Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 32

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. Book Reviews

    1. Fundamental Concepts in Heterogeneous Catalysis. By Jens K. Nørskov, Felix Studt, Frank Abild-Pedersen and Thomas Bligaard.

      Francesc Illas

      Article first published online: 27 JUL 2015 | DOI: 10.1002/anie.201506018

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      John Wiley and Sons, Hoboken 2014. 208 pp., hardcover, € 83.70.—ISBN 978-1118888957

  2. Communications

    1. Diborane(6)

      The Hexacyanodiborane(6) Dianion [B2(CN)6]2−

      Johannes Landmann, Dr. Jan A. P. Sprenger, Michael Hailmann, Vera Bernhardt-Pitchougina, Prof. Dr. Helge Willner, Dr. Nikolai Ignat'ev, Priv.-Doz. Dr. Eduard Bernhardt and Prof. Dr. Maik Finze

      Article first published online: 27 JUL 2015 | DOI: 10.1002/anie.201504579

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      Highly stable B[BOND]B σ-bond: The homoleptic hexacyanodiborane(6) dianion [B2(CN)6]2− (see picture) is chemically very robust and its salts are thermally highly stable. Salts of the diborane(6) dianion are readily accessible in high yields from salts of the anions B(CN)32− and [BHal(CN)3] (Hal=F, Br). Mechanistic studies show that the [B2(CN)6]2− dianion is formed by an unprecedented SN2-type reaction.

    2. Main-Group Radicals

      Isolation and Characterization of a Bismuth(II) Radical

      Ryan J. Schwamm, Dr. Jeffrey R. Harmer, Dr. Matthias Lein, Dr. Christopher M. Fitchett, Dr. Simon Granville and Dr. Martyn P. Coles

      Article first published online: 27 JUL 2015 | DOI: 10.1002/anie.201504632

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      Reduction of a BiIII compound affords the first isolable BiII radical (see scheme; Cl green, Si magenta, O red, N blue). X-ray diffraction confirms a two-coordinate metal with no short intermolecular contacts; SQUID measurements indicate a paramagnetic compound with a single unpaired electron. EPR and DFT results are consistent with a metal-centered radical, with the unpaired electron predominantly in a p-type orbital on Bi.

    3. Atom–Molecule Reactions

      From Gas-Phase to Liquid-Water Chemical Reactions: The Fluorine Atom Plus Water Trimer System

      Prof. Guoliang Li, Prof. Qian-Shu Li, Dr. Yaoming Xie and Prof. Henry F. Schaefer III

      Article first published online: 27 JUL 2015 | DOI: 10.1002/anie.201505075

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      The potential energy profile for the F+(H2O)3[RIGHTWARDS ARROW]HF+(H2O)2OH reaction has been investigated using the “gold standard” CCSD(T) method with correlation-consistent basis sets up to cc-pVQZ. Four different reaction pathways have been found and these are related, both geometrically and energetically.

    4. Pseudoreversible Reaction

      Ruthenium-Catalyzed O- to S-Alkyl Migration: A Pseudoreversible Barton–McCombie Pathway

      William Mahy, Dr. Pawel Plucinski, Dr. Jesús Jover and Prof. Dr. Christopher G. Frost

      Article first published online: 27 JUL 2015 | DOI: 10.1002/anie.201505280

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      A radical step in a new direction: A practical ruthenium-catalyzed O- to S-alkyl migration affords structurally diverse thiooxazolidinones in excellent yields. Experimental and computational studies suggest a pseudoreversible radical pathway drawing mechanistic parallels to the classic Barton–McCombie reaction.

    5. Asymmetric Annulation

      Hydroxoiridium/Chiral Diene Complexes as Effective Catalysts for Asymmetric Annulation of α-Oxo- and Iminocarboxamides with 1,3-Dienes

      Miyuki Hatano and Dr. Takahiro Nishimura

      Article first published online: 27 JUL 2015 | DOI: 10.1002/anie.201505382

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      [3+2] annulation: The asymmetric [3+2] annulation of α-oxo- and α-iminocarboxamides with 1,3-dienes catalyzed by hydroxoiridium/chiral diene complexes was achieved. The reaction gives the corresponding γ-lactams in high yields with high enantioselectivity.

    6. Magnetic Anisotropy

      Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+ in Aqueous Solution

      Dr. Octavia A. Blackburn, Dr. Nicholas F. Chilton, Katharina Keller, Dr. Claudia E. Tait, Dr. William K. Myers, Prof. Eric J. L. McInnes, Dr. Alan M. Kenwright, Prof. Paul D. Beer, Prof. Christiane R. Timmel and Prof. Stephen Faulkner

      Article first published online: 27 JUL 2015 | DOI: 10.1002/anie.201503421

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      F makes the difference: [Yb⋅DTMA⋅OH2]3+ and [Yb⋅DTMA⋅F]2+ are in slow exchange on the NMR timescale (kex<2000 s−1), and profound differences are observed in the NMR and EPR spectra of these species. This behavior is explained by changes in the magnetic anisotropy of the YbIII ground state from easy-axis to easy-plane type (see picture).

  3. Essays

    1. Supramolecular Systems

      You have full text access to this OnlineOpen article
      Rise of the Molecular Machines

      Dr. Euan R. Kay and Prof. David A. Leigh

      Article first published online: 27 JUL 2015 | DOI: 10.1002/anie.201503375

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      They’re coming! From Feynman to ribosome mimics, the evolution of artificial molecular machines is told in terms of key inventions and the questions the field continues to face, including design philosophies and what to make and why.

  4. Book Reviews

    1. Fundamentals and Applications of Organic Electrochemistry. Synthesis, Materials, Devices. By Toshio Fuchigami, Mahito Atobe and Shinsuke Inagi.

      Siegfried R. Waldvogel

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201505828

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      John Wiley and Sons, Hoboken 2014. 238 pp., hardcover, € 75.00.—ISBN 978-1118653173

  5. Communications

    1. Carbohydrate Immunology | Hot Paper

      Chemical Synthesis Elucidates the Immunological Importance of a Pyruvate Modification in the Capsular Polysaccharide of Streptococcus pneumoniae Serotype 4

      Dr. Claney L. Pereira, Andreas Geissner, Dr. Chakkumkal Anish and Prof. Dr. Peter H. Seeberger

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201504847

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      Unusually Protective. In the search for a glycan epitope for protection against Streptococcus pneumoniae serotype 4, total synthesis of the repeating unit (see structure) enabled the identification of pyruvate as a crucial determinant of immunogenicity. This lays the foundation for the development of a new antibacterial vaccine candidate against Streptococcus pneumoniae serotype 4.

    2. Hypervalent Compounds

      Silicates as Latent Alkyl Radical Precursors: Visible-Light Photocatalytic Oxidation of Hypervalent Bis-Catecholato Silicon Compounds

      Dr. Vincent Corcé, Lise-Marie Chamoreau, Dr. Etienne Derat, Prof. Dr. Jean-Philippe Goddard, Dr. Cyril Ollivier and Prof. Dr. Louis Fensterbank

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201504963

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      Silicates can be used as latent alkyl radical precursors. Upon visible-light photocatalytic oxidation of easily accessed and bench-stable bis-catecholato silicates, a series of functionalized alkyl radicals, including highly reactive primary ones have been engaged in homolytic transformations. This oxidative photocatalyzed process can be efficiently merged with nickel catalysis for C[BOND]C coupling.

    3. Photocatalysis

      Room-Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

      Franck Le Vaillant, Dr. Thibaut Courant and Prof. Dr. Jerome Waser

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201505111

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      EBX-cellent: A range of alkynes can be synthesized in good yields by the direct reaction of readily available carboxylic acids with ethynylbenziodoxolone (EBX) reagents in the presence of an iridium photocatalyst (see figure). This decarboxylative alkynylation reaction proceeds at room temperature under visible light irradiation, and could be applied to silyl-, aryl-, and alkyl-substituted alkynes.

    4. Biodegradable Polymers

      Acid-Labile Thermoresponsive Copolymers That Combine Fast pH-Triggered Hydrolysis and High Stability under Neutral Conditions

      Dr. Qilu Zhang, Zhanyao Hou, Benoit Louage, Dr. Dingying Zhou, Nane Vanparijs, Prof. Dr. Bruno G. De Geest and Prof. Dr. Richard Hoogenboom

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201505145

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      Breaking the rules: Thermoresponsive polymers with both dimethyldioxolane and hydroxyethyl side chains were hydrolyzed rapidly under slightly acidic conditions while being stable at pH 7.4 or during storage: important properties for biomedical applications. Thus, hydrolysis of the acid-labile cyclic-acetal groups was accelerated by the presence of hydroxy groups, which led to enhanced hydration of the collapsed copolymer globules (see picture).

    5. Polymorphism

      Structure Elucidation and Characterization of Different Thyroxine Polymorphs

      Santanu Mondal and Prof. Dr. Govindasamy Mugesh

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201505281

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      You’d better shape up: Two new polymorphs of the thyroid hormone thyroxine were characterized and it was found that polymorphism has a significant effect on the solubility and stability of this clinically useful compound. The conformational changes alter the electronic properties of the iodine atoms and the reactivity of the C[BOND]I bonds, which could have a significant effect on the hormone activity.

    6. Oligosaccharides

      Synthetic Enterobacterial Common Antigen (ECA) for the Development of a Universal Immunotherapy for Drug-Resistant Enterobacteriaceae

      Dr. Lin Liu, Jingying Zha, Dr. Antonio DiGiandomenico, Dr. Douglas McAllister, Dr. C. Kendall Stover, Dr. Qun Wang and Prof. Geert-Jan Boons

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201505420

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      Hitting the sweet spot: All Enterobacteriaceae express the polysaccharide enterobacterial common antigen (ECA), which is an attractive target for the development of universally acting immunotherapies. ECA-derived oligosaccharides were chemically synthesized and used to uncover immunodominant epitopes and develop a monoclonal antibody showing broad recognition of Enterobacteriaceae.

    7. Protein Profiling

      Proteome-Wide Profiling of Targets of Cysteine-reactive Small Molecules by using Ethynyl Benziodoxolone Reagents

      Daniel Abegg, Dr. Reto Frei, Luca Cerato, Dr. Durga Prasad Hari, Chao Wang, Prof. Dr. Jerome Waser and Prof. Dr. Alexander Adibekian

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201505641

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      Good grip: Alkynyl benziodoxolones (EBX reagents) swiftly and highly selectively react with cysteine residues in cellular lysates and in living cells under physiological conditions. A “clickable” EBX probe allowed identification of the biological targets of natural product curcumin. This new method for cysteine labeling is particularly useful for various chemical proteomics applications.

    8. Homogeneous Catalysis

      Alkaline-Earth-Promoted CO Homologation and Reductive Catalysis

      Mathew D. Anker, Prof. Michael S. Hill, Dr. John P. Lowe and Dr. Mary F. Mahon

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201505851

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      I should COCO: Reaction between a β-diketiminato magnesium hydride and carbon monoxide results in the isolation of a dimeric cis-enediolate species through the reductive coupling of two CO molecules. Under catalytic conditions with PhSiH3, an observable magnesium formyl species may be intercepted for the mild reductive cleavage of the CO triple bond.

  6. Cover Pictures

    1. Copper and Silver Carbene Complexes without Heteroatom-Stabilization: Structure, Spectroscopy, and Relativistic Effects

      M. Sc. Matthias W. Hussong, Dipl.-Chem. Wilhelm T. Hoffmeister, Dr. Frank Rominger and Prof. Dr. Bernd F. Straub

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201506279

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      Without heteroatom stabilization the carbenoid character of isostructural Group 11 metal carbene complexes increases in the order Au≪Cu<Ag as shown by B. F. Straub et al. in their Communication (10.1002/anie.201504117). The silver snow leopard breaking a bar of its cage symbolizes the marginal silver-to-carbene back-bonding and the high carbenoid character. The escaping copper lynx shows the short lifetime of the copper carbene complex. The gold tiger symbolizes the remarkable stability of the gold carbene complex. The “E=mc2” refers to the relativistic effects in gold’s valence shell.

  7. Communications

    1. Radical Reactions

      Silver-Catalyzed Cross-Coupling of Isocyanides and Active Methylene Compounds by a Radical Process

      Jianquan Liu, Zhenhua Liu, Dr. Peiqiu Liao, Dr. Lin Zhang, Prof. Tao Tu and Prof. Xihe Bi

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201504254

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      Silver-tongued radicals: A novel C[BOND]C bond-forming reaction was developed through the silver-catalyzed radical cross-coupling of isocyanides and active methylene compounds to deliver β-aminoenones and tricarbonylmethanes. These two transformations are 100 % atom economical and the formation of β-aminoenones is stereoselective. A radical mechanism is proposed on the basis of experimental studies.

    2. Photocatalysis

      The Cleavage of a C[BOND]C Bond in Cyclobutylanilines by Visible-Light Photoredox Catalysis: Development of a [4+2] Annulation Method

      Jiang Wang and Prof. Dr. Nan Zheng

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201504076

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      Cyclohexene derivatives are obtained by a mild procedure using visible-light photocatalysis. Monocyclic and bicyclic cyclobutylanilines successfully undergo intermolecular [4+2] annulation with terminal and internal alkynes to generate a variety of amine-substituted cyclohexenes including new hydrindan and decalin derivatives with good to excellent diastereoselectivity. dtbbpy=4,4′-di-tert-butyl-2,2′-bipyridine, ppy=2-phenylpyridine.

    3. Ion–DNA Interactions

      Can A Denaturant Stabilize DNA? Pyridine Reverses DNA Denaturation in Acidic pH

      Dr. Guillem Portella, Dr. Montserrat Terrazas, Dr. Núria Villegas, Prof. Dr. Carlos González and Prof. Dr. Modesto Orozco

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201503770

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      The thermal stability of duplex DNA can be decreased by addition of pyridine, a well-known denaturant. In acidic solutions, pyridine is protonated and displays its role as DNA renaturant, which increases the melting temperature of the duplex further than a solution of NaCl at the same concentration. This behavior is specifically observed for pyridine.

    4. Structure Elucidation

      Discovery and Structure Determination of an Unusual Sulfide Telluride through an Effective Combination of TEM and Synchrotron Microdiffraction

      Felix Fahrnbauer, Dr. Tobias Rosenthal, Tilo Schmutzler, Priv.-Doz. Dr. Gerald Wagner, Dr. Gavin B. M. Vaughan, Dr. Jonathan P. Wright and Prof. Dr. Oliver Oeckler

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201503657

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      Treasure quest: The complementary use of electron diffraction and microfocused synchrotron radiation enables innovative and accurate structure analyses of novel compounds in heterogeneous microcrystalline materials. The sulfide telluride Pb8Sb8S15Te5 was discovered this way. It adopts an unusual tetragonal structure type with building blocks that resemble NaCl-type fragments as well as chain-like units typical for sulfides.

    5. Fused-Ring Systems

      Extended Corannulenes: Aromatic Bowl/Sheet Hybridization

      Dr. Amit K. Dutta, Prof. Dr. Anthony Linden, Dr. Laura Zoppi, Prof. Dr. Kim K. Baldridge and Prof. Dr. Jay S. Siegel

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201503553

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      Caught and bowled: Photophysical and voltammetric studies together with high-level computations have been carried out on polynuclear aromatic hydrocarbons with distinct planar and bowl regions. A buckybowl–graphene hybrid was synthesized (see X-ray structure) as a model by activation of a C(Ar)[BOND]F bond. Curvature and extended π-effects were found to affect the properties of such materials.

    6. EPR Spectroscopy

      g-Engineering in Hybrid Rotaxanes To Create AB and AB2 Electron Spin Systems: EPR Spectroscopic Studies of Weak Interactions between Dissimilar Electron Spin Qubits

      Dr. Antonio Fernandez, Dr. Eufemio Moreno Pineda, Dr. Christopher A. Muryn, Dr. Stephen Sproules, Dr. Fabrizio Moro, Dr. Grigore A. Timco, Prof. Eric J. L. McInnes and Prof. Richard E. P. Winpenny

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201504487

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      Spin control: Hybrid [2]rotaxanes and pseudorotaxanes, such as {[Cu(hfac)2][PyCH2NH2CH2CH2Ph][Cr7Ni(μ-F)8(O2CtBu)16]} (see picture; Hhfac=1,1,1,6,6,6-hexafluoroacetylacetone), are reported where the magnetic interaction between dissimilar spins is controlled to create AB and AB2 electron spin systems, allowing independent control of weakly interacting S=equation image centers. Atom colors: Cr=green, Ni=purple, Cu=dark blue, F=yellow, O=red, C=gray, N=pale blue.

    7. Membrane Proteins

      The Role of the NDQ Motif in Sodium-Pumping Rhodopsins

      Dr. Keiichi Inoue, Dr. Masae Konno, Dr. Rei Abe-Yoshizumi and Prof. Hideki Kandori

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201504549

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      Ion transport: The conserved NDQ (Asn, Asp, Gln) motif in Krokinobacter rhodopsin 2 (KR2), a novel light-driven outward Na+ pump, is found to play a specific role. The D116 residue receives and sequesters protons for Na+ uptake and the uptake process is kinetically optimized by Q123. The N112 residue participates in Na+ binding in the O photointermediate. Thus, the NDQ motif works cooperatively for vectorial Na+ transport.

    8. Lantibiotics

      Pinensins: The First Antifungal Lantibiotics

      Dr. Kathrin I. Mohr, Dr. Carsten Volz, Dr. Rolf Jansen, Dr. Victor Wray, Dr. Judith Hoffmann, Dipl.-Ing. Steffen Bernecker, Priv.-Doz. Dr. Joachim Wink, Dr. Klaus Gerth, Prof. Dr. Marc Stadler and Prof. Dr. Rolf Müller

      Article first published online: 24 JUL 2015 | DOI: 10.1002/anie.201500927

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      (L)antifungals: Decades of research in the field of lantibiotics have led to the discovery of numerous compounds with antibacterial activity. Herein, the first antifungal lantibiotics are presented. Pinensins originate from a Gram-negative producer, Chitinophaga pinensis. Antifungal activity, structure elucidation, and an in-depth bioinformatic analysis of the biosynthetic gene cluster establish the basis for promising future research with the aim of fighting fungal infections.

    9. Transition-Metal Catalysis

      Nickel-Catalyzed Cyclopropanation with NMe4OTf and nBuLi

      Stefan A. Künzi, Dr. Juan Manuel Sarria Toro, Dr. Tim den Hartog and Prof. Dr. Peter Chen

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201505482

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      Setting the record straight: Nickel catalyzes the cyclopropanation of unactivated olefins with in situ generated lithiomethyl trimethylammonium triflate as a methylene donor. A mechanism is proposed that involves the generation of a reactive nickel carbene to explain several interesting observations. Additionally, these findings shed light on a report by Franzen and Wittig published in 1960 that was later retracted owing to irreproducibility.

    10. Aza-Diels–Alder Reactions

      Regio- and Enantioselective Aza-Diels–Alder Reactions of 3-Vinylindoles: A Concise Synthesis of the Antimalarial Spiroindolone NITD609

      Haifeng Zheng, Prof. Dr. Xiaohua Liu, Chaoran Xu, Yong Xia, Dr. Lili Lin and Prof. Dr. Xiaoming Feng

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201505717

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      An asymmetric aza-Diels–Alder reaction of 3-vinylindoles with isatin-derived ketimines leads to spiroindolone derivatives with high regio-, diastereo-, and enantioselectivity and also provides facile access to the valuable antimalarial drug NITD609. The stereoselectivity is thought to arise from π–π interactions between the two reactants and the chiral N,N′-dioxide ligand.

  8. Cover Pictures

    1. A New Perspective on Li–SO2 Batteries for Rechargeable Systems

      Hee-Dae Lim, Hyeokjun Park, Hyungsub Kim, Jinsoo Kim, Byungju Lee, Youngjoon Bae, Hyeokjo Gwon and Prof. Kisuk Kang

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201506193

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      A rechargeable Li–SO2 battery developed from a primary Li–SO2 cell is reported by K. Kang et al. in their Communication (DOI: 10.1002/anie.201504306). Lithium ions (yellow) and sulfur dioxide (blue) reversibly react with each other, leading to a high energy density and a superior energy efficiency of the rechargeable Li–SO2 battery. The energy efficiency of the rechargeable system is further enhanced by using catalysts.

    2. Single-Crystal Semiconductors with Narrow Band Gaps for Solar Water Splitting

      Assoc. Prof. Dr. Tuo Wang and Prof. Dr. Jinlong Gong

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201506277

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      Narrow-band-gap single-crystal semiconductors have been considered inappropriate for solar water splitting largely because of the photocorrosion issue. However, several exciting breakthroughs have shown that the instability and other drawbacks of these materials can be overcome. In their Minireview (DOI: 10.1002/anie.201503346), T. Wang and J. Gong describe recent research advances and highlight the most important approaches to using these semiconductors as efficient photoelectrodes.

    3. Chemical Evolution of a Bacterial Proteome

      Dr. Michael Georg Hoesl, M. Sc. Stefan Oehm, Dr. Patrick Durkin, Dr. Elise Darmon, Dr. Lauri Peil, Dr. Hans-Rudolf Aerni, Prof. Dr. Juri Rappsilber, Prof. Dr. Jesse Rinehart, Prof. Dr. David Leach, Prof. Dr. Dieter Söll and Prof. Dr. Nediljko Budisa

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201506522

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      A first step towards the creation of synthetic cells is described by N. Budisa et al. in their Communication on (DOI: 10.1002/anie.201502868). The chemical composition and the genetic code of an auxotrophic E. coli were changed in the frame of a long-term evolution experiment. During the experiment the cells were gradually forced to replace the natural building block tryptophan with thienopyrrolylalanine in their proteomes. This is the first step in the creation of synthetic life, which should be genetically and metabolically so far away from that found in nature that it cannot survive outside of the laboratory.

  9. Communications

    1. Raman Spectroscopy

      Experimental Detection of the Intrinsic Difference in Raman Optical Activity of a Photoreceptor Protein under Preresonance and Resonance Conditions

      Shojiro Haraguchi, Miwa Hara, Dr. Takahito Shingae, Dr. Masato Kumauchi, Prof. Dr. Wouter D. Hoff and Prof. Dr. Masashi Unno

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201505466

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      Pick and choose: Photoactive yellow protein was used to measure the effect of changing the excitation wavelength (λex) on the Raman optical activity (ROA) spectra of a protein. The data demonstrate that selecting an appropriate excitation wavelength is a key factor for extracting structural information on the protein active site using ROA spectroscopy.

    2. Organic Reductants | Hot Paper

      You have full text access to this OnlineOpen article
      Pushing the Limits of Neutral Organic Electron Donors: A Tetra(iminophosphorano)-Substituted Bispyridinylidene

      Samuel S. Hanson, Dr. Eswararao Doni, Kyle T. Traboulsee, Dr. Graeme Coulthard, Prof. Dr. John A. Murphy and Prof. Dr. C. Adam Dyker

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201505378

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      Unlocking max potential: The four strongly π-donating iminophosphorano substituents of compound 1 impart an impressive redox potential of −1.70 V versus saturated calomel electrode (SCE) for the 12+/1 redox couple, and make 1 the first organic donor able to reduce malononitriles and diakylarenesulfonamides without photoexcitation.

    3. Zeolite Catalysts | Very Important Paper

      Self-Pillared, Single-Unit-Cell Sn-MFI Zeolite Nanosheets and Their Use for Glucose and Lactose Isomerization

      Dr. Limin Ren, Dr. Qiang Guo, Prashant Kumar, Marat Orazov, Dandan Xu, Prof. Saeed M. Alhassan, Prof. K. Andre Mkhoyan, Prof. Mark E. Davis and Prof. Michael Tsapatsis

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201505334

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      The adventures of thin tin: Sn is introduced in the framework of single-unit-cell (2 nm thick) zeolite MFI lamellae, which are intergrown in a self-pillared arrangement to obtain a hierarchical micro/mesoporous Lewis acid catalyst. Its conversion and selectivity are better than those of other micro- and mesoporous Sn-containing catalysts for isomerization of mono- and di-sacharides.

    4. Peptides

      Design of Decorin-Based Peptides that Bind to Collagen I and their Potential as Adhesion Moieties in Biomaterials

      Dr. Stefania Federico, Dr. Benjamin F. Pierce, Dr. Susanna Piluso, Dr. Christian Wischke, Prof. Dr. Andreas Lendlein and Dr. Axel T. Neffe

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201505227

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      The ties that bind: The highly repetitive structure of the collagen-binding protein decorin allowed the design of peptides representative of each of its two distinct sides. Strongly binding peptides (red) derived from the inner surface were conjugated to a dye or dimerized. These peptides bind to collagen and provide a biomimetic tool for tailoring biomaterials by controlling mechanical properties or compound diffusion in collagen gels.

    5. Nanotheranostics

      X-ray Radiation-Controlled NO-Release for On-Demand Depth-Independent Hypoxic Radiosensitization

      Dr. Wenpei Fan, Prof. Wenbo Bu, Prof. Zhen Zhang, Dr. Bo Shen, Hui Zhang, Dr. Qianjun He, Dr. Dalong Ni, Dr. Zhaowen Cui, Dr. Kuaile Zhao, Dr. Jiwen Bu, Prof. Jiulin Du, Dr. Jianan Liu and Prof. Jianlin Shi

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504536

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      A novel nanotheranostic system based on X-ray radiation-controlled NO-release enables simultaneous luminescent imaging and controllable NO-sensitized radiation enhancement effects without depth dependence. The results will lead to the on-demand therapy of deep-seated solid tumors with very few adverse effects by simply manipulating the appropriate X-ray dose.

    6. Asymmetric Catalysis

      An Enantioselective Synthesis of Spirobilactams through Copper-Catalyzed Intramolecular Double N-Arylation and Phase Separation

      Jianguang Liu, Yingying Tian, Jialing Shi, Shasha Zhang and Prof. Dr. Qian Cai

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504589

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      Spirocyclic structures are versatile building blocks for functional chiral molecules. A copper-catalyzed double N-arylation was developed for the enantioselective synthesis of chiral spirobilactams. Enantioenriched spirobilactams were obtained with excellent ee values through precipitation of the racemate and simple solid–solution phase separation.

    7. Heterocycle Synthesis

      Synthesis of 3,4,5-Trisubstituted Isoxazoles from Morita–Baylis–Hillman Acetates by an NaNO2/I2-Mediated Domino Reaction

      Shashikant U. Dighe, Sushobhan Mukhopadhyay, Shivalinga Kolle, Dr. Sanjeev Kanojiya and Sanjay Batra

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504529

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      An efficient synthesis of highly substituted isoxazoles from the reaction of allyl acetates with NaNO2 by using I2 under oxidative conditions is demonstrated. The reactions proceed through an I2-assisted activation of the C[BOND]H bond α to the nitro group, nucleophilic addition, and subsequent [3+2] cycloaddition. DMF=N,N-dimethylformamide, DMSO=dimethylsulfoxide.

    8. C[BOND]H Activation

      RhIII-Catalyzed C[BOND]H Activation with Pyridotriazoles: Direct Access to Fluorophores for Metal-Ion Detection

      Dr. Ju Hyun Kim, Tobias Gensch, Dr. Dongbing Zhao, Linda Stegemann, Priv.-Doz. Dr. Cristian A. Strassert and Prof. Dr. Frank Glorius

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504757

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      Form(ation) follows function: The first C[BOND]H bond activation with pyridotriazoles as a coupling partner is made possible by using a RhIII catalyst. The pyridotriazoles serve as new carbene precursors in C[BOND]H activation allowing direct access to fluorescent scaffolds bearing a pyridine-type ligating group. These fluorophores can be applied as dual sensors for colorimetric sensing of Cu2+ ions and fluorescence sensing for Zn2+ ions.

    9. Perovskites | Hot Paper

      Rattling in the Quadruple Perovskite CuCu3V4O12

      Dr. Yasuhide Akizuki, Dr. Ikuya Yamada, Dr. Koji Fujita, Kazuya Taga, Dr. Takateru Kawakami, Dr. Masaichiro Mizumaki and Prof. Katsuhisa Tanaka

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504784

      Thumbnail image of graphical abstract

      Oversize me: CuCu3V4O12 is synthesized using a high-pressure technique. This compound adopts the cubic A-site ordered perovskite-type structure (space group Imequation image) with a valence distribution of Cu2+Cu2+3V4+4O12. It has oversized icosahedral cages in which loosely bound A-site Cu2+ ions rattle with a characteristic temperature (Einstein temperature) of ΘE≈55 K. This is the first demonstration of rattling in perovskites.

    10. Light-Emitting Diodes | Hot Paper

      Waterproof Alkyl Phosphate Coated Fluoride Phosphors for Optoelectronic Materials

      Dr. Hoang-Duy Nguyen, Dr. Chun Che Lin and Prof. Dr. Ru-Shi Liu

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504791

      Thumbnail image of graphical abstract

      The moisture instability of fluoride phosphors has limited their application in optoelectronic devices. Their waterproof properties can be improved by a hydrophobic coating layer, such as an alkyl phosphate. The luminous efficacy of warm white-light-emitting diodes (WLEDs) based on such coated phosphors is remarkably stable even under high-humidity and high-temperature conditions.

    11. Glycosylations

      Stereoselective Synthesis of α-3-Deoxy-D-manno-oct-2-ulosonic Acid (α-Kdo) Glycosides Using 5,7-O-Di-tert-butylsilylene-Protected Kdo Ethyl Thioglycoside Donors

      Jia-Sheng Huang, Wei Huang, Xue Meng, Xin Wang, Peng-Cheng Gao and Prof. Dr. Jin-Song Yang

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201505176

      Thumbnail image of graphical abstract

      A Kdo K.O.: The title compound is a common structural constituent of polysaccharides present in bacteria. An approach to stereospecific synthesis of α-Kdo glycosides was developed by using 5,7-O-di-tert-butylsilylene-protected Kdo ethyl thioglycoside donors (1). Various α-Kdo glycosidic linkages were constructed in good to excellent chemical yields with complete α-selectivity (2). M.S.=molecular sieves, NIS=N-iodosuccinimide, Tf=trifluoromethanesulfonyl.

    12. Cross-Coupling

      Catalytic Synthesis of N-Unprotected Piperazines, Morpholines, and Thiomorpholines from Aldehydes and SnAP Reagents

      Michael U. Luescher and Prof. Dr. Jeffrey W. Bode

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201505167

      Thumbnail image of graphical abstract

      SnAPcat! The identification of new ligands and reaction conditions provides a robust catalytic method for the synthesis of N-unprotected heterocycles using SnAP reagents. This catalytic variant expands the substrate scope to include previously inaccessible piperazines, morpholines, and thiomorpholines and establishes the basis for a catalytic enantioselective process through the use of chiral ligands.

    13. Protein Folding

      Frustration Sculpts the Early Stages of Protein Folding

      Dr. Eva Di Silvio, Prof. Maurizio Brunori and Prof. Stefano Gianni

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504835

      Thumbnail image of graphical abstract

      Diverging demands between folding and function cause a pattern of local frustration in proteins. By comparing the folding of proteins sharing nearly identical sequence and structure but displaying different frustration, it may be observed how frustration sculpts the early stages of folding whereas the late stages are more robust and biased by native topology.

    14. Gold Nanoparticle Stabilization

      Cooperative Gold Nanoparticle Stabilization by Acetylenic Phosphaalkenes

      Dr. Andreas Orthaber, Dr. Henrik Löfås, Dr. Elisabet Öberg, Dr. Anton Grigoriev, Dr. Andreas Wallner, Dr. S. Hassan M. Jafri, Dr. Marie-Pierre Santoni, Prof. Dr. Rajeev Ahuja, Prof. Dr. Klaus Leifer, Prof. Dr. Henrik Ottosson and Prof. Dr. Sascha Ott

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504834

      Thumbnail image of graphical abstract

      A dynamic ligand shell for the stabilization of small gold nanoparticles is obtained through cooperative binding of acetylenic phosphaalkenes. A variety of experimental and analytical methods demonstrates that the C[TRIPLE BOND]C as well as the P[DOUBLE BOND]C unit of the acetylenic phosphaalkene are essential for nanoparticle stabilization.

    15. Molecular Evolution

      A Versatile Approach Towards Nucleobase-Modified Aptamers

      Fabian Tolle, Dr. Gerhard M. Brändle, Daniel Matzner and Prof. Dr. Günter Mayer

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201503652

      Thumbnail image of graphical abstract

      Click to select: A versatile method for modular expansion of the chemical space of nucleic acid libraries has been developed. This method enables the generation of nucleobase-modified aptamers with unprecedented recognition properties. In situ reintroduction of the modification after enzymatic replication gives broad access to many chemical modifications, thus enabling the application of in vitro selection approaches beyond what is feasible to date.

    16. Foldamers

      Fine Tuning of β-Peptide Foldamers: a Single Atom Replacement Holds Back the Switch from an 8-Helix to a 12-Helix

      Dr. Amandine Altmayer-Henzien, Dr. Valérie Declerck, Dr. Jonathan Farjon, Prof. Dr. Denis Merlet, Dr. Régis Guillot and Prof. Dr. David J. Aitken

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504126

      Thumbnail image of graphical abstract

      Keep it long and slim. Although a stable 12-helix conformer is available to oligo-β-peptides constructed from cyclic monomers, when an aza-adapted N terminus is incorporated, the resulting hydrazino turn feature leads the foldamer to preferentially adopt a more slim-line 8-helix. This effect illustrates atomic-level programmable design for the fine tuning of peptide foldamer architectures.

    17. Carbohydrates

      Regioselective and 1,2-cis-α-Stereoselective Glycosylation Utilizing Glycosyl-Acceptor-Derived Boronic Ester Catalyst

      Akira Nakagawa, Masamichi Tanaka, Shun Hanamura, Dr. Daisuke Takahashi and Prof. Dr. Kazunobu Toshima

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504182

      Thumbnail image of graphical abstract

      Donors and acceptors: The title reaction of 1α,2α-anhydro glycosyl donors and diol glycosyl acceptors proceeded smoothly to give the corresponding 1,2-cis-α-glycosides with high stereo- and regioselectivities. The glycosylation method was successfully applied to the synthesis of an isoflavone glycoside.

    18. Lipid Bilayers

      Amphiphilic Nanoparticles Control the Growth and Stability of Lipid Bilayers with Open Edges

      Sun Hae Ra Shin, Prof. Hee-Young Lee and Prof. Kyle J. M. Bishop

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504362

      Thumbnail image of graphical abstract

      Nanoparticle surfactants that present mixtures of hydrophilic and hydrophobic ligands on their surface bind selectively at the open edge of bilayer membranes to stabilize amphiphile assemblies and control their growth. This general mechanism can be applied to inhibit formation of undesired assemblies such as cholesterol gallstones and to direct the growth of lipid nanostructures.

    19. Hydrogen-Evolution Reaction

      Coupling Mo2C with Nitrogen-Rich Nanocarbon Leads to Efficient Hydrogen-Evolution Electrocatalytic Sites

      Yipu Liu, Prof. Guangtao Yu, Prof. Guo-Dong Li, Yuanhui Sun, Prof. Tewodros Asefa, Prof. Wei Chen and Prof. Xiaoxin Zou

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504376

      Thumbnail image of graphical abstract

      Hybrid catalyst: An efficient hybrid hydrogen-evolution electrocatalyst containing molybdenum carbide nanoparticles embedded in nitrogen-rich carbon nanolayers has been synthesized in one-step from inexpensive precursors. The synergistic effect between Mo2C and N dopants was found to yield very active nonmetallic HER catalytic sites on the carbon nanolayers.

    20. Lithium-Ion Batteries

      Hydrothermal Synthesis of Unique Hollow Hexagonal Prismatic Pencils of Co3V2O8n H2O: A New Anode Material for Lithium-Ion Batteries

      Dr. Fangfang Wu, Prof. Shenglin Xiong, Prof. Yitai Qian and Prof. Shu-Hong Yu

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201503487

      Thumbnail image of graphical abstract

      Hydrothermal synthesis: A new phase of Co3V2O8n H2O hollow hexagonal prismatic pencils has been synthesized hydrothermally by varying the amount of NaOH in the reaction in the presence of NH4+ ions and absence of any template or surfactant (see picture). The excellent electrochemical activity results from the unique structure of Co3V2O8n H2O and probably from synergetic effects of different metal ions.

    21. Imaging Agents

      Synthesis and Evaluation of GdIII-Based Magnetic Resonance Contrast Agents for Molecular Imaging of Prostate-Specific Membrane Antigen

      Dr. Sangeeta Ray Banerjee, Dr. Ethel J. Ngen, Matthew W. Rotz, Dr. Samata Kakkad, Ala Lisok, Richard Pracitto, Mrudula Pullambhatla, Dr. Zhengping Chen, Dr. Tariq Shah, Dr. Dmitri Artemov, Dr. Thomas J. Meade, Dr. Zaver M. Bhujwalla and Dr. Martin G. Pomper

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201503417

      Thumbnail image of graphical abstract

      Good visibility: The relaxometric properties of a rationally designed high-affinity trimeric GdIII-based contrast agent were evaluated in prostate cancer cells and in an in vivo experimental model (see picture; ΔR1 measures contrast enhancement from 0 % (blue) to 50 % (red)) to demonstrate the feasibility of magnetic resonance molecular imaging of cells and tissues expressing prostate-specific membrane antigen (PSMA).

  10. Minireviews

    1. Sustainable Chemistry

      Single-Crystal Semiconductors with Narrow Band Gaps for Solar Water Splitting

      Assoc. Prof. Dr. Tuo Wang and Prof. Dr. Jinlong Gong

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201503346

      Thumbnail image of graphical abstract

      With suitable band gaps and low bulk recombination, single-crystal semiconductors with narrow band gaps have shown excellent performance in solar water splitting. This Minireview describes recent research advances in using these semiconductors as efficient photoelectrodes, where surface protection, cocatalyst loading, surface energetics matching, and surface texturization are proposed as the most important approaches to realized high activity.

  11. Communications

    1. Biomolecular Self-Assembly

      A Single Stereodynamic Center Modulates the Rate of Self-Assembly in a Biomolecular System

      Yitao Zhang, Roy M. Malamakal and Prof. David M. Chenoweth

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504459

      Thumbnail image of graphical abstract

      The influence of asymmetric carbon on biopolymer folding is of great importance as a general pre-organizing element in life processes. It is shown that a single C to N mutation in a collagen model peptide leads to a higher order structure with similar thermal unfolding but drastically different kinetic refolding behavior.

    2. Photochemistry

      White Light Emission from an Integrated Upconversion Nanostructure: Toward Multicolor Displays Modulated by Laser Power

      Cheng Zhang, Liang Yang, Jun Zhao, Bianhua Liu, Dr. Ming-Yong Han and Prof. Zhongping Zhang

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201504518

      Thumbnail image of graphical abstract

      Seeing the light: An upconversion nanostructure comprises several lanthanide ions integrated in a single system. The balance of numerous narrow emission bands covering the full visible spectrum results in white-light emission. The emission colors can be determined by changing the excitation power density (see picture), which manipulates the photon transfer pathways to bring potential applications such as multicolor displays or imaging.

    3. Synthetic Methods

      Palladium-Catalyzed Hydroamidocarbonylation of Olefins to Imides

      Haoquan Li, Dr. Kaiwu Dong, Dr. Helfried Neumann and Prof. Matthias Beller

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201503954

      Thumbnail image of graphical abstract

      Efficiency drive: The direct and efficient synthesis of imides from simple alkenes and amides can be achieved in good yield and with linear selectivity by employing the title reaction. As an example, the synthesis of the anxiolytic drug Aniracetam has been accomplished in an atom-economic manner by an intramolecular carbonylative ring-closing reaction.

    4. Fluorination

      Diphenyliodonium-Catalyzed Fluorination of Arynes: Synthesis of ortho-Fluoroiodoarenes

      Dr. Yuwen Zeng, Dr. Guangyu Li and Prof. Dr. Jinbo Hu

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201503308

      Thumbnail image of graphical abstract

      iCatalysis: A diphenyliodonium salt proved to be a privileged catalyst for nucleophilic fluorination of arynes using CsF as a fluorine source. A subsequent electrophilic iodination with C4F9I was also found to be crucial to ensure the efficient fluorination step.

    5. Persistent Luminescence

      Semiconducting Polymer Nanoparticles with Persistent Near-infrared Luminescence for In Vivo Optical Imaging

      Dr. Mikael Palner, Dr. Kanyi Pu, Shirley Shao and Prof. Jianghong Rao

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201502736

      Thumbnail image of graphical abstract

      Long lifetime and non-toxic: Nanoparticles made of the conjugated polymer MEH-PPV and a near-infrared (NIR) dye can generate NIR persistence luminescence emission with a lifetime of nearly one hour at room temperature. This new optical property was evaluated for optical imaging applications in living mice.

  12. Minireviews

    1. Redox-Active NOx Ligands

      Redox-Active NOx Ligands in Palladium-Mediated Processes

      Prof. Ian J. S. Fairlamb

      Article first published online: 23 JUL 2015 | DOI: 10.1002/anie.201411487

      Thumbnail image of graphical abstract

      Prominent role? The redox activity of NOx anions in Pd-catalyzed processes has recently attracted notable attention. It has led to the development of new synthetic methodologies in C[BOND]H bond activation (acetoxylation, fluorination, and nitration), Wacker oxidation, and diacetoxylation of terminal alkenes. The results are placed into context with historical findings on the use of NOx ligands in Pd-mediated chemistry.

  13. Communications

    1. Hydrogen Storage System | Hot Paper

      Rechargeable Hydrogen Storage System Based on the Dehydrogenative Coupling of Ethylenediamine with Ethanol

      Dr. Peng Hu, Yehoshoa Ben-David and Prof. Dr. David Milstein

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201505704

      Thumbnail image of graphical abstract

      In support of the hydrogen economy: An efficient and simple homogeneous hydrogen carrier system was developed based on the dehydrogenative coupling of ethylenediamine with ethanol to form diacetylethylenediamine. The same ruthenium pincer catalyst is used for both hydrogen loading and unloading reactions.

    2. Energy Conversion

      Dissolution Engineering of Platinum Alloy Counter Electrodes in Dye-Sensitized Solar Cells

      Prof. Qunwei Tang, Huihui Zhang, Yuanyuan Meng, Dr. Benlin He and Prof. Liangmin Yu

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201505339

      Thumbnail image of graphical abstract

      Less dissolution: PtM0.05 (M=Ni, Co, Fe, Pd, Mo, Cu, Cr, and Au) alloys were synthesized by simple electrodeposition and employed as counter-electrode (CE) electrocatalysts for liquid-junction dye-sensitized solar cells (DSSCs). Alloying of platinum with transition metals for forming competitive reactions is believed to be a promising strategy for increasing the dissolution resistance of CE electrocatalysts.

    3. Natural Products

      Enantioselective Total Synthesis of (−)-Hosieine A

      Jie Ouyang, Rui Yan, Xianwei Mi and Prof. Dr. Ran Hong

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201505251

      Thumbnail image of graphical abstract

      An unprecedented nitroso-ene cyclization to construct the 2-azabicyclo[3.2.1]octane ring system was developed during the first total synthesis of (−)-Hosieine A, a novel Lupin alkaloid possessing high affinity towards the α4β2 receptor with nanomolar level potency. Noteworthy transformations are the phosphine-enabled stereoselective bromohydrination and facile radical debromination initiated by Et3B/air.

    4. Photochemistry

      Precise Design of Phosphorescent Molecular Butterflies with Tunable Photoinduced Structural Change and Dual Emission

      Chenkun Zhou, Yu Tian, Dr. Zhao Yuan, Dr. Mingu Han, Jamie Wang, Prof. Lei Zhu, Maliheh Shaban Tameh, Prof. Chen Huang and Prof. Biwu Ma

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201505185

      Thumbnail image of graphical abstract

      Spread your wings and fly: A series of butterfly-like phosphorescent binuclear platinum complexes can undergo controlled photoinduced structural change (PSC) by Pt–Pt distance shortening and exhibit tunable dual emission in the steady state. The precise manipulation of the PSC processes and the dual emission is achieved by molecular engineering of the excited-state potential energy surface.

    5. Photobiology

      Protein-Induced Color Shift of Carotenoids in β-Crustacyanin

      Dr. Ana P. Gamiz-Hernandez, Iva Neycheva Angelova, Dr. Robert Send, Prof.Dr. Dage Sundholm and Prof. Dr. Ville R. I. Kaila

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201501609

      Thumbnail image of graphical abstract

      True blue: The pigment protein β-crustacyanin, which is responsible for the blue color of lobsters, tunes the color of its two bound astaxanthin chromophores through electrostatic polarization and steric planarization.

    6. Cluster Compounds

      From Mesomorphic Phosphine Oxide to Clustomesogens Containing Molybdenum and Tungsten Octahedral Cluster Cores

      Dr. Viorel Cîrcu, Dr. Yann Molard, Dr. Maria Amela-Cortes, Ahmed Bentaleb, Dr. Philippe Barois, Dr. Vincent Dorcet and Dr. Stéphane Cordier

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201503205

      Thumbnail image of graphical abstract

      Clustomesogens are metal atom clusters containing liquid crystalline materials. They have been obtained by grafting neutral cyanobiphenyl- or cholesteryl-containing tailor-made dendritic mesomorphic triphenylphosphine oxide ligands on luminescent (M6Cli8)4+ octahedral cluster cores (M=Mo, W).

    7. Reaction Yields

      A Priori Estimation of Organic Reaction Yields

      Dr. Fateme S. Emami, Dr. Amir Vahid, Elizabeth K. Wylie, Sara Szymkuć, Dr. Piotr Dittwald, Karol Molga and Prof. Bartosz A. Grzybowski

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201503890

      Thumbnail image of graphical abstract

      Getting to grips with yields: A thermodynamically guided calculation of free energies of substrate and product molecules allows the a priori estimation of the yields of organic reactions to be made. The model is first trained on a diverse set of reactions and reaction yields, and can then estimate the yields of other reactions with the accuracy of ±15 %.

    8. Imaging Probes | Hot Paper

      A Small-Molecule Probe for Selective Profiling and Imaging of Monoamine Oxidase B Activities in Models of Parkinson’s Disease

      Dr. Lin Li, Dr. Cheng-Wu Zhang, Dr. Jingyan Ge, Linghui Qian, Bing-Han Chai, Prof. Dr. Qing Zhu, Prof. Dr. Jun-Seok Lee, Prof. Dr. Kah-Leong Lim and Prof. Dr. Shao Q. Yao

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201504441

      Thumbnail image of graphical abstract

      Seeing is believing: A dual-purpose small-molecule activity-based probe (M2) was developed for imaging the activity of monoamine oxidase B (MAO-B). In situ proteome profiling and live-cell bioimaging of endogenous MAO-B activities from a variety of biological samples, including Parkinson’s disease models, can thus be carried out simultaneously.

  14. Reviews

    1. Self-Healing Materials

      Biomimetic Self-Healing

      Dr. Charles E. Diesendruck, Prof. Dr. Nancy R. Sottos, Prof. Dr. Jeffrey S. Moore and Prof. Dr. Scott R. White

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201500484

      Thumbnail image of graphical abstract

      On the mend: Evolution has endowed biological organisms with the ability to self-heal. Inspired by the principles of nature, scientists have been trying to create synthetic materials with self-healing capabilities that can regenerate their mechanical integrity and specific functions after damage.

  15. Communications

    1. Synthetic Methods

      Palladium-Catalyzed Dearomative Cyclocarbonylation by C[BOND]N Bond Activation

      Hui Yu, Guoying Zhang and Prof. Dr. Hanmin Huang

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201504805

      Thumbnail image of graphical abstract

      Dearomatization: A highly efficient dearomative cyclocarbonylation reaction proceeds by palladium-catalyzed C[BOND]N bond activation, dearomatization, CO insertion, and a Heck reaction. This transformation represents the first general catalytic method for the synthesis of valuable bioactive quinolizinones.

    2. Carboranes

      Palladium-Catalyzed Direct Dialkenylation of Cage B[BOND]H Bonds in o-Carboranes through Cross-Coupling Reactions

      Hairong Lyu, Yangjian Quan and Prof. Dr. Zuowei Xie

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201504481

      Thumbnail image of graphical abstract

      Giving directions: Pd-catalyzed direct dialkenylation of cage B(4,5)[BOND]H bonds in o-carboranes has been achieved using a carboxylic acid directing group, leading to the preparation of a series of 4,5-[trans-(ArCH[DOUBLE BOND]CH)]2-o-carboranes in high yields and with excellent regioselectivity.

    3. Total Synthesis

      Biomimetic Total Synthesis of (−)-Penibruguieramine A Using Memory of Chirality and Dynamic Kinetic Resolution

      Jae Hyun Kim, Seokwoo Lee and Prof. Dr. Sanghee Kim

      Article first published online: 21 JUL 2015 | DOI: 10.1002/anie.201504954

      Thumbnail image of graphical abstract

      Chiral survival: The fully stereocontrolled total synthesis of (−)-penibruguieramine A is described. The principles of “memory of chirality” (MOC) and “dynamic kinetic resolution” (DKR) are applied to the biomimetic aldol reaction for the asymmetric synthesis, using proline as the only chiral source.

    4. Expanded Porphyrins

      A Stable Organic π-Radical of a Zinc(II)–Copper(I)–Zinc(II) Complex of Decaphyrin

      Dr. Yasuo Tanaka, Dr. Tomoki Yoneda, Prof. Dr. Ko Furukawa, Dr. Taro Koide, Hirotaka Mori, Dr. Takayuki Tanaka, Prof. Dr. Hiroshi Shinokubo and Prof. Dr. Atsuhiro Osuka

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201505130

      Thumbnail image of graphical abstract

      Radical racetrack: CuII metalation of a [46]decaphyrin bis(ZnII) complex gave a ZnII-CuI-ZnII heterotrimetal complex of decaphyrin consisting of a central CuI ion and a monoanionic 45π radical of decaphyrin. Despite the radical nature, the complex is fairly stable under ambient conditions. This stability is probably due to the effective delocalization of an unpaired electron over the whole π-conjugation network of the decaphyrin.

  16. Highlights

    1. Epigenetics

      N6-Methyladenine: A Potential Epigenetic Mark in Eukaryotic Genomes

      Dr. Daniel Summerer

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504594

      Thumbnail image of graphical abstract

      N6-methyladenine (6mA) is known to be an epigenetic mark in bacterial genomes. Three studies have now demonstrated the existence of significant levels of 6mA in the genomes of several phylogenetically distinct eukaryotes, along with findings that suggest that 6mA may act as a dynamic epigenetic mark in the regulation of eukaryotic gene expression.

  17. Cover Pictures

    1. A Crystal Structure of a Functional RNA Molecule Containing an Artificial Nucleobase Pair

      Dr. Armando R. Hernandez, Dr. Yaming Shao, Dr. Shuichi Hoshika, Zunyi Yang, Dr. Sandip A. Shelke, Dr. Julien Herrou, Dr. Hyo-Joong Kim, Dr. Myong-Jung Kim, Prof. Joseph A. Piccirilli and Prof. Steven A. Benner

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201506280

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      With added nucleotide “letters”, nucleic acids can be incorporated into RNA in a functional form. In their Communication (10.1002/anie.201504731), the Piccirilli and Benner groups joined to deliver the first molecular structure (symbolized by the “photographs” in the picture) of a functional RNA molecule built from a six nucleotide alphabet (G, A, U, C, and the artificial nucleotides Z and P).

    2. SLAP: Small Labeling Pair for Single-Molecule Super-Resolution Imaging

      Dr. Ralph Wieneke, Anika Raulf, Alina Kollmannsperger, Prof. Mike Heilemann and Prof. Robert Tampé

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201506234

      Thumbnail image of graphical abstract

      A Small Labeling Pair (SLAP) for single-molecule imaging techniques is reported by M. Heilemann, R. Tampé, and co-workers in their Communication (DOI: 10.1002/anie.201503215). The small-molecule recognition unit (Ni-trisNTA) and the genetically encoded minimal protein (His6-10-tag) enable rapid, site-specific, and stoichiometric labeling with high density. The close proximity achieved with SLAP accounts for the higher spatial resolution with nanoscopy (orange) compared to wide-field imaging (gray).

  18. Communications

    1. Biosensors | Hot Paper

      An Activity-Based Probe for Studying Crosslinking in Live Bacteria

      Dr. Samir Gautam, Dr. Taehan Kim, Dr. Takuji Shoda, Dr. Sounok Sen, Deeksha Deep, Ragini Luthra, Maria Teresa Ferreira, Prof. Dr. Mariana G. Pinho and Prof. Dr. David A. Spiegel

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201503869

      Thumbnail image of graphical abstract

      Linked in: A nontoxic fluorescent probe that mimics the peptidoglycan stem peptide can be used to install fluorophores at sites of crosslinking within the bacterial cell wall (see picture). The probe is specific for penicillin-binding protein 4 (PBP4) in Staphylococcus aureus, and thus allows visualization and relative quantification of PBP4-mediated crosslinking in this important human pathogen.

    2. Peptide Macrocyclization

      A Thiol–Ene Coupling Approach to Native Peptide Stapling and Macrocyclization

      Dr. Yuanxiang Wang and Prof. Dr. Danny Hung-Chieh Chou

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201503975

      Thumbnail image of graphical abstract

      The selective modification of cysteine residues in native, unprotected peptides with a variety of stapling modifications for helix stabilization or general macrocyclization is achieved by a new peptide stapling and macrocyclization method. This method uses thiol–ene reactions between two cysteine residues and a diene and gives high yields.

    3. Biosynthesis | Hot Paper

      A Single Enzyme Transforms a Carboxylic Acid into a Nitrile through an Amide Intermediate

      Micah T. Nelp and Prof. Vahe Bandarian

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504505

      Thumbnail image of graphical abstract

      Double duty: In bacterial and archeal biosynthesis of 7-deazpurines, a single enzyme, ToyM, catalyzes the two-step conversion of the carboxylic acid 7-carboxy-7-deazaguanine (CDG) into the corresponding nitrile, 7-cyano-7-deazaguanine (preQ0). The mechanism of this unusual direct transformation proceeds via the adenylation of CDG. This activates it to form the amide intermediate 7-amido-7-deazaguanine (ADG), which is in turn activated to form the nitrile.

  19. Cover Pictures

    1. Visible-Light-Induced Click Chemistry

      Jan O. Mueller, Dr. Friedrich G. Schmidt, Dr. James P. Blinco and Prof. Christopher Barner-Kowollik

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201506194

      Thumbnail image of graphical abstract

      An ultra-rapid visible-light-driven method for catalyst-free ligation is reported. In their Communication (DOI: 10.1002/anie.201504716), C. Barner-Kowollik and co-workers describe a highly efficient conjugation between an azirine moiety (white) and diverse dipolarophiles (red) under irradiation from blue LEDs. Following the photogeneration of a nitrile ylide (cyan structure), complete conversion into the cycloadduct takes place through a click-type reaction.

  20. Communications

    1. Drug Delivery

      Switchable Lipids: Conformational Change for Fast pH-Triggered Cytoplasmic Delivery

      Warren Viricel, Dr. Amira Mbarek and Prof. Dr. Jeanne Leblond

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504661

      Thumbnail image of graphical abstract

      Switch it on! The integration of pH-sensitive switchable lipids (see picture) into poly(ethylene glycol)-coated liposome formulations enabled the efficient cytoplasmic delivery of polar compounds through an endosomal-escape mechanism. The liposome formulations containing the switchable lipids were stable at pH 7.4 and upon storage but instantly destabilized at endosomal pH values (pH 5–5.5).

  21. Cover Pictures

    1. Photocatalytic Formic Acid Conversion on CdS Nanocrystals with Controllable Selectivity for H2 or CO

      Dr. Moritz F. Kuehnel, David W. Wakerley, Dr. Katherine L. Orchard and Dr. Erwin Reisner

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201506236

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      The bifunctionality of CdS quantum dots for the light-driven conversion of formic acid into gaseous fuels is demonstrated by E. Reisner et al. in their Communication (10.1002/anie.201502773). Depending on the conditions and particle surface groups, irradiated CdS nanocrystals produce hydrogen and carbon dioxide through dehydrogenation of formic acid or carbon monoxide and water through dehydration. Hydrogen evolution occurs at an unprecedented rate compared to analogous systems, and this process establishes formic acid as a material for carbon monoxide storage.

    2. Precise Design of Phosphorescent Molecular Butterflies with Tunable Photoinduced Structural Change and Dual Emission

      Chenkun Zhou, Yu Tian, Dr. Zhao Yuan, Dr. Mingu Han, Jamie Wang, Prof. Lei Zhu, Maliheh Shaban Tameh, Prof. Chen Huang and Prof. Biwu Ma

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201506195

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      A series of butterfly-like molecules that undergo controlled photoinduced structural changes (PSCs) and exhibit tunable dual emission are reported by B. Ma, C. Huang, and co-workers in their Communication (DOI: 10.1002/anie.201505185). The precise control of the PSC processes and the dual emission is achieved by molecular engineering of the potential energy surface of the excited state.

    3. Discovery of a Single Monooxygenase that Catalyzes Carbamate Formation and Ring Contraction in the Biosynthesis of the Legonmycins

      Sheng Huang, Dr. Jioji Tabudravu, Somayah S. Elsayed, Jeanne Travert, Doe Peace, Ming Him Tong, Dr. Kwaku Kyeremeh, Dr. Sharon M. Kelly, Dr. Laurent Trembleau, Dr. Rainer Ebel, Prof. Dr. Marcel Jaspars, Dr. Yi Yu and Dr. Hai Deng

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201506192

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      The multifunctional Baeyer–Villiger enzyme LgnC catalyzes the transformation of indolizidines into pyrrolizidines by carbamate formation, hydrolysis, decarboxylation-driven ring contraction, and hydroxylation. In their Communication (DOI: 10.1002/anie.201502902), H. Deng, Y. Yu et al. show that these are the crucial steps for the biosynthesis of the legonmycins, new bacterial pyrrolizidine alkaloids named after their association with Legon, Ghana.

  22. Communications

    1. Iminoborane | Hot Paper

      Encapsulating Inorganic Acetylene, HBNH, Using Flanking Coordinative Interactions

      Anindya K. Swarnakar, Dr. Christian Hering-Junghans, Koichi Nagata, Dr. Michael J. Ferguson, Dr. Robert McDonald, Prof. Dr. Norihiro Tokitoh and Prof. Dr. Eric Rivard

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504867

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      Lightning in a bottle: An adduct of the elusive parent “inorganic acetylene” HBNH was prepared from a main-group azide by means of a general process consisting of N2 loss and 1,2-hydrogen migration. The mechanism of this reaction was examined by calculations and isotope-labeling studies.

    2. DNA Structures

      Single-Molecule Visualization of the Activity of a Zn2+-Dependent DNAzyme

      Prof. Dr. Masayuki Endo, Yosuke Takeuchi, Dr. Yuki Suzuki, Tomoko Emura, Kumi Hidaka, Dr. Fuan Wang, Prof. Dr. Itamar Willner and Prof. Dr. Hiroshi Sugiyama

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504656

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      In the frame: The single-molecule catalytic activity of a Zn2+-dependent DNAzyme was investigated in a DNA origami nanostructure. The DNAzyme and substrate strands were assembled in the DNA frames in different configurations. Reaction progress was directly visualized by observing the structural changes of the incorporated DNA strands by high-speed atomic force microscopy (see picture).

    3. Epoxidation Catalysis | Hot Paper

      Direct Epoxidation of Propylene over Stabilized Cu+ Surface Sites on Titanium-Modified Cu2O

      Dr. Xiaofang Yang, Dr. Shyam Kattel, Ke Xiong, Dr. Kumudu Mudiyanselage, Dr. Sergei Rykov, Dr. Sanjaya D. Senanayake, Dr. José A. Rodriguez, Dr. Ping Liu, Dr. Dario J. Stacchiola and Prof. Dr. Jingguang G. Chen

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504538

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      Ti-ed up: Cu+ active sites on a Cu2O surface can be stabilized with TiOx by forming a mixed oxide, TiCuOx. The basicity of the surface-bound oxygen atoms thus decreases which inhibits combustion and promotes the formation of an oxametallacycle intermediate with propylene leading to higher selectivity for propylene epoxidation.

    4. Photocatalysis

      Specific Photochemical Dehydrocoupling of N-Heterocyclic Phosphanes and Their Use in the Photocatalytic Generation of Dihydrogen

      Oliver Puntigam, László Könczöl, Prof. Dr. László Nyulászi and Prof. Dr. Dietrich Gudat

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504504

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      Hydrogen cycle: Highly selective photochemical dehydrocoupling converts N-heterocyclic phosphanes to diphosphanes and H2, and is a key step in a reaction cycle enabling photocatalytic reductive generation of H2 from Et3NH+. Computational studies suggest that the reaction is initiated by the formation of dimeric molecular associates whose electronic excitation yields H2 and two phosphanyl radicals.

    5. Organozinc Reagents

      Preparation of Solid, Substituted Allylic Zinc Reagents and Their Reactions with Electrophiles

      Mario Ellwart and Prof. Dr. Paul Knochel

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504354

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      Think Allyl Zinc: The reaction of allylic chlorides or bromides with zinc powder in the presence of lithium chloride and magnesium pivalate leads to the formation of solid allylic zinc reagents that show excellent thermal stability. These allylic reagents undergo Pd-catalyzed cross-coupling reactions, as well as highly regioselective and diastereoselective carbonyl additions.

    6. Oxidase Mimetics

      A Structural and Functional Model for the 1-Aminocyclopropane-1-carboxylic Acid Oxidase

      Dr. Madleen Sallmann, B. Sc. Fabio Oldenburg, Dr. Beatrice Braun, Dr. Marius Réglier, Dr. A. Jalila Simaan and Prof. Dr. Christian Limberg

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201502529

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      A ripening model: The depicted complex mimics the structure and the function of the aminocyclopropane-1-carboxylic acid oxidase (ACCO). It reacts with both O2 and H2O2, respectively, to yield ethylene, which allows for inferences with respect to the enzymatic mechanism.

    7. Silacarbon Complexes

      Stabilization of Heterodiatomic SiC Through Ligand Donation: Theoretical Investigation of SiC(L)2 (L=NHCMe, CAACMe, PMe3)

      Dr. Diego M. Andrada and Prof. Gernot Frenking

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201502450

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      Planar or twisted? Quantum-chemical calculations have been carried out at the BP86/TZ2P+ level for the compounds SiC(L)2 (L=NHCMe, CAACMe, PMe3; NHC=N-heterocyclic carbene, CAAC=cyclic (alkyl)aminocarbene). The optimized geometries exhibit a trans arrangement of the ligands L at SiC with a planar coordination when L=NHCMe and PMe3, while a twisted conformation is calculated when L=CAACMe (see structures; Si crimson, P pink, N blue).

  23. Minireviews

    1. Silylation

      Catalytic Silylations of Alcohols: Turning Simple Protecting-Group Strategies into Powerful Enantioselective Synthetic Methods

      Prof. Dr. Li-Wen Xu, Yun Chen and Prof. Dr. Yixin Lu

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504127

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      Silicon talks: Owing to the development of methods for the site- and stereoselective functionalization of hydroxy groups, silyl ether formation has evolved from being a simple reaction for functional-group protection into a powerful enantioselective process. This Minireview highlights recent findings in the emerging field of enantioselective alcohol silylation.

  24. Communications

    1. Target Identification

      Revealing the Macromolecular Targets of Fragment-Like Natural Products

      Dr. Tiago Rodrigues, Daniel Reker, Jens Kunze, Dr. Petra Schneider and Prof. Dr. Gisbert Schneider

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504241

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      Target acquired: Hitherto unknown macromolecular targets of the fragment-like natural products goitrin, isomacroin, and graveolinine were discovered through the use of a computational target-prediction tool tailored for natural products. The results suggest that such methods will find application in target discovery for natural products and could inspire the design of new chemical entities for chemical biology and molecular medicine.

    2. Biosynthesis

      Discovery of a Single Monooxygenase that Catalyzes Carbamate Formation and Ring Contraction in the Biosynthesis of the Legonmycins

      Sheng Huang, Dr. Jioji Tabudravu, Somayah S. Elsayed, Jeanne Travert, Doe Peace, Ming Him Tong, Dr. Kwaku Kyeremeh, Dr. Sharon M. Kelly, Dr. Laurent Trembleau, Dr. Rainer Ebel, Prof. Dr. Marcel Jaspars, Dr. Yi Yu and Dr. Hai Deng

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201502902

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      Solo performance: The legonmycins, new bacterial pyrrolizidine alkaloids, are assembled by a non-ribosomal peptide synthetase. The multifunctional FAD-containing enzyme LgnC catalyzes the transformation of indolizidine intermediates into pyrrolizidines by carbamate formation, followed by hydrolysis, decarboxylation-driven ring contraction, and hydroxylation as the crucial steps of legonmycin biosynthesis.

    3. Catalytic Hydrogenation

      Direct Ruthenium-catalyzed Hydrogenation of Carboxylic Acids to Alcohols

      Dr. Xinjiang Cui, Dr. Yuehui Li, Dr. Christoph Topf, Dr. Kathrin Junge and Prof. Dr. Matthias Beller

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201503562

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      Direct route to alcohols: The combination of a specific ruthenium complex and Lewis acids is found to be active for the direct hydrogenation of carboxylic acids to alcohols. A variety of carboxylic acids including biomass-based derivatives are converted into the desired alcohols in high yields.

    4. Hybrid Materials

      Room-Temperature, Strain-Tunable Orientation of Magnetization in a Hybrid Ferromagnetic Co Nanorod–Liquid Crystalline Elastomer Nanocomposite

      Dr. Ophélie Riou, Dr. Barbara Lonetti, Dr. Reasmey P. Tan, Justine Harmel, Dr. Katerina Soulantica, Dr. Patrick Davidson, Dr. Anne-Françoise Mingotaud, Dr. Marc Respaud, Dr. Bruno Chaudret and Dr. Monique Mauzac

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201504320

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      A highly anisotropic magnetic material with a strain tunable orientation of the magnetic direction was synthesized. In this material Co nanorods are aligned through a cross-linking process performed in the presence of an external magnetic field. The nanorod alignment can be switched at will at room temperature.

    5. Lewis Acid Catalysts

      Self-Assembled Nanocomposite Organic Polymers with Aluminum and Scandium as Heterogeneous Water-Compatible Lewis Acid Catalysts

      Dr. Hiroyuki Miyamura, Arisa Sonoyama, Dr. Davit Hayrapetyan and Prof. Dr. Shū Kobayashi

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201503874

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      Heterogeneous water-compatible Lewis acid catalysts were developed by self-assembly of polymer, carbon black, tetravalent aluminum reductant, and scandium salts using a polymer incarceration technique. The heterogeneous catalysts were successfully applied to various C[BOND]C bond forming reactions in pure water or aqueous media without leaching of metals.

    6. Peptide Modification

      Selective Rhodium-Catalyzed Reduction of Tertiary Amides in Amino Acid Esters and Peptides

      Dr. Shoubhik Das, Dr. Yuehui Li, Christoph Bornschein, Sabine Pisiewicz, Dr. Konstanze Kiersch, Dr. Dirk Michalik, Dr. Fabrice Gallou, Dr. Kathrin Junge and Prof. Dr. Matthias Beller

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201503584

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      Peptide modification: Application of a commercially available rhodium precursor and bis(diphenylphosphino)propane (dppp) ligand together with phenyl silane as a reductant allows for specific reductive derivatization of biologically interesting peptides.

    7. Chemical Bonding | Hot Paper

      The Nature of Bonding between Argon and Mixed Gold–Silver Trimers

      Armin Shayeghi, Prof. Dr. Roy L. Johnston, Dr. David M. Rayner, Prof. Dr. Rolf Schäfer and Dr. André Fielicke

      Article first published online: 17 JUL 2015 | DOI: 10.1002/anie.201503845

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      Relatively different: The evolution of noble-metal–noble-gas bonds in cationic argon complexes of mixed gold–silver trimers is studied considering the dependence on the composition of the clusters. The bond nature in the closed-shell molecules is probed by FIR-MPD spectroscopy supported by DFT calculations, reflecting the relativistic differences between gold and silver.

  25. Cover Pictures

    1. Pyridylidene-Mediated Dihydrogen Activation Coupled with Catalytic Imine Reduction

      Johanna Auth, Dr. Jaroslav Padevet, Dr. Pablo Mauleón and Prof. Dr. Andreas Pfaltz

      Article first published online: 16 JUL 2015 | DOI: 10.1002/anie.201506235

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      The trapping of H2 with a pyridylidene generated from a pyridinium salt and base is reported by A. Pfaltz, P. Mauleón et al. in their Communication (DOI: 10.1002/anie.201503233). By coupling H2 activation with subsequent hydride transfer to an imine, a catalytic process was established. Treatment of the N-phenylimine of phenyl trifluoromethyl ketone with N-mesityl-3,5-bis(2,6-dimethylphenyl)pyridinium triflate and LiN(SiMe3)2 under 50 bar of H2 resulted in high conversion into the corresponding amine.

  26. Highlights

    1. Batteries

      Critical Requirements for Rapid Charging of Rechargeable Al- and Li-Ion Batteries

      Dr. Sanghan Lee and Prof. Dr. Jaephil Cho

      Article first published online: 16 JUL 2015 | DOI: 10.1002/anie.201504466

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      On a charge: Currently, considerable demand exists for rechargeable batteries with both high energy density and low manufacturing cost, for use in mobile electronic devices and electric vehicles. Rapid charging is also a highly desirable criterion. Various recent approaches to realizing these requirements are presented.

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