Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 44

Early View (Online Version of Record published before inclusion in an issue)

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemPlusChem, Zeitschrift für Chemie

  1. Communications

    1. Nonlinear Optical Materials | Hot Paper

      Synthesis, Structure, and Frequency-Doubling Effect of Calcium Cyanurate

      Dr. Markus Kalmutzki, Dr. Markus Ströbele, Dipl.-Chem. Frank Wackenhut, Prof. Dr. Alfred J. Meixner and Prof. Dr. H.-Jürgen Meyer

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407708

      Thumbnail image of graphical abstract

      The alkaline-earth cyanurate Ca3(O3C3N3)2 (CCY) was produced in a solid-state metathesis reaction through the cyclotrimerization of cyanate ions. The crystal structure of CCY is closely related to the structure of β-BBO. Crystalline CCY promises to be amongst the most efficient frequency doubling materials.

    2. Natural Product Synthesis

      Enantioselective, Protecting-Group-Free Total Synthesis of Sarpagine Alkaloids—A Generalized Approach

      M. Sc. Sebastian Krüger and Dr. Tanja Gaich

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407280

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      A general synthesis of saragine alkaloids proceeds through an eight-step sequence. The enantioselective total synthesis of (+)-vellosimine, (+)-N-methylvellosimine, and (+)-10-methoxyvellosimine has been accomplished without using protecting groups. A “privileged intermediate” is generated in the last step, from which all other members of the alkaloid family can be synthesized.

    3. Drug Design

      Cyclic-Disulfide-Based Prodrugs for Cytosol-Specific Drug Delivery

      Gabor Butora, Ning Qi, Wenlang Fu, Truyen Nguyen, Hsueh-Cheng Huang and Ian W. Davies

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407130

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      Open on delivery: Cyclic-disulfide-based prodrugs are especially suitable for the highly efficient intracellular delivery of antiviral and antimetabolic nucleoside monophosphates. The key feature of this design is a reduction-triggered charge-dissipating cyclodeesterification of an alicyclic disulfide, followed by facile intramolecular self-quenching of the transient thiirane (see scheme; GSH=glutathione).

    4. Reversible Iron Exsolution

      Reversible Topochemical Exsolution of Iron in BaFe2+2(PO4)2

      Dr. Rénald David, Dr. Houria Kabbour, Dr. Dmitry Filimonov, Prof. Dr. Marielle Huvé, Dr. Alain Pautrat and Dr. Olivier Mentré

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201404476

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      Digging holes and refilling them: BaFe2(PO4)2 is the first 2D-Ising ferromagnetic oxide, and it has a unique re-entrant structural transition at low temperature. Furthermore, it topochemically oxidizes into a variety of fully ordered 2D Fe-depleted compounds with mixed Fe2+/Fe3+ valence, even at room temperature, with modified properties. This process is reversible, and Fe can be reincorporated under H2 flux or electron beam.

    5. Light-Harvesting Polymers

      Long-Distance Electronic Energy Transfer in Light-Harvesting Supramolecular Polymers

      Christian B. Winiger, Dr. Shaoguang Li, Dr. Ganesh R. Kumar, Dr. Simon M. Langenegger and Prof. Dr. Robert Häner

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407968

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      Collect and deliver: Pyrene-doped supramolecular polymers assembled from short amphiphilic phenanthrene oligomers exhibit light-harvesting properties. Energy transfer from the light absorbing phenanthrenes to the pyrene acceptor molecules proceeds in a highly efficient way over distances well beyond 100 nm, suggesting a quantum coherent mechanism.

  2. Cover Pictures

    1. Switchable Amplification of Vibrational Circular Dichroism as a Probe of Local Chiral Structure

      Dr. Sérgio R. Domingos, M. Sc. Hans J. Sanders, Prof. Dr. František Hartl, Prof. Dr. Wybren J. Buma and Prof. Dr. Sander Woutersen

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201410100

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      Vibration circular dichroism (VCD) spectroscopy is used to determine the absolute configuration and conformation of chiral molecules in solution but low signal intensities and spectral congestion often prohibit the investigation of local structure. In their Communication (DOI: 10.1002/anie.201407376), W. J. Buma, S. Woutersen et al. describe the attachment of a ferrocene-based electrochemically switchable amplifier to a molecular system, which enables the local amplification of the VCD signal.

  3. Communications

    1. Stimuli-Responsive Materials | Very Important Paper

      Breathing Pores on Command: Redox-Responsive Spongy Membranes from Poly(ferrocenylsilane)s

      Kaihuan Zhang, Xueling Feng, Dr. Xiaofeng Sui, Dr. Mark A. Hempenius and Prof. G. Julius Vancso

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201408010

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      Redox-active porous membranes were synthesized from poly(ferrocenylsilane) PFS-based poly(ionic liquid)s (see picture; pore formation using ammonia/water). Reversible switching between more open and more closed porous structures, induced by oxidation and reduction, was demonstrated.

    2. Natural Antioxidants

      Short-lived Phenoxyl Radicals Formed from Green-Tea Polyphenols and Highly Reactive Oxygen Species: An Investigation by Time-Resolved EPR Spectroscopy

      Dr. Dmytro Neshchadin, Dr. Stephen N. Batchelor, Prof. Dr. Itzhak Bilkis and Prof. Dr. Georg Gescheidt

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407995

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      How does tea fight dangerous radicals? Hydrogen abstraction from catechin and green-tea polyphenols by highly reactive O-centered H-abstracting species was studied at the molecular level and in real time by time-resolved EPR spectroscopy. Our results show that all phenolic OH groups display identical reactivity. Accordingly, statistical (entropic) factors essentially predominate in initial antioxidative events.

    3. Protein Extraction from Tissue

      Ultrafast Extraction of Proteins from Tissues Using Desorption by Impulsive Vibrational Excitation

      Marcel Kwiatkowski, Marcus Wurlitzer, Maryam Omidi, Ling Ren, Sebastian Kruber, Refat Nimer, Dr. Wesley D. Robertson, Priv.-Doz. Dr. Andrea Horst, Prof. Dr. R. J. Dwayne Miller and Prof. Dr. Hartmut Schlüter

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407669

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      Proteins can be blasted out of intact tissues and into the gas phase in less than a millisecond with a picosecond IR laser (PIRL). The proteins are desorbed by impulsive excitation (DIVE) of intramolecular vibrational states of water molecules in the cell. PIRL-DIVE can be used to extract significant amounts of proteins ranging in size from a few kDa up to several MDa.

    4. Organocatalysis

      Metal-Free Enantioselective Electrophilic Activation of Allenamides: Stereoselective Dearomatization of Indoles

      Ciro Romano, Dr. Minqiang Jia, Prof. Magda Monari, Elisabetta Manoni and Prof. Marco Bandini

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407518

      Thumbnail image of graphical abstract

      Breaking the aromaticity: The enantioselective dearomatization of indoles with allenamides is achieved through Brønsted acid catalysis. A range of 3,3-disubstituted indolines as well as indolenines is synthesized in a highly chemo-, regio-, and stereoselective manner.

    5. Nanotechnology

      Photofunctional Nanomodulators for Bioexcitation

      Dr. Eijiro Miyako, Dr. Julie Russier, Dr. Matteo Mauro, Dr. Cristina Cebrian, Prof. Hiromu Yawo, Dr. Cécilia Ménard-Moyon, Dr. James A. Hutchison, Dr. Masako Yudasaka, Prof. Sumio Iijima, Prof. Luisa De Cola and Dr. Alberto Bianco

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407169

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      Carbon nanohorns were functionalized with a dye to develop a new type of light-driven nanomodulator. This system generates heat and reactive oxygen species (ROS) under biologically transparent near-infrared (NIR) laser irradiation. These properties can be applied for single-cell analyses and innovative cell therapies.

    6. C[BOND]H functionalization | Hot Paper

      Practical and Highly Selective C[BOND]H Functionalization of Structurally Diverse Ethers

      Miao Wan, Zhilin Meng, Prof. Hongxiang Lou and Prof. Lei Liu

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201407083

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      A practical trityl ion mediated C[BOND]H functionalization of ethers has been disclosed. The reaction proceeds at ambient temperature with high chemoselectivity and good functional-group tolerance. The protocol displays excellent regio- and diastereoselectivities for unsymmetric ethers, thus stereoselectively yielding highly functionalized trans-disubstituted tetrahydrofuran, tetrahydropyran, dihydropyran, and isochroman moieties.

    7. Self-Assembly

      You have full text access to this OnlineOpen article
      Facile and Scalable Preparation of Pure and Dense DNA Origami Solutions

      Evi Stahl, Dr. Thomas G. Martin, Florian Praetorius and Prof. Dr. Hendrik Dietz

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201405991

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      PEG packs them all: A depletion-based method is used for the preparation of self-assembled megadalton-scale DNA objects up to the limit of solubility, including the possibility for bringing such objects into a solid phase. Due to its fidelity and simplicity this method might benefit the development of new types of applications that use self-assembled DNA objects.

    8. Transition Metals

      Oxidative Metalation as a Route to Size-Mismatched Macrocyclic Complexes: Osmium Corroles

      Dr. Abraham B. Alemayehu, Dr. Kevin J. Gagnon, Prof. Dr. James Terner and Prof. Dr. Abhik Ghosh

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201405890

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      Last man standing! After the synthesis of platinum corroles, osmium was the last remaining middle and late 5d metal to be inserted into the contracted porphyrin analogue. Oxidative metalation has now provided a moderately high-yielding route to osmium corroles. DEGME=diethylene glycol monomethyl ether.

    9. Lipid Membranes

      Simultaneous In Situ Quantification of Two Cellular Lipid Pools Using Orthogonal Fluorescent Sensors

      Dr. Shu-Lin Liu, Dr. Ren Sheng, Matthew J. O'Connor, Yang Cui, Dr. Youngdae Yoon, Svetlana Kurilova, Dr. Daesung Lee and Dr. Wonhwa Cho

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201408153

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      Same time, same place: The time-resolved quantification of multiple lipids in a lipid membrane provides insight into the complex mechanisms of lipid-mediated cell signaling and regulation. Sensors were prepared by incorporating two environmentally sensitive fluorophores with minimal spectral overlap into engineered lipid-binding proteins.

    10. Trifluoromethylation

      Diastereoselective Synthesis of Vicinally Bis(trifluoromethylated) Alkylboron Compounds through Successive Insertions of 2,2,2-Trifluorodiazoethane

      Prof. Gary A. Molander and DaWeon Ryu

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201408191

      Thumbnail image of graphical abstract

      Why stop at one? A recently reported route to α-trifluoromethylated alkylboron compounds by an α-transfer mechanism has now been extended to the synthesis of unprecedented vicinally bis(trifluoromethylated) alkylboron compounds with high diastereoselectivity (see scheme). The utility of these products, each of which was isolated as a single diastereomer, is highlighted by their functionalization through transformation of the C[BOND]B bond.

    11. Hydroboration | Hot Paper

      Hydroboration of Arynes with N-Heterocyclic Carbene Boranes

      Dr. Tsuyoshi Taniguchi and Prof. Dr. Dennis P. Curran

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201408345

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      A new partnership with a future: N-Heterocyclic carbene (NHC) boranes coupled with arynes in a hydroboration reaction to produce various B-aryl-substituted NHC-boranes (see scheme), which are stable and have many potential uses. The proposed hydride-transfer character of the mechanism was supported by the ortho regioselectivity observed for the hydroboration of arynes with an electron-withdrawing substituent.

  4. Minireviews

    1. Natural Products

      Cascade Reactions: A Driving Force in Akuammiline Alkaloid Total Synthesis

      Joel M. Smith, Jesus Moreno, Ben W. Boal and Prof. Neil K. Garg

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201406866

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      The akuammiline alkaloids are a family of terrestrial natural products which have a rich history and display promising therapeutic potential. Until recently, syntheses of these natural products have remained elusive. This minireview describes several recently completed synthetic efforts, and illustrates how the akuammilines have provided inspiration for the discovery of novel cascade processes.

  5. Cover Pictures

    1. Internalization of Silica Nanoparticles into Fluid Liposomes: Formation of Interesting Hybrid Colloids

      Dr. Raphael Michel, Dr. Ellina Kesselman, Tobias Plostica, Prof. Dr. Dganit Danino and Prof. Dr. Michael Gradzielski

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201410024

      Thumbnail image of graphical abstract

      Liposome–nanoparticle hybrid colloids were obtained by internalization of silica nanoparticles into fluid liposomes. In their Communication (DOI: 10.1002/anie.201406927), M. Gradzielski, R. Michel, et al. show that the structure of these long-time stable hybrid colloids is conveniently controlled by the initial mixing ratio of nanoparticles to liposomes. The internalization can be followed under conditions under which the process proceeds slowly allowing for the observation of the different steps of the mechanism.

    2. Polyoxometalate Ionic Liquids as Self-Repairing Acid-Resistant Corrosion Protection

      M. Sc. Sven Herrmann, M. Sc. Monika Kostrzewa, Prof. Dr. Andreas Wierschem and Prof. Dr. Carsten Streb

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201410023

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      Self-healing corrosion protection is provided by functional polyoxometalate ionic liquids (POM-ILs) coated onto metal surfaces. C. Streb et al. utilize in their Communication (10.1002/anie.201408171) POM-ILs, which are hydrophobic, acid-resistant, and form mechanically stable films, to protect copper metal against acid corrosion. Mechanical damage to the coating is self-repaired in less than one minute through the unique rheological properties of the compounds.

  6. Communications

    1. Antimicrobial Peptides | Hot Paper

      Combining Topology and Sequence Design for the Discovery of Potent Antimicrobial Peptide Dendrimers against Multidrug-Resistant Pseudomonas aeruginosa

      Michaela Stach, Thissa N. Siriwardena, Dr. Thilo Köhler, Prof. Dr. Christian van Delden, Priv.-Doz. Dr. Tamis Darbre and Prof. Dr. Jean-Louis Reymond

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201409270

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      Multidrug-resistant bacteria, such as Pseudomonas aeruginosa and Acinetobacter baumannii, are a major public health threat. By combining topology and amino acid sequence design, new antimicrobial peptide dendrimers with high activity against these pathogens were found, which represents a new and general approach for the discovery of antimicrobial agents.

    2. Proteomics

      Over 10 000 Peptide Identifications from the HeLa Proteome by Using Single-Shot Capillary Zone Electrophoresis Combined with Tandem Mass Spectrometry

      Dr. Liangliang Sun, Dr. Alexander S. Hebert, Xiaojing Yan, Yimeng Zhao, Dr. Michael S. Westphall, Matthew J. P. Rush, Dr. Guijie Zhu, Dr. Matthew M. Champion, Prof. Dr. Joshua J. Coon and Prof. Dr. Norman J. Dovichi

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201409075

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      Let’s see some ID: 2100 protein and 10 000 peptide identifications (IDs) from a HeLa cell proteome digest were obtained in a single 100 min capillary zone electrophoresis (CZE)–tandem mass spectrometry (MS/MS) analysis. These results represent an almost tenfold improvement in peptide and protein IDs compared with previous single-shot analyses using this technology.

    3. C[BOND]H Activation

      Construction of Axial Chirality by Rhodium-Catalyzed Asymmetric Dehydrogenative Heck Coupling of Biaryl Compounds with Alkenes

      Jun Zheng and Prof. Dr. Shu-Li You

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201408805

      Thumbnail image of graphical abstract

      An axe to grind? Novel axially chiral biaryls were synthesized by the direct C[BOND]H bond olefination of biaryl compounds, using a chiral [Cp*RhIII] catalyst (1), in good to excellent yields and enantioselectivities. The biaryls were found as suitable ligands for rhodium-catalyzed asymmetric conjugate addition reactions.

    4. Phospholipid Membranes | Hot Paper

      In Situ Vesicle Formation by Native Chemical Ligation

      Dr. Roberto J. Brea, Christian M. Cole and Prof. Neal K. Devaraj

      Article first published online: 24 OCT 2014 | DOI: 10.1002/anie.201408538

      Thumbnail image of graphical abstract

      Spontaneous growth: Native chemical ligation (NCL) can be used to prepare phospholipids spontaneously at neutral pH from thioesters. The lipids self-assemble in situ to form vesicles up to several micrometers in diameter. Thanks to the chemoselectivity of NCL, this method of membrane formation in situ is compatible with biological materials.

  7. Author Profiles

    1. Todd B. Marder

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201409785

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      I advise my students to see the world and keep an open mind. My favorite quote is “Never try to discourage thinking for you are sure to succeed” (Bertrand Russell).

  8. Cover Pictures

    1. Unravelling the Correlation between the Aspect Ratio of Nanotubular Structures and Their Electrochemical Performance To Achieve High-Rate and Long-Life Lithium-Ion Batteries

      Dr. Yuxin Tang, Dr. Yanyan Zhang, Jiyang Deng, Dr. Dianpeng Qi, Wan Ru Leow, Jiaqi Wei, Dr. Shengyan Yin, Prof. Zhili Dong, Prof. Rachid Yazami, Prof. Zhong Chen and Prof. Xiaodong Chen

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201410022

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      Understanding the relationship between the nanostructure of an electrode and its electrochemical performance is crucial for the development of high-perfomance lithium-ion batteries. In their Communication (DOI: 10.1002/anie.201406719), Z. Chen, X. Chen, and co-workers report that the aspect ratio of nanotubular materials determines battery performance at high charging/discharging rates. Their proof-of-concept batteries are very promising for energy-storage systems in electrical vehicles.

    2. Recognition of Nucleic Acid Junctions Using Triptycene-Based Molecules

      Stephanie A. Barros and Prof. David M. Chenoweth

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201410021

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      Rationally designed nucleic acid junction binders based on a triptycene scaffold were found to significantly stabilize DNA and RNA three-way junctions (3WJs). In their Communication (DOI: 10.1002/anie.201407061), D. M. Chenoweth and S. A. Barros report that the scaffold provides a new architecture for the development of junction binders with enhanced recognition properties. Initial cytotoxicity data in two human ovarian carcinoma cell lines are promising.

    3. A Reversible and Selective Inhibitor of Monoacylglycerol Lipase Ameliorates Multiple Sclerosis

      Dr. Gloria Hernández-Torres, Dr. Mariateresa Cipriano, Erika Hedén, Emmelie Björklund, Dr. Ángeles Canales, M. Sc. Debora Zian, M. Sc. Ana Feliú, Dr. Miriam Mecha, Dr. Carmen Guaza, Prof. Dr. Christopher J. Fowler, Prof. Dr. Silvia Ortega-Gutiérrez and Prof. Dr. María L. López-Rodríguez

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201410020

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      The inhibition of monoacylglycerol lipase (MAGL), the enzyme responsible for the inactivation of the endocannabinoid 2-arachidonoylglycerol, is a strategy for the treatment of multiple sclerosis. In their Communication (DOI: 10.1002/anie.201407807), M. L. López-Rodríguez and co-workers describe a potent, reversible, and selective inhibitor of MAGL that slows the clinical progression of MS without inducing undesirable CB1-mediated side effects.

    4. Biosynthesis of the Halogenated Mycotoxin Aspirochlorine in Koji Mold Involves a Cryptic Amino Acid Conversion

      Pranatchareeya Chankhamjon, Dr. Daniela Boettger-Schmidt, Dr. Kirstin Scherlach, Barbara Urbansky, Dr. Gerald Lackner, Daniel Kalb, Hans-Martin Dahse, Prof. Dr. Dirk Hoffmeister and Prof. Dr. Christian Hertweck

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201409948

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      The koji mold Aspergillus oryzae, which is widely used in food fermentations (e.g., sake production), produces the toxin aspirochlorine. C. Hertweck et al. elucidated in their Communication (DOI: 10.1002/anie.201407624) the biosynthetic pathway of this chlorinated epipolythiodioxopiperazine. An iterative non-ribosomal peptide synthetase assembles the diketopiperazine core from two phenylalanine units, one of which then undergoes an unprecedented conversion to glycine. Enzymatic halogenation of the second Phe unit significantly contributes to the biological activity of aspirochlorine.

    5. Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries

      Dr. Santanab Giri, Swayamprabha Behera and Prof. Puru Jena

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201409947

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      Currently used electrolytes in Li-ion batteries mostly contain toxic halogens. In their Communication (DOI: 10.1002/anie.201408648), P. Jena et al. use first-principles calculations to show that all these electrolytes are based on superhalogens, i.e., that the vertical electron detachment energies of the moieties that constitute the anions are larger than those of any halogen atom. Several superhalogens do not contain a single halogen atom and their potential as effective electrolytes was studied. Among the identified halogen-free electrolytes, Li(CB11H12) is shown to have the greatest potential.

    6. Nanospheres, Nanotubes, Toroids, and Gels with Controlled Macroscopic Chirality

      Sandra Arias, Dr. Félix Freire, Prof. Dr. Emilio Quiñoá and Prof. Dr. Ricardo Riguera

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201409945

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      The supramolecular assembly of helical polymers, namely poly(aryl acetylenes), with monovalent metal cations (Li+, Na+, and Ag+) leads to a number of different macroscopically chiral nanostructures, such as nanospheres, nanotubes, toroids, and gels, with the capacity to encapsulate a variety of organic and inorganic substances. The cover picture illustrates this fruitful “chemical tornado”, which is presented by F. Freire, R. Riguera, et al. in their Communication (DOI: 10.1002/anie.201406884).

  9. Communications

    1. Azaporphyrin Ligands

      A 3-Pyridyl-5,15-Diazaporphyrin Nickel(II) Complex as a Bidentate Metalloligand for Transition Metals

      Ayaka Yamaji, Prof. Dr. Ji-Young Shin, Prof. Dr. Yoshihiro Miyake and Prof. Dr. Hiroshi Shinokubo

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408852

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      Porphyrin coordination: A 3-pyridyl-5,15-diazaporphyrin NiII complex acts as a bidentate metalloligand forming stable metal complexes with PtII, RuII, and RhI centers (see picture). Single-crystal X-ray analysis confirms the formation of dative bonds between the meso-nitrogen atoms and the metal ions.

    2. Fuel Cells

      Mapping Platinum Species in Polymer Electrolyte Fuel Cells by Spatially Resolved XAFS Techniques

      Dr. Shinobu Takao, Dr. Oki Sekizawa, Dr. Shin-ichi Nagamatsu, Dr. Takuma Kaneko, Dr. Takashi Yamamoto, Dr. Gabor Samjeské, Dr. Kotaro Higashi, Dr. Kensaku Nagasawa, Dr. Takuya Tsuji, Dr. Motohiro Suzuki, Dr. Naomi Kawamura, Dr. Masaichiro Mizumaki, Prof. Dr. Tomoya Uruga and Prof. Dr. Yasuhiro Iwasawa

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408845

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      Catalyst characterization: Platinum species in a Pt/C cathode catalyst layer were mapped by spatially resolved X-ray absorption fine structure (XAFS) methods. Information on the oxidation and leaching of Pt cathode nanoparticles in degraded polymer electrolyte fuel cells (PEFCs) is obtained, which is relevant for the mechanism of PEFC degradation.

    3. RNA Arrays

      Enzymatic Fabrication of High-Density RNA Arrays

      Dr. Cheng-Hsien Wu, Matthew T. Holden and Prof. Lloyd M. Smith

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408747

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      Molecular duplicating: A new technique converts DNA arrays to high-density arrays of RNA. The process functions by synthesizing a DNA array containing short RNA primers, followed by steps of transcription and DNase digestion to produce only the desired RNA sequences bound to the surface.

    4. Azepines

      A Catalytic Diastereoselective Formal [5+2] Cycloaddition Approach to Azepino[1,2-a]indoles: Putative Donor–Acceptor Cyclobutanes as Reactive Intermediates

      Raynold Shenje, M. Cynthia Martin and Prof. Dr. Stefan France

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408429

      Thumbnail image of graphical abstract

      The diastereoselective synthesis of azepino[1,2-a]indoles is enabled by a formal [5+2] cycloaddition approach. The reaction presumably proceeds through a Lewis acid catalyzed formal [2+2] cycloaddition of an alkene with an N-indolyl alkylidene β-amide ester to form a donor–acceptor cyclobutane intermediate, which subsequently undergoes an intramolecular ring-opening cyclization.

  10. Highlights

    1. Synthetic Methods

      Thiyl Radicals: From Simple Radical Additions to Asymmetric Catalysis

      Hariharaputhiran Subramanian, Ramkumar Moorthy and Prof. Dr. Mukund P. Sibi

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201408781

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      Thiyl radicals at play: Thiyls are significant free-radical intermediates both in biology and chemistry. The recent search for new enantioselective methods in radical chemistry has led to the inclusion of these radicals in the toolbox of chiral organocatalysts.

  11. Reviews

    1. Vesicle Transport

      The Molecular Machinery of Neurotransmitter Release (Nobel Lecture)

      Prof. Thomas C. Südhof

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201406359

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      The most important property of synaptic transmission is its speed, which is crucial for the overall workings of the brain. In his Nobel Lecture, T. C. Südhof explains how the synaptic vesicle and the plasma membrane undergo rapid fusion during neurotransmitter release and how this process is spatially organized, such that opening of Ca2+-channels allows rapid translation of the entering Ca2+ signal into a fusion event.

  12. Communications

    1. Protein Folding | Hot Paper

      Capturing the Mechanical Unfolding Pathway of a Large Protein with Coiled-Coil Probes

      Qing Li, Zackary N. Scholl and Prof. Piotr E. Marszalek

      Article first published online: 22 OCT 2014 | DOI: 10.1002/anie.201407211

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      An antiparallel coiled coil (CC) mechanical probe that can be used to assess the unfolding mechanism of a protein is developed. When a protein is studied by single-molecule force spectroscopy, the probe enables the assignment of force peaks to structural elements when the unfolding process passes through the location of the CC probe without significant disturbance of the host protein structure.

    2. Zintl Cluster Compounds

      On the Formation of Intermetalloid Clusters: Titanocene(III)diammin as a Versatile Reactant Toward Nonastannide Zintl Clusters

      Dr. Christian B. Benda, Dr. Markus Waibel and Prof. Dr. Thomas F. Fässler

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201407855

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      MSn8—Like the seeds of a blowball: In the presence of Zintl anions, titanocene(IV) dichloride is reduced in liquid ammonia, and a titanocene(III) diammin complex is formed. Stepwise ligand exchange reactions lead to a variety of intermediate TinSnm clusters that give insight into the formation of larger intermetalloid clusters.

    3. Nitrous Oxide

      Synthesis of Triazenes with Nitrous Oxide

      Gregor Kiefer, Dr. Tina Riedel, Prof. Paul J. Dyson, Dr. Rosario Scopelliti and Prof. Kay Severin

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408597

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      Synthesis with laughing gas: Triazenes can be obtained by the reaction of N2O with secondary lithium amides and Grignard reagents. The new synthetic method allows access to triazenes with alkenyl and alkynyl substituents at the 1-position. Some of the alkynyl triazenes show selective anticancer activity in cell cultures.

    4. Heterogeneous Catalysis

      Thermal Non-Oxidative Aromatization of Light Alkanes Catalyzed by Gallium Nitride

      Dr. Lu Li, Xiaoyue Mu, Wenbo Liu, Xianghua Kong, Shizhao Fan, Prof. Dr. Zetian Mi and Prof. Dr. Chao-Jun Li

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408754

      Thumbnail image of graphical abstract

      Light weights: The readily available nondoped GaN material possesses superior thermal stability and catalytic activity towards the non-oxidative aromatization of light alkanes (from C1 to C6) at elevated temperature. Theoretical calculations propose an energetically favorable adsorption interaction between methane and the m-plane of GaN.

    5. Hypervalent Compounds

      Mild Silver-Mediated Geminal Difluorination of Styrenes using an Air- and Moisture-Stable Fluoroiodane Reagent

      Nadia O. Ilchenko, Dr. Boris O. A. Tasch and Prof. Kálmán J. Szabó

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408812

      Thumbnail image of graphical abstract

      Phenomenal phenonium: A formal F2 addition to styrenes was carried out by using stable and safe fluorinating reagents under mild reaction conditions. The reaction proceeds via a phenonium intermediate.

  13. Highlights

    1. Homogeneous Catalysis

      Iron-Catalyzed Hydrogenation of Esters to Alcohols

      Dr. Philippe Dupau, Minh-Loan Tran Do, Dr. Sylvain Gaillard and Prof. Dr. Jean-Luc Renaud

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201407613

      Thumbnail image of graphical abstract

      Iron made it”: Recent breakthroughs in the hydrogenation of esters to alcohols by well-defined iron pincer complexes are highlighted. These complexes demonstrate promising efficiency and selectivities.

  14. Communications

    1. Crystal Structures

      The Polymorphs of L-Phenylalanine

      Franziska Stefanie Ihlefeldt, Fredrik Bjarte Pettersen, Aidan von Bonin, Malgorzata Zawadzka and Prof. Carl Henrik Görbitz

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201406886

      Thumbnail image of graphical abstract

      It was long considered impossible to prepare crystals of L-phenylalanine, the prototypical aromatic amino acid. High-quality crystals have now been obtained that provide solid-state data for two polymorphs. For one of these polymorphs the C2 space group previously assigned was revised to P21 (with Z′=4). Nice crystals can also be grown from solutions of dl-phenylalanine, but these are not proper racemic crystals.

    2. Core–Shell Structures

      One-Nanometer-Precision Control of Al2O3 Nanoshell through Solution-Based Synthesis Route

      Wei Zhang, Zi-Xiang Chi, Wen-Xin Mao, Prof. Rong-Wen Lv, Prof. An-Min Cao and Prof. Li-Jun Wan

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201406856

      Thumbnail image of graphical abstract

      Uniform surface coatings of Al2O3 with a thickness controllable at the one nanometer level were achieved by a solution-based synthesis route. Application of this coating methodology to LiCoO2 showed that its battery performance as a cathode material can be optimized by means of systematic surface control.

  15. Obituaries

    1. Franz Hillenkamp (19362014)

      Peter Roepstorff

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201409504

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      Franz Hillenkamp was one of the pioneers in contemporary mass spectrometry, and in 1985, he discovered, together with his postdoc Michael Karas, the principle of matrix assisted laser desorption ionization mass spectrometry (MALDI-MS).

  16. News

  17. Cover Pictures

    1. Translating Bacterial Detection by DNAzymes into a Litmus Test

      Kha Tram, Pushpinder Kanda, Prof. Dr. Bruno J. Salena, Prof. Dr. Shuangyan Huan and Prof. Dr. Yingfu Li

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201409655

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      Color change is common in nature and often signifies a seasonal transition, such as from summer to autumn. In their Communication (DOI: 10.1002/anie.201407021), S. Huan, Y. Li and co-workers report a new colorimetric detection method that takes advantage of an old technology. The design makes use of a DNAzyme, urease, and magnetic beads to translate the presence of E. coli bacteria into an increase in the pH value, thereby enabling colorimetric detection using the litmus test.

  18. Communications

    1. Heterocycle Synthesis

      Rhodium-Catalyzed NH Insertion of Pyridyl Carbenes Derived from Pyridotriazoles: A General and Efficient Approach to 2-Picolylamines and Imidazo[1,5-a]pyridines

      Yi Shi, Dr. Anton V. Gulevich and Prof. Dr. Vladimir Gevorgyan

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408335

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      Insert here: A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH-containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2-picolylamine derivatives. The developed transformation was further utilized in a facile one-pot synthesis of imidazo[1,5-a]pyridines. esp=α,α,α′,α′-tetramethyl-1,3-benzenedipropionic acid, Ts=4-toluenesulfonyl.

    2. Anti-Corrosion Coatings | Hot Paper

      Polyoxometalate Ionic Liquids as Self-Repairing Acid-Resistant Corrosion Protection

      M. Sc. Sven Herrmann, M. Sc. Monika Kostrzewa, Prof. Dr. Andreas Wierschem and Prof. Dr. Carsten Streb

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408171

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      This corrosion: Hydrophobic polyoxometalate-based ionic liquids (POM-ILs) are used as temporary acid-resistant coatings for copper metal. Complete protection against acid vapors and liquid acids is observed and the POM-IL coating can withstand mechanical damage by a self-repairing mechanism. The compounds are easily removed and recovered for subsequent usage.

    3. Lithium Batteries | Hot Paper

      Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li+/H+ Exchange in Aqueous Solutions

      Dr. Cheng Ma, Dr. Ezhiylmurugan Rangasamy, Dr. Chengdu Liang, Prof. Jeffrey Sakamoto, Dr. Karren L. More and Dr. Miaofang Chi

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408124

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      In sharp contrast to other garnets, the cubic Li7La3Zr2O12 preserved its structure upon Li+/H+ exchange in aqueous solutions. Subsequent immersion in a 2 M LiOH solution gave reverse Li+/H+ exchange, and the structure remained unchanged. Thus cubic Li7La3Zr2O12 has the desired properties to be the solid electrolyte in aqueous lithium batteries.

    4. Enzymatic Route to Cyclic Peptides | Hot Paper

      An Efficient Method for the In Vitro Production of Azol(in)e-Based Cyclic Peptides

      Dr. Wael E. Houssen, Andrew F. Bent, Dr. Andrew R. McEwan, Nathalie Pieiller, Dr. Jioji Tabudravu, Dr. Jesko Koehnke, Greg Mann, Rosemary I. Adaba, Dr. Louise Thomas, Dr. Usama W. Hawas, Dr. Huanting Liu, Dr. Ulrich Schwarz-Linek, Prof. Margaret C. M. Smith, Prof. James H. Naismith and Prof. Marcel Jaspars

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408082

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      Heterocycle-containing cyclic peptides are promising scaffolds for the pharmaceutical industry, but their chemical synthesis is very challenging. A new universal method has been devised to prepare these compounds using a set of engineered marine-derived enzymes and substrates.

    5. Nanostructures

      A Twisting Electronic Nanoswitch Made of DNA

      Dr. Yu Chuan Huang and Prof. Dipankar Sen

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201407729

      Thumbnail image of graphical abstract

      A mechatronic DNA nanoswitch is composed of a tight, topologically constrained composite of four DNA strands, in which a core of four guanine-rich single strands structurally and electronically links together four DNA double helices. The addition and removal of K+ or Sr2+ cations promote the formation of alternative conformers, which show strikingly distinct electronic properties.

    6. Noncovalent Interactions

      Sequence and Chiral Selectivity of Drug–DNA Interactions Revealed by Force Spectroscopy

      Qiongzheng Hu and Prof. Shoujun Xu

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201407093

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      A force to be reckoned with: Intercalation of a drug molecule in a DNA duplex causes a variation in the binding force of the duplex. The differential binding force (ΔF) can be probed precisely using the force-induced remnant magnetization spectroscopy technique. The technique allows the sequence specificity of DNA and chiral selectivity of drug molecules to be revealed.

  19. Book Reviews

    1. Bridging Heterogeneous and Homogeneous Catalysis. Concepts, Strategies, and Applications. Edited by Can Li and Yan Liu.

      John Meurig Thomas

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408712

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      Wiley-VCH, Weinheim, 2014. 656 pp., hardcover, € 159.00.—ISBN 978-3527335831

  20. Communications

    1. Water Splitting

      Enhanced Water Splitting at Thin Film Tungsten Trioxide Photoanodes Bearing Plasmonic Gold–Polyoxometalate Particles

      Dr. Renata Solarska, Krzysztof Bienkowski, Dr. Sylwia Zoladek, Aldona Majcher, Dr. Tomasz Stefaniuk, Prof. Pawel J. Kulesza and Prof. Jan Augustynski

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408374

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      A mesoporous photoanode consisting of WO3 decorated with polyoxometalate-capped Au nanoparticles (NPs) showed a significant enhancement of the visible-light-assisted photoelectrolysis of water. Shielding of the NPs avoids the formation of recombination centers at the photoanode surface. The large increase of water splitting photocurrents is assigned to a combined plasmonic and catalytic effect of the Au NPs on the WO3 surface.

    2. Electrocatalysis | Very Important Paper

      Scanning Electrochemical Microscopy of Individual Catalytic Nanoparticles

      Tong Sun, Yun Yu, Brian J. Zacher and Prof. Michael V. Mirkin

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408408

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      Tip size matters: Extremely small polished platnium electrodes were used as scanning electrochemical microscopy tips to attain spatial resolution higher than that of ordinary atomic force microscopy imaging or super-resolution optical techniques. Electron transfer and catalytic hydrogen evolution at individual metal nanoparticles were visualized (HOPG=highly ordered pyrolytic graphite).

    3. Plasmonics

      Shedding Light on the Extinction-Enhancement Duality in Gold Nanostar-Enhanced Raman Spectroscopy

      Dr. Ming Li, Dr. Jeon Woong Kang, Dr. Ramachandra Rao Dasari and Prof. Ishan Barman

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201409314

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      Gold nanostars: The relationship between the enhancement by surface-enhanced Raman spectroscopy (SERS) and the localized surface plasmon resonance (LSPR) band is investigated (see picture). The competition between the field enhancement and the optical extinction causes the maximum enhancement factor occurring at a blue-shifted LSPR band from the excitation wavelength rather than at the on-resonance position.

    4. Electrocatalysts

      ZIF-8 Derived Graphene-Based Nitrogen-Doped Porous Carbon Sheets as Highly Efficient and Durable Oxygen Reduction Electrocatalysts

      Hai-xia Zhong, Jun Wang, Yu-wei Zhang, Wei-lin Xu, Prof. Wei Xing, Dan Xu, Prof. Dr. Yue-fei Zhang and Prof. Dr. Xin-bo Zhang

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408990

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      Nitrogen-doped: A new oxygen reduction reaction electrocatalyst was obtained from ZIF-derived porous carbon and graphene. The catalyst exhibits high activity, superior tolerance to methanol, and good stability in comparison to commercial Pt/C catalyst.

    5. Imaging of Bacteria

      PET Imaging of Bacterial Infections with Fluorine-18-Labeled Maltohexaose

      Dr. Xinghai Ning, Dr. Wonewoo Seo, Dr. Seungjun Lee, Dr. Kiyoko Takemiya, Dr. Mohammad Rafi, Dr. Xuli Feng, Dr. Daiana Weiss, Dr. Xiaojian Wang, Larry Williams, Vernon M. Camp, Malveaux Eugene, Prof. W. Robert Taylor, Prof. Mark Goodman and Prof. Niren Murthy

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408533

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      Highly sensitive: A positron emission tomography (PET) tracer composed of 18F-labeled maltohexaose (MH18F) can image bacteria in vivo with a sensitivity and specificity that are orders of magnitude higher than those of fluorodeoxyglucose. MH18F can detect early-stage infections composed of as few as 105 E. coli colony-forming units (CFUs), and can identify drug resistance in bacteria in vivo.

    6. Tumor Imaging

      Targeted Imaging and Proteomic Analysis of Tumor-Associated Glycans in Living Animals

      Ran Xie, Lu Dong, Rongbing Huang, Senlian Hong, Ruoxing Lei and Prof. Xing Chen

      Article first published online: 21 OCT 2014 | DOI: 10.1002/anie.201408442

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      Sweet target: A strategy for the targeted imaging of tumor-associated glycans is reported and makes use of ligand-targeted liposomes encapsulating azidosugars. The azidosugars were selectively incorporated into the melanoma glycans in a xenograft mouse model and were then reacted with fluorophores using copper-free click chemistry for in vivo imaging or with affinity tags for proteomic analysis.

    7. Heterogeneous Catalysis

      Efficient Coupling of Solar Energy to Catalytic Hydrogenation by Using Well-Designed Palladium Nanostructures

      Dr. Ran Long, Zhoulv Rao, Keke Mao, Yu Li, Chao Zhang, Qiliang Liu, Dr. Chengming Wang, Prof. Zhi-Yuan Li, Prof. Xiaojun Wu and Prof. Yujie Xiong

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201407785

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      Taking shape: A Ru3+-mediated synthesis has been developed for unique Pd concave nanostructures which can directly harvest UV-to-visible light for styrene hydrogenation (see figure). The catalytic efficiency under full-spectrum irradiation at room temperature turns out to be comparable to that of the thermally (70 °C) driven reaction. The yields are higher than those obtained using Pd nanocrystals such as nanocubes and octahedrons.

    8. Kinetic Resolution

      Tungsten-Catalyzed Regio- and Enantioselective Aminolysis of trans-2,3-Epoxy Alcohols: An Entry to Virtually Enantiopure Amino Alcohols

      Dr. Chuan Wang and Prof. Dr. Hisashi Yamamoto

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408732

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      The first enantioselective aminolysis of 2,3-epoxy alcohols is described and involves the use of a tungsten catalyst with a bis(hydroxamic acid) (BHA) ligand. A sequential reaction process combining epoxidation and ring opening (by kinetic resolution) provides a new method for the preparation of virtually enantiopure amino alcohols.

    9. Enzyme Catalysis

      A Dehydratase Domain in Ambruticin Biosynthesis Displays Additional Activity as a Pyran-Forming Cyclase

      Gesche Berkhan and Dr. Frank Hahn

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201407979

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      Two birds with one stone: Through reaction of the recombinant polyketide synthase domain AmbDH3 with synthetic substrate surrogates, this domain was shown to have an unprecedented dual role as a dehydratase and a pyran-forming cyclase. The domain shows high stereoselectivity and relaxed substrate specificity, thus making it a potential tool for the chemoenzymatic synthesis of chiral oxygen-containing heterocycles.

    10. Iron(IV) Complexes

      A cis-Divacant Octahedral and Mononuclear Iron(IV) Imide

      Keith Searles, Prof. Dr. Skye Fortier, Dr. Marat M. Khusniyarov, Dr. Patrick J. Carroll, Dr. Jörg Sutter, Prof. Dr. Karsten Meyer, Prof. Dr. Daniel J. Mindiola and Prof. Dr. Kenneth G. Caulton

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201407156

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      The iron-y of an imide: A rare low-spin FeIV imide complex [(pyrr2py)Fe[DOUBLE BOND]NAd] (pyrr2py2−=bis(pyrrolyl)pyridine; Ad= 1-adamantyl) confined to a cis-divacant octahedral geometry was prepared by reduction of N3Ad with the FeII precursor [(pyrr2py)Fe(OEt2)]. The complex exhibits temperature-independent paramagnetism. In comparison to an authentic FeIII complex, such as [(pyrr2py)FeCl], the pyrr2py2− ligand is virtually redox innocent.

    11. Metal Hydrides

      Orbital-Like Motion of Hydride Ligands around Low-Coordinate Metal Centers

      Manuel A. Ortuño, Dr. Pietro Vidossich, Dr. Salvador Conejero and Prof. Dr. Agustí Lledós

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201407572

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      Mobile hydrides: A new type of dynamic process involving hydrides in low-coordinate NHC-based complexes has been computationally characterized. This dynamics can be described as an orbital-like motion of hydride ligands around the metal center. This novel insight leads to a better interpretation of NMR spectra.

    12. Dinitrogen Conversion

      Catalytic Dinitrogen Reduction at the Molybdenum Center Promoted by a Bulky Tetradentate Phosphine Ligand

      Dr. Qian Liao, Dr. Nathalie Saffon-Merceron and Dr. Nicolas Mézailles

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408664

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      Stoichiometric N2 reduction at a Mo center stabilized by bulky tetradentate phosphine ligand allowed the isolation of Mo–aminoimide and Mo–imido complexes. Both are suitable catalysts for the synthesis of NTMS3 from N2 and TMSCl through a mechanism involving a TMS radical.

    13. C[BOND]H Activation

      Highly Linear Selective Cobalt-Catalyzed Addition of Aryl Imines to Styrenes: Reversing Intrinsic Regioselectivity by Ligand Elaboration

      Wengang Xu and Prof. Naohiko Yoshikai

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408028

      Thumbnail image of graphical abstract

      Paired off: The title reaction has been achieved with cobalt-based catalytic systems featuring bis(2,4-dimethoxyphenyl)(phenyl)phosphine (L) and either 2-methoxypyridine or DBU (LB), thus affording a variety of 1,2-diarylethanes in good yields. Ligand screening and deuterium-labeling studies show the ligand and Lewis base to be important in the crucial C[BOND]C reductive elimination step. Cy=cyclohexyl, PMP=para-methoxyphenyl.

    14. Quinones and Deubiquitinases

      Harnessing the Oxidation Susceptibility of Deubiquitinases for Inhibition with Small Molecules

      Shimrit Ohayon, Maya Refua, Adi Hendler, Prof. Amir Aharoni and Prof. Ashraf Brik

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408411

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      Rub a DUB style: Reactive oxygen species generated by small molecules such as ortho quinones rapidly deactivate deubiquitinases (DUBs) by selective and irreversible oxidiation of the catalytic cysteine residue. DTT=dithiothreitol.

    15. Liquid Crystals

      Supramolecular [60]Fullerene Liquid Crystals Formed By Self-Organized Two-Dimensional Crystals

      Xiaoyan Zhang, Dr. Chih-Hao Hsu, Dr. Xiangkui Ren, Yan Gu, Prof. Bo Song, Dr. Hao-Jan Sun, Prof. Shuang Yang, Prof. Erqiang Chen, Prof. Yingfeng Tu, Prof. Xiaohong Li, Prof. Xiaoming Yang, Prof. Yaowen Li and Prof. Xiulin Zhu

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408438

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      Soft materials: A series of fullerene dyads self-organize to form two-dimensional crystals through π–π interactions between fullerenes. Lamellar packing of the 2D crystals gives rise to the formation of a new family of thermotropic supramolecular liquid crystals with hierarchical structures.

    16. H2 Production

      Hydrogenated Anatase: Strong Photocatalytic Dihydrogen Evolution without the Use of a Co-Catalyst

      Dr. Ning Liu, Christopher Schneider, Dr. Detlef Freitag, Dr. Umamaheswari Venkatesan, Dr. V. R. Reddy Marthala, Prof.Dr. Martin Hartmann, Benjamin Winter, Prof.Dr. Erdmann Spiecker, Dr. Andres Osvet, Eva M. Zolnhofer, Prof.Dr. Karsten Meyer, Dr. Tomohiko Nakajima, Xuemei Zhou and Prof.Dr. Patrik Schmuki

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201408493

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      Without a noble metal: The high-pressure hydrogenation of commercially available anatase or mixed-phase anatase/rutile TiO2 powder resulted in a highly effective and stable photocatalyst for H2 evolution without the need for an additional co-catalyst. This activation was not observed for rutile, but for anatase/rutile mixtures, a strong synergistic effect was found.

    17. Asymmetric Catalysis

      Rationally Designed Multifunctional Supramolecular Iminium Catalysis: Direct Vinylogous Michael Addition of Unmodified Linear Dienol Substrates

      Yun Gu, Dr. Yao Wang, Tian-Yang Yu, Prof. Dr. Yong-Min Liang and Prof. Dr. Peng-Fei Xu

      Article first published online: 19 OCT 2014 | DOI: 10.1002/anie.201406786

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      Fall into line: The title catalysis strategy has been developed for addressing the long-standing problem of the direct vinylogous Michael addition of unmodified linear dienol substrates. The desired 1,7-dioxo compounds were obtained with good yields and excellent regio- and enantioselectivity. DCE=1,2-dichloroethane, TMS=trimethylsilyl.

    18. Diagnostic GPI

      Diagnosis of Toxoplasmosis Using a Synthetic Glycosylphosphatidylinositol Glycan

      Dr. Sebastian Götze, Dr. Nahid Azzouz, Dr. Yu-Hsuan Tsai, Prof. Dr. Uwe Groß, Anika Reinhardt, Dr. Chakkumkal Anish, Prof. Dr. Peter H. Seeberger and Dr. Daniel Varón Silva

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201406706

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      Good news for cat lovers! A glycosylphosphatidylinositol (GPI) glycan resembling an antigen on the parasite T. gondii was synthesized and immobilized on a microarray. This setup can be used to diagnose toxoplasmosis. Latent and acute toxoplasmosis can be readily distinguished.

    19. Total Synthesis | Hot Paper

      A Cascade Strategy Enables a Total Synthesis of (−)-Gephyrotoxin

      Shuyu Chu, Dr. Stephen Wallace and Prof. Dr. Martin D. Smith

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201409038

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      The concise synthesis of (−)-gephyrotoxin from L-pyroglutaminol involves a diastereoselective intramolecular enamine/Michael cascade reaction that forms two rings and two stereocenters and generates a stable tricyclic iminium cation. A hydroxy-directed reduction of this intermediate plays a key role in establishing the required cis-configured decahydroquinoline ring system.

    20. Isomer Separation

      C60-Mediated Molecular Shape Sorting: Separation and Purification of Geometrical Isomers

      Moumita Rana, R. Bharathanatha Reddy, Bibhuti Bhusan Rath and Dr. Ujjal K. Gautam

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201408981

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      Pick and choose: The ability of C60 to form crystals with molecules of a suitable geometry under ambient conditions was used to develop a method to separate geometrical isomers of molecules such as xylene and trimethylbenzene. The versatility of this approach is demonstrated by preparing a C60–trimethylbenzene solvate crystal, where the purity of the separated isomers is much higher than the commercially available products.

    21. Cooperative Effects

      Synthesis and Ligand Modification Chemistry of a Molybdenum Dinitrogen Complex: Redox and Chemical Activity of a Bis(imino)pyridine Ligand

      Grant W. Margulieux, Zoë R. Turner and Prof. Paul J. Chirik

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201408725

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      Good golly Miss ‘Moly’: A molybdenum dinitrogen complex supported by a redox-active bis(imino)pyridine ligand has been synthesized and structurally characterized. Unique N[BOND]H addition chemistry involving metal–ligand cooperativity has been observed with ammonia and aryl hydrazines, as well as primary and secondary amines. Such transformations are of relevance for synthetic schemes for the interconversion of ammonia and its elements.

    22. Porphyrinoids

      Neo-Fused Hexaphyrin: A Molecular Puzzle Containing an N-Linked Pentaphyrin

      Pingchun Wei, Kai Zhang, Dr. Xin Li, Deying Meng, Prof. Dr. Hans Ågren, Prof. Dr. Zhongping Ou, Prof. Dr. Seikweng Ng, Prof. Dr. Hiroyuki Furuta and Prof. Dr. Yongshu Xie

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201408307

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      Fusion, confusion? Ring fusion of neo-confused hexaphyrin ( 1 led to the bicyclic neo-fused hexaphyrin 2, and subsequent CuII coordination triggered a ring opening reaction to afford a contracted N-linked pentaphyrin 3. The reactive N[BOND]C bonds in the porphyrinoid macrocycles play an important role.

    23. Natural Product Synthesis | Hot Paper

      Total Synthesis of the Tetracyclic Antimalarial Alkaloid (±)-Myrioneurinol

      Anthony J. Nocket and Prof. Dr. Steven M. Weinreb

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407810

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      Malaria’s worst nightmare: A total synthesis of the tetracyclic antimalarial Myrioneuron alkaloid (±)-myrioneurinol features three highly diastereoselective reactions as the key steps: an intramolecular Michael addition of a lactam titanium enolate to an α,β-unsaturated ester, a conjugate addition of a malonate enolate to a nitrosoalkene, and an intramolecular aza-Sakurai reaction.

    24. Boron Compounds

      Isolation of a Three-Coordinate Boron Cation with a Boron–Sulfur Double Bond

      Dr. Daniel Franz, Dr. Elisabeth Irran and Prof. Dr. Shigeyoshi Inoue

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407809

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      A healthy relationship: The first three-coordinate boron cation with a boron–sulfur double bond has the shortest B[BOND]S distance reported for a molecular complex. In the calculated LUMO, the contribution from the boron center confirms that the compound is a boron-centered cation. The HOMO−1 reveals the π interaction which is the cause of the close contact between B and S.

    25. Semihydrogenation

      A Palladium Nanoparticle–Nanomicelle Combination for the Stereoselective Semihydrogenation of Alkynes in Water at Room Temperature

      Eric D. Slack, Christopher M. Gabriel and Prof. Dr. Bruce H. Lipshutz

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407723

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      Nano, meet nano! The addition of NaBH4 to Pd(OAc)2 in water containing nanomicelles leads to generation of H2 and Pd nanoparticles. This combination leads to clean and highly selective conversion of alkynes to Z-alkenes at room temperature. The aqueous mixture is smoothly recycled without loss of reagent activity, stereochemical outcome, or yield. Furthermore, many functional groups are tolerated under these green conditions.

    26. Chirality Transfer

      Supramolecular Architectures from Bent-Core Dendritic Molecules

      Dr. Miguel Cano, Dr. Antoni Sánchez-Ferrer, Prof. Dr. José Luis Serrano, Dr. Nélida Gimeno and Prof. Dr. M. Blanca Ros

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407705

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      Twist of fate: Achiral, ionic bent-core dendrimers can not only lead to different bent-core liquid crystals (BCLCs) but also to a variety of aggregates in water, such as rods, spheres, nontwisted, or twisted fibers, and helical ribbons that lead to tubules. The conformational chirality of bent-core molecules in BCLCs can also be translated to chiral supramolecular architectures in the presence of a solvent.

    27. Circular Helicates

      Formation of a Dimer of Trinuclear Helicates which Encapsulates an Array of Six Hydrogen-Bonded Anions

      Robert A. Faulkner, Dr. Lindsay P. Harding, Joshua Higginson, Prof. Craig R. Rice and Christopher Slater

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407645

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      Cu does the twist: Cu2+ ions react with ligand L, containing two bidentate pyridyl-thiazole units linked by 1,3-diaminophenylene, to form a dinuclear double helicate [Cu2L2]4+. [Cu2L2]4+ reacts with OPO3H2 ions (0.5 equiv) to give the unsaturated double helicate [Cu2L2(OPO3H2)]3+. Further reaction of [Cu2L2(OPO3H2)]3+ with OPO3H2 yields a trinuclear circular helicate which self-assembles into a hexameric cluster [{Cu3L3(OPO3H2)3}2]6+ (see structure).

    28. Self-Healing Materials

      A Rapidly Self-Healing Supramolecular Polymer Hydrogel with Photostimulated Room-Temperature Phosphorescence Responsiveness

      Hui Chen, Prof. Xiang Ma, Dr. Shuaifan Wu and Prof. He Tian

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407402

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      A supramolecular polymeric hydrogel forms by host–guest recognition between a β-cyclodextrin polymer and an α-bromonaphthalene polymer without any additional gelators. This hydrogel can self-heal within only about one minute under ambient atmosphere without any additive, and can be excited to engender photostimulated room temperature phosphorescence (RTP) emission when azobenzene polymer is introduced.

  21. Essays

    1. History of Science

      Theodore William Richards: Apostle of Atomic Weights and Nobel Prize Winner in 1914

      Prof. Dr. Dudley R. Herschbach

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201407464

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      In recognition of his exact determinations of the atomic weights of a large number of the chemical elements, T. W. Richards received the Nobel Prize in Chemistry in 1914. His meticulous techniques resulted in “a degree of accuracy never before attained”. This Essay follows Richards from his precocious youth to becoming a celebrated chemist and emphasizes his dedication to foresee likely sources of error and how to avoid them.

  22. Highlights

    1. Photoredox Catalysis

      Oxidative Photoredox-Catalytic Activation of Aliphatic Nucleophiles for C(sp3)–C(sp2) Cross-Coupling Reactions

      Dr. Emanuela Jahn and Dr. Ullrich Jahn

      Article first published online: 16 OCT 2014 | DOI: 10.1002/anie.201408748

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      In the light you will find the road (Led Zeppelin): Visible-light photoredox catalysis leads the way in overcoming the reactivity limitations of alkyl nucleophiles in cross-coupling reactions. Iridium-triggered oxidative photoredox activation of alkyltrifluoroborate or carboxylic acids affords alkyl radicals, which undergo nickel-catalyzed cross-coupling reactions.

  23. Communications

    1. Metalloenzymes

      Iron(III) Located in the Dinuclear Metallo-β-Lactamase IMP-1 by Pseudocontact Shifts

      Thomas J. Carruthers, Dr. Paul D. Carr, Dr. Choy-Theng Loh, Dr. Colin J. Jackson and Prof. Gottfried Otting

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408693

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      Metal detector: Pseudocontact shifts measured by NMR spectroscopy allow the accurate determination of the location of paramagnetic metal ions in the active site of dinuclear metalloenzymes. Using this method a [FeZn]-complex of the metallo-β-lactamase IMP-1 could be identified and characterized.

    2. Metal Atom Wires

      A Motif for Infinite Metal Atom Wires

      Xi Yin, Steven A. Warren, Yung-Tin Pan, Kai-Chieh Tsao, Dr. Danielle L. Gray, Dr. Jeffery Bertke and Prof.Dr. Hong Yang

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408461

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      Totally wired: A new motif for the synthesis of 1D metal atom wire crystal is described in which Pd/Pt heterometallic and Pd atom chain structures were formed. The picture depicts an SEM micrograph of a needle-like crystal of the metal atom wire compound and representations of its molecular building blocks.

    3. Organocatalysis

      Lewis Base Catalyzed Aerobic Oxidative Intermolecular Azide–Zwitterion Cycloaddition

      Wenjun Li and Prof. Dr. Jian Wang

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408265

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      The works: The discovery of a novel aerobic oxidative intermolecular azide–zwitterion reaction catalyzed by an organocatalyst is presented. It is demonstrated that the merger of the Lewis base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and electron-deficient olefins generates reactive zwitterion intermediates, which readily participate in cycloaddition reactions with an array of azides, thus providing facile entry to fully or highly substituted 1,2,3-triazole frameworks.

    4. Helical Structures

      Construction of a Highly Distorted Benzene Ring in a Double Helicene

      Dr. Sigma Hashimoto, Soichiro Nakatsuka, Prof. Dr. Masaharu Nakamura and Prof. Dr. Takuji Hatakeyama

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408390

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      Bent on helices: A P-fused double helicene consisting of a highly distorted benzene, with a bending angle of 23°, has been synthesized by a tandem intramolecular phospha-Friedel–Crafts reaction. Despite distortion and reduced aromaticity, the proposed molecule shows thermal and chemical stability, and can be converted into the corresponding C2-symmetric bis(phosphine).

    5. Oxygen Storage | Hot Paper

      Metal–Organic Frameworks for Oxygen Storage

      Dr. Jared B. DeCoste, Dr. Mitchell H. Weston, Patrick E. Fuller, Trenton M. Tovar, Gregory W. Peterson, Dr. M. Douglas LeVan and Dr. Omar K. Farha

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408464

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      MOFs store oxygen too: Two metal–organic frameworks with open metal sites store oxygen at capacities far greater than that of an empty cylinder and are comparable to the state-of-the-art oxygen storage materials. Self-assembled materials allow for rational design of materials for adsorption of specific gases.

    6. Supported Catalysts

      Bulky Aryloxide Ligand Stabilizes a Heterogeneous Metathesis Catalyst

      Dr. Matthew P. Conley, Dr. William P. Forrest, Dr. Victor Mougel, Prof. Dr. Christophe Copéret and Prof. Dr. Richard R. Schrock

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408880

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      Like a rock: Grafting a W-oxo alkylidene, containing bulky adamantyl-substituted phenoxy ligands, onto partially dehydroxylated silica generates a very active and stable metathesis catalyst. This large ligand allows efficient terminal alkene homocoupling with a turnover number (TON) exceeding 75 000.

    7. Bioimaging

      Mitochondria-Targeted Cancer Therapy Using a Light-Up Probe with Aggregation-Induced-Emission Characteristics

      Dr. Qinglian Hu, Dr. Meng Gao, Guangxue Feng and Prof.Dr. Bin Liu

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408897

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      Lighting up mitochondria: A mitochondria-targeting probe (AIE-mito-TPP) has been developed, comprising a triphenylphosphine (TPP) moiety conjugated to a fluorogen, which can undergo aggregation-induced emission (AIE). The preferential aggregation and subsequent emission of AIE-mito-TPP within cancer-cell mitochondria makes them a potential agent for cancer-cell imaging and therapy.

  24. Cover Pictures

    1. Membrane-Spanning DNA Nanopores with Cytotoxic Effect

      Dr. Jonathan R. Burns, Noura Al-Juffali, Dr. Sam M. Janes and Dr. Stefan Howorka

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201409587

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      Reducing the viability of cancerous tissues is relevant in biomedicine and basic research. In their Communication (DOI: 10.1002/anie.201405719), S. Howorka et al. show that cancer cells can be killed by rupturing their plasma membrane with DNA nanopores. The piercing of cells only occurs when the DNA pores carry an outer hydrophobic belt for bilayer insertion. Future development will pave the way for targeting specific cancer types or for the more general shuttling of drugs into cells.

  25. Communications

    1. C[BOND]H Functionalization | Very Important Paper

      Ruthenium–Porphyrin-Catalyzed Diastereoselective Intramolecular Alkyl Carbene Insertion into C[BOND]H Bonds of Alkyl Diazomethanes Generated In Situ from N-Tosylhydrazones

      Annapureddy Rajasekar Reddy, Cong-Ying Zhou, Zhen Guo, Jinhu Wei and Prof. Dr. Chi-Ming Che

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408102

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      Nose to tail: With a ruthenium–porphyrin catalyst, alkyl diazomethanes generated in situ from N-tosylhydrazones underwent efficient intramolecular C(sp3)[BOND]H insertion to give substituted tetrahydrofurans and pyrrolidines (see scheme) in a reaction that can be viewed as a reductive coupling between C[DOUBLE BOND]O and C[BOND]H bonds to form a new C[BOND]C bond. This transformation was applied in a concise synthesis of (±)-pseudoheliotridane.

    2. Iron Catalysis

      Iron-Induced Regio- and Stereoselective Addition of Sulfenyl Chlorides to Alkynes by a Radical Pathway

      Dr. Masayuki Iwasaki, Tomoya Fujii, Prof. Dr. Kiyohiko Nakajima and Prof. Dr. Yasushi Nishihara

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408121

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      Radical action: Regio- and stereoselective chlorothiolation of alkynes is achieved with an inexpensive and abundant iron catalyst. The reaction simultaneously installs chloro and sulfenyl moieties on terminal and internal alkynes, providing synthetically useful tri- and tetrasubstituted alkenes with excellent selectivity by a radical pathway. The utility of the reaction is shown by transformations of the adducts using cross-coupling reactions.

    3. Kinase Sensing

      Differential Sensing of MAP Kinases Using SOX-Peptides

      Dr. Diana Zamora-Olivares, Dr. Tamer S. Kaoud, Dr. Jiney Jose, Prof. Andrew Ellington, Prof. Kevin N. Dalby and Prof. Eric V. Anslyn

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201408256

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      SOX it to the kinases: Five SOX peptides are used to classify groups of mitogen-activated protein kinases (MAPK) and their isoforms using chemometrics. The score plots show excellent classification and accuracy, while support vector machine analysis serves to quantify ERK and an ERK inhibitor concentration in kinase mixtures. Examination of the loading plots reveals cross-reactivity among the peptides, and some unexpected results.

    4. Biocatalysis

      Artificial Multienzyme Supramolecular Device: Highly Ordered Self-Assembly of Oligomeric Enzymes In Vitro and In Vivo

      Dr. Xin Gao, Shuai Yang, Chengcheng Zhao, Prof. Yuhong Ren and Prof. Dongzhi Wei

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201405016

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      The more the merrier: A two-dimensional layer-like supramolecular assembly of octameric leucine dehydrogenase and dimeric formate dehydrogenase was generated in vitro and in vivo by combining enzyme oligomerization and protein–protein interaction properties. This multienzyme structure had greater stability and higher NAD(H) recycling efficiency than unassembled enzymes when applied to a coenzyme recycling system.

    5. Antitumor Vaccines

      A Fully Synthetic Four-Component Antitumor Vaccine Consisting of a Mucin Glycopeptide Antigen Combined with Three Different T-Helper-Cell Epitopes

      Dipl.-Chem. Björn Palitzsch, Dipl.-Chem. Sebastian Hartmann, Dipl.-Chem. Natascha Stergiou, Dipl.-Chem. Markus Glaffig, Prof. Dr. Edgar Schmitt and Prof. Dr. Horst Kunz

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201406843

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      The criss-cross formation of squaric acid diamides was used in the synthesis of anticancer vaccines in which a tumor-associated MUC1 glycopeptide antigen is combined with three different bacterial T-helper-cell epitopes. Without support by complete Freund’s adjuvant, the four-component vaccine elicits strong a immune responses in mice and predominantly protective IgG antibodies that recognize human breast cancer cells.

    6. Coordination Complexes

      Synthesis of Square-Planar Aluminum(III) Complexes

      Emily J. Thompson, Thomas W. Myers and Louise A. Berben

      Article first published online: 15 OCT 2014 | DOI: 10.1002/anie.201407098

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      On a plain: Two square-planar complexes of aluminum(III) with chloride and hydride ligands have been synthesized (see picture; C gray, N blue, Al crimson, Cl green). These are supported by tridentate bis(imino)pyridine ligands that are reduced by two electrons. The AlIII ion in each is Lewis acidic enough to bind 2,6-lutidine.