6 FEB 2015 | DOI: 10.1002/anie.201411109

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      A composite that consists of carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres (MNCS/CNT) can strongly chemisorb polysulfides and was used as a cathode material for lithium–sulfur batteries. Moreover, the highly conductive nitrogen-doped carbon material enables direct and easy redox reactions of the adsorbed polysulfides, which leads to good electrode kinetics.

    31. Supramolecular Chemistry

      High-Contrast Red–Green–Blue Tricolor Fluorescence Switching in Bicomponent Molecular Film (pages 4330–4333)

      Hyeong-Ju Kim, Dr. Dong Ryeol Whang, Dr. Johannes Gierschner, Chong Han Lee and Prof. Soo Young Park

      Article first published online: 6 FEB 2015 | DOI: 10.1002/anie.201411568

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      Reversible red–green–blue luminescence switching with a high ratiometric color contrast (λem=594, 527, 458 nm for red, green, and blue, respectively) was realized by different external stimuli such as heat, solvent-vapor exposure, and mechanical force. It was shown that Förster resonance energy transfer in a bicomponent mixture could be efficiently switched on and off through supramolecular control.

    32. Asymmetric Catalysis

      Cation-Triggered Switchable Asymmetric Catalysis with Chiral Aza-CrownPhos (pages 4334–4337)

      Guang-Hui Ouyang, Yan-Mei He, Yong Li, Jun-Feng Xiang and Prof. Dr. Qing-Hua Fan

      Article first published online: 11 FEB 2015 | DOI: 10.1002/anie.201411593

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      Quick on the trigger: A new kind of phosphoramidite ligand, modified by an aza-crown ether, has been designed and synthesized. The activity of its rhodium catalyst can be reversibly switched “ON” and “OFF” in the asymmetric hydrogenation of dehydroamino acid esters by modulations derived from host–guest interactions.

    33. Electrocatalysis

      Recycling Application of Li–MnO2 Batteries as Rechargeable Lithium–Air Batteries (pages 4338–4343)

      Yuxiang Hu, Tianran Zhang, Fangyi Cheng, Qing Zhao, Xiaopeng Han and Jun Chen

      Article first published online: 11 FEB 2015 | DOI: 10.1002/anie.201411626

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      Never say die: Depleted Li–MnO2 batteries could be further utilized as rechargeable Li–O2 batteries with admitted oxygen. Thus, when the manganese oxide electrode was lithiated in situ and exposed to air (see picture), the resulting battery showed superior performance, including high capacity, a low overpotential, high rate capability, and high cycling stability.

    34. Polarizing CH–π bonds

      Modulating Weak Interactions for Molecular Recognition: A Dynamic Combinatorial Analysis for Assessing the Contribution of Electrostatics to the Stability of CH–π Bonds in Water (pages 4344–4348)

      Ester Jiménez-Moreno, Dr. Ana M. Gómez, Dr. Agatha Bastida, Dr. Francisco Corzana, Dr. Gonzalo Jiménez-Oses, Dr. Jesús Jiménez-Barbero and Dr. Juan Luis Asensio

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201411733

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      Electrostatic and charge-transfer contributions to CH–π complexes can be modulated by attaching electron-withdrawing substituents to the carbon atom. Although they have a clearly stabilizing effect in the gas phase, the influence of this chemical modification for the behavior in water is more difficult to predict. Dynamic combinatorial chemistry is used to provide a definitive and quantitative answer to this question.

    35. Metal–Organic Frameworks

      Cu3(hexaiminotriphenylene)2: An Electrically Conductive 2D Metal–Organic Framework for Chemiresistive Sensing (pages 4349–4352)

      Dr. Michael G. Campbell, Dr. Dennis Sheberla, Sophie F. Liu, Prof. Timothy M. Swager and Prof. Mircea Dincă

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201411854

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      A MOF with a nose: Previous efforts to use metal–organic frameworks (MOFs) for chemical sensing have been hindered by poor signal transduction due to a lack of electrical conductivity. A new conductive 2D MOF can be used for the chemiresistive sensing of ammonia. It is shown that the sensing response can be varied by the choice of the metal node.

    36. Biosynthesis

      An Unusual Terpene Cyclization Mechanism Involving a Carbon–Carbon Bond Rearrangement (pages 4353–4356)

      Dr. Ayuko Meguro, Yudai Motoyoshi, Kazuya Teramoto, Shota Ueda, Yusuke Totsuka, Yumi Ando, Dr. Takeo Tomita, Dr. Seung-Young Kim, Dr. Tomoyuki Kimura, Dr. Masayuki Igarashi, Dr. Ryuichi Sawa, Prof. Dr. Tetsuro Shinada, Prof. Dr. Makoto Nishiyama and Prof. Dr. Tomohisa Kuzuyama

      Article first published online: 16 FEB 2015 | DOI: 10.1002/anie.201411923

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      Biosynthetic virtuosity: Cyclooctat-9-en-7-ol synthase (CotB2) catalyzes the synthesis of an unusual 5-8-5 fused-ring structure with six chiral centers from the achiral C20 substrate geranylgeranyl diphosphate. By combining in vivo studies with in vitro reactions, an unusual cyclization mechanism was elucidated, which involves a carbon–carbon backbone rearrangement and three long-range hydride shifts. OPP=pyrophosphate.

    37. Bioinorganic Chemistry

      Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates (pages 4357–4361)

      Dr. Apparao Draksharapu, Davide Angelone, Dr. Matthew G. Quesne, Sandeep K. Padamati, Dr. Laura Gómez, Dr. Ronald Hage, Prof. Dr. Miquel Costas, Prof. Dr. Wesley R. Browne and Dr. Sam P. de Visser

      Article first published online: 6 FEB 2015 | DOI: 10.1002/anie.201411995

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      Understanding metalloenzymes: A synthetic FeIII-OCl complex has been generated and spectroscopically characterized at room temperature. Such nonheme iron(III) hypohalite intermediates have been implicated in biological halogenation reactions and may offer clues to understanding the activity of iron halogenases.

    38. π-Diborene Complexes

      Unexpected Luminescence Behavior of Coinage Metal π-Diborene Complexes (pages 4362–4366)

      Dr. Philipp Bissinger, Dr. Andreas Steffen, Dr. Alfredo Vargas, Dr. Rian D. Dewhurst, Dr. Alexander Damme and Prof. Dr. Holger Braunschweig

      Article first published online: 6 FEB 2015 | DOI: 10.1002/anie.201408993

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      Boron illuminates: Unprecedented photophysical properties were observed for luminescent π-diborene complexes of Cu and Ag, including unusually high fluorescence quantum yields in solution. This indicates that little to no intersystem crossing between S1 and Tn occurs despite the strong spin–orbit coupling of the metal atoms. The replacement of carbon with boron thus yields luminescent isolobal analogues of otherwise non-emissive olefin complexes of Cu and Ag.

    39. Protein NMR Spectroscopy

      Site-Specific Solid-State NMR Studies of “Trigger Factor” in Complex with the Large Ribosomal Subunit 50S (pages 4367–4369)

      Dr. Emeline Barbet-Massin, Chih-Ting Huang, Dr. Venita Daebel, Dr. Shang-Te Danny Hsu and Prof. Bernd Reif

      Article first published online: 5 FEB 2015 | DOI: 10.1002/anie.201409393

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      NMR beyond 1 MDa: Magic-angle spinning (MAS) solid-state NMR experiments of the ribosome binding domain of the trigger factor (TF-RBD) in complex with the 50S ribosome yield defined chemical shift changes for α2 in TF-RBD. The combined use of proton detection and high MAS frequencies (60 kHz) enables the investigation of approximately 20 μg quantities of labeled protein.

    40. σ-Aromaticity

      The σ-Aromatic Clusters [Zn3]+ and [Zn2Cu]: Embryonic Brass (pages 4370–4374)

      Dr. Kerstin Freitag, Dr. Christian Gemel, Dr. Paul Jerabek, Prof. Dr. Iris M. Oppel, Dr. Rüdiger W. Seidel, Prof. Dr. Gernot Frenking, Hung Banh, Katharina Dilchert and Prof. Dr. Roland A. Fischer

      Article first published online: 12 FEB 2015 | DOI: 10.1002/anie.201410737

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      Bold as brass: The bonding situations of the Cp* ligand-protected clusters [Zn3]+ (1) and [Zn2Cu] (2) were investigated by quantum chemical calculations revealing a high degree of σ-aromaticity similar to the trihydrogen ion [H3]+. The new species serve as molecular building units of CunZnm nanobrass clusters as indicated by liquid-injection field desorption ionization (LIFDI) mass spectrometry.

    41. Methylene Blue Photophysics

      Enhancing Intersystem Crossing in Phenotiazinium Dyes by Intercalation into DNA (pages 4375–4378)

      Dr. Juan J. Nogueira, Dr. Markus Oppel and Prof. Leticia González

      Article first published online: 6 FEB 2015 | DOI: 10.1002/anie.201411456

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      Intercalation of methylene blue into DNA protects the dye from hydrogen bonding with external water molecules. This activates an intersystem crossing pathway mediated by electronic spin–orbit coupling, which is inactive in aqueous solution. Thus, the photodynamic therapy efficacy of methylene blue is enhanced upon binding to DNA.

    42. Receptor Ligands

      Monitoring Ligand-Induced Conformational Changes for the Identification of Estrogen Receptor Agonists and Antagonists (pages 4379–4382)

      Svenja C. Mayer-Wrangowski and Prof. Dr. Daniel Rauh

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201410148

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      Agonistic and antagonistic small-molecule regulators induce distinct conformational changes within the ligand-binding domain of the estrogen receptor, thereby altering the receptor's activity. A direct binding assay for the detection of estrogen receptor ligands was developed that distinguishes between different binding modes and is suitable for high-throughput screening.

    43. C[BOND]H Activation

      Efficient Access to Titanaaziridines by C[BOND]H Activation of N-Methylanilines at Ambient Temperature (pages 4383–4387)

      Manfred Manßen, Dr. Nicolai Lauterbach, Jaika Dörfler, Dr. Marc Schmidtmann, Wolfgang Saak, Prof. Dr. Sven Doye and Prof. Dr. Rüdiger Beckhaus

      Article first published online: 17 MAR 2015 | DOI: 10.1002/anie.201500796

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      Killing two birds with one stone: A bis(η51-pentafulvene)titanium complex reacts with secondary N-methylamines resulting in simultaneous N[BOND]H and C[BOND]H activation and formation of titanaaziridines. These reactions can even be performed below room temperature und generate three-membered titanacycles. The first molecular structure of a titanium methyleneaniline complex is determined.

    44. Phosphorus Nitrides

      A High-Pressure Polymorph of Phosphorus Oxonitride with the Coesite Structure (pages 4388–4391)

      Dominik Baumann, Robin Niklaus and Prof. Dr. Wolfgang Schnick

      Article first published online: 9 FEB 2015 | DOI: 10.1002/anie.201410526

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      Under pressure: The coesite structure type was observed in a high-pressure polymorph of phosphorus oxonitride (PON). This is the first example of this structure occurring outside of SiO2. This result represents a major step towards the synthesis of a stishovite-type polymorph of PON.

    45. Intact P4 and As4 Complexes

      Fixation and Release of Intact E4 Tetrahedra (E=P, As) (pages 4392–4396)

      M. Sc. Fabian Spitzer, Prof. Dr. Marek Sierka, Prof. Mario Latronico, Prof. Dr. Piero Mastrorilli, Dr. Alexander V. Virovets and Prof. Dr. Manfred Scheer

      Article first published online: 10 FEB 2015 | DOI: 10.1002/anie.201411451

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      Too fragile? Just wrap it! Sensitive P4 and As4 can be stabilized in [(NacnacCu)2(μ,η2:2-E4)] (E=P, As), which serves as storage material. The E4 tetrahedra are intact, which was confirmed by calculations and experimentally by liberation with a Lewis base (LB). [NacnacCu(η2-P4)] was also isolated, which contains an intact, side-on coordinated P4 entity. Its dynamic behavior was examined by different NMR techniques.

    46. Electron-Induced Ethanol Synthesis

      Electron-Induced Hydration of an Alkene: Alternative Reaction Pathways (pages 4397–4400)

      Jonas Warneke, Ziyan Wang, Prof. Dr. Petra Swiderek and Dr. Jan Hendrik Bredehöft

      Article first published online: 6 FEB 2015 | DOI: 10.1002/anie.201412147

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      Going soft: Post-irradiation thermal desorption spectrometry (TDS) has shown that electron-induced reactions in condensed mixtures of ethylene and water lead to the synthesis of ethanol. This synthesis is not only induced by soft electron impact ionization but also by electron attachment to ethylene and a subsequent acid/base reaction with water.

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