Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 11

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. Inhibitors

      Biology-Oriented Synthesis of a Withanolide-Inspired Compound Collection Reveals Novel Modulators of Hedgehog Signaling

      Dr. Jakub Švenda, Dipl.-Biochem. Michael Sheremet, M. Sc. Lea Kremer, Lukáš Maier, Dr. Jonathan O. Bauer, Prof. Dr. Carsten Strohmann, Dr. Slava Ziegler, Dr. Kamal Kumar and Prof. Dr. Herbert Waldmann

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201500112

      Thumbnail image of graphical abstract

      BIOS delivers a collection of compounds with the trans-hydrindane dehydro-δ-lactone scaffold, which are based on the withanolide natural products, in a stereoselective fashion. A biological investigation of the compounds revealed novel and potent inhibitors of the Hedgehog signaling pathway, which bind to the protein Smoothened.

    2. Asymmetric Catalysis

      Direct Catalytic Enantio- and Diastereoselective Ketone Aldol Reactions of Isocyanoacetates

      Dr. Raquel de la Campa, Dr. Irene Ortín and Prof. Dr. Darren J. Dixon

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201411852

      Thumbnail image of graphical abstract

      A stereoselective aldol reaction of unactivated ketones and isocyanoacetate pronucleophiles is catalyzed by a binary catalyst system consisting of an aminophosphine precatalyst and silver(I) oxide and affords oxazoline products with a fully substituted β-carbon atom. The reaction is efficient and broad in scope and proceeds with high diastereo- and enantioselectivity.

    3. Organocatalysis

      Aminomethylation of Enals through Carbene and Acid Cooperative Catalysis: Concise Access to β2-Amino Acids

      Dr. Jianfeng Xu, Xingkuan Chen, Dr. Ming Wang, Pengcheng Zheng, Bao-An Song and Prof. Dr. Yonggui Robin Chi

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201412132

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      Harmonious cooperation: An N-heterocyclic carbene (NHC) and (in situ generated) Brønsted acid cooperatively catalyze the aminomethylation of α,β-unsaturated aldehydes. This cooperative catalytic reaction provides a redox neutral strategy for quick access to β2-amino esters in an enantioselective manner.

    4. Asymmetric Catalysis

      Catalytic Asymmetric Mannich-Type Reaction of N-Alkylidene-α-Aminoacetonitrile with Ketimines

      Shaoquan Lin, Dr. Yuji Kawato, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201412377

      Thumbnail image of graphical abstract

      Getting in key: A soft Lewis acid/hard Brønsted base cooperative catalyst allows for efficient stereoselectives coupling of N-alkylidene-α-aminoacetonitrile and aliphatic ketimines to access vicinal diamines bearing consecutive tetra- and trisubstituted stereogenic centers. The use of a soft Lewis basic thiophosphinoyl group on the ketimines is key to promoting the reaction with as little as 3 mol % catalyst loading.

    5. Polymersomes | Hot Paper

      Polymersomes Prepared from Thermoresponsive Fluorescent Protein–Polymer Bioconjugates: Capture of and Report on Drug and Protein Payloads

      Chin Ken Wong, Alistair J. Laos, Dr. Alexander H. Soeriyadi, Prof. Jörg Wiedenmann, Prof. Paul M. G. Curmi, Prof. J. Justin Gooding, Dr. Christopher P. Marquis, Prof. Martina H. Stenzel and Assoc. Prof. Pall Thordarson

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201412406

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      Temperature-induced self-assembly: A temperature-sensitive green fluorescent (amilFP497) protein–polymer bioconjugate forms polymersomes above 37 °C which encapsulate a mixture of pink fluorescent protein (PE545) and a red drug molecule (DOX). The spatial location of the payload is revealed by fluorescence lifetime microscopy.

    6. Spin Crossover

      FeII Spin-Crossover Phenomenon in the Pentadecanuclear {Fe9[Re(CN)8]6} Spherical Cluster

      Dr. Szymon Chorazy, Dr. Robert Podgajny, Dr. Koji Nakabayashi, Prof. Dr. Jan Stanek, Dr. Michał Rams, Prof. Dr. Barbara Sieklucka and Prof. Dr. Shin-ichi Ohkoshi

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201500288

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      Selective switching: A single FeII ion embedded in the center of nanosized {Fe9Re6} cyanido-bridged cluster exhibits a complete thermally induced spin-crossover phase transition between a paramagnetic high-spin (HS; S=2) and diamagnetic low-spin state (LS; S=0). The HS and LS states dominate at high and low temperatures, respectively (see picture; sphere colors: red=FeII(HS), blue=FeII(LS), brown=ReV).

    7. Decarboxylative Fluorination | Hot Paper

      Targeted Fluorination with the Fluoride Ion by Manganese-Catalyzed Decarboxylation

      Xiongyi Huang, Dr. Wei Liu, Prof. Jacob M. Hooker and Prof. John T. Groves

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201500399

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      Nucleophile first: An efficient manganese porphyrin catalyzed decarboxylative fluorination reaction based on a nucleophilic fluorine source is described. The potential of the described method for use in PET imaging has been demonstrated by the successful 18F labeling of various aliphatic carboxylic acids, representing the first decarboxylative 18F labeling method with no-carrier-added [18F]fluoride.

    8. C[BOND]H Activation | Hot Paper

      Ruthenium(II)-Catalyzed C[BOND]H Activation/Alkyne Annulation by Weak Coordination with O2 as the Sole Oxidant

      M. Sc. Svenja Warratz, Dr. Christoph Kornhaaß, M. Sc. Ana Cajaraville, Benedikt Niepötter, Prof. Dr. Dietmar Stalke and Prof. Dr. Lutz Ackermann

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201500600

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      Air and water: Ruthenium(II) biscarboxylates allow for the annulation of alkynes and alkenes by oxidative C[BOND]H functionalizations with molecular oxygen as the sole oxidant. The C[BOND]H/O[BOND]H functionalization process occurs with excellent selectivities under mild reaction conditions, with water produced as the only by-product.

    9. Asymmetric Hydrogenation

      Nickel-Catalyzed Asymmetric Transfer Hydrogenation of Hydrazones and Other Ketimines

      Haiyan Xu, Dr. Peng Yang, Pratanphorn Chuanprasit, Prof. Dr. Hajime Hirao and Prof. Dr. Jianrong (Steve) Zhou

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201501018

      Thumbnail image of graphical abstract

      Cheap and abundant nickel was used for the catalytic transfer hydrogenation of hydrazones and related compounds (see scheme; R=acyl, aryl; R1=alkyl, CF3; R2=aryl, alkyl). The nickel/binapine catalyst may exert stereocontrol through weak attractive interactions, thus behaving like an enzyme.

  2. Cover Pictures

    1. Microfluidic Synthesis of Rigid Nanovesicles for Hydrophilic Reagents Delivery

      Lu Zhang, Qiang Feng, Jiuling Wang, Prof. Dr. Jiashu Sun, Prof. Dr. Xinghua Shi and Prof. Dr. Xingyu Jiang

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201501645

      Thumbnail image of graphical abstract

      Nanocarriers for the delivery of hydrophilic reagents are important in drug therapy and disease diagnosis. In their Communication (10.1002/anie.201500096) J. Sun, X. Jiang, and co-workers report a three-stage microfluidic chip that can assemble water core/PLGA shell/lipid layer rigid nanovesicles (RNV) in one step for hydrophilic-reagent delivery (PLGA=poly(lactic-co-glycolic acid)). For a multi-drug-resistant tumor model, co-delivery of siMDR1 and doxorubicin using RNVs has an enhanced anti-tumor effect in both in vitro and in vivo experiments.

  3. Communications

    1. Reaction Mechanisms

      Electron Flow in Reaction Mechanisms—Revealed from First Principles

      Dr. Gerald Knizia and Dr. Johannes E. M. N. Klein

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201410637

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      Curly arrows from ab initio calculations: Curly arrows in reaction mechanisms are shown to correspond to changes in intrinsic bond orbitals (IBOs) along reaction paths. With this quantum chemical basis, even complex reaction mechanisms can be derived and visualized in a simple, direct, and intuitive form.

    2. Supramolecular Chemistry

      Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air

      Prof. Dr. Chi Yang, Dr. Ravi K. Arvapally, Dr. Sammer M. Tekarli, Gustavo A. Salazar, Dr. Oussama Elbjeirami, Dr. Xiaoping Wang and Prof. Dr. Mohammad A. Omary

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201411462

      Thumbnail image of graphical abstract

      Glowing supramolecular octopi: A fluorous/organic biphasic supramolecular octopus pair with two nanoscopic cavities was constructed by coupling of a fluorous Ag3 macrocycle with a metalloporphyrin through strong quadrupole–quadrupole interactions. The unique configuration of this system enhances the phosphorescence of the metalloporphyrin under ambient conditions.

    3. Synthetic Methods

      Oxidative C[BOND]H Bond Functionalization and Ring Expansion with TMSCHN2: A Copper(I)-Catalyzed Approach to Dibenzoxepines and Dibenzoazepines

      Tobias Stopka, Leyre Marzo, Mercedes Zurro, Dr. Simon Janich, Prof. Ernst-Ulrich Würthwein, Dr. Constantin G. Daniliuc, Dr. José Alemán and Prof. Olga García Mancheño

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201411726

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      Cut a long story short: Tricyclic dibenzoxepines and dibenzazepines are important therapeutic agents for pharmaceuticals, but their syntheses are generally rather tedious. A copper(I)-catalyzed oxidative C[BOND]H bond functionalization and ring expansion sequence with TMSCHN2 has been developed to yield these important derivatives in a facile and straightforward way.

    4. Glycopeptides

      A Defined α-Helix in the Bifunctional O-Glycosylated Natriuretic Peptide TcNPa from the Venom of Tropidechis carinatus

      Timothy Reeks, Alun Jones, Dr. Andreas Brust, Dr. Sindhuja Sridharan, Leo Corcilius, Dr. Brendan L. Wilkinson, Dr. Morten Thaysen-Andersen, Prof. Richard J. Payne, Prof. R. Manjunatha Kini, Prof. Norelle L. Daly and Prof. Paul F. Alewood

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201411914

      Thumbnail image of graphical abstract

      Snake toxin: A novel natriuretic peptide (NP) from Tropidechis carinatus contains an O-linked Gal-β(1-3)-GalNAc mucin-type glycan on the C-terminal threonine 27 residue. The secondary structure is in the form of an α-helix and has been identified for the first time from NMR analysis. Both synthesized glycosylated and nonglycosylated variants display bifunctional activity with NPR-A and NPR-B receptors.

    5. Ionic Liquids

      Transformation of Atmospheric CO2 Catalyzed by Protic Ionic Liquids: Efficient Synthesis of 2-Oxazolidinones

      Jiayin Hu, Jun Ma, Qinggong Zhu, Zhaofu Zhang, Congyi Wu and Prof. Buxing Han

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201411969

      Thumbnail image of graphical abstract

      CO2 capture: Under mild, metal-free conditions, protic ionic liquids, such as 1,8-diazabicyclo[5.4.0]-7-undecenium 2-methylimidazolide [DBUH][MIm], can catalyze the reaction between CO2 and propargylic amines to form 2-oxazolidinones. Both the cation and anion of the ionic liquids play key roles in accelerating the reaction.

    6. Sequence-Controlled Polymerization

      Alternating Copolymerization by Nitroxide-Mediated Polymerization and Subsequent Orthogonal Functionalization

      Matthias Tesch, Johannes A. M. Hepperle, Henning Klaasen, Matthias Letzel and Prof. Dr. Armido Studer

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201412206

      Thumbnail image of graphical abstract

      Alternating through double click: The title reaction of A with hexafluoroisopropyl acrylate (HFIPA) provides alternating polymer B, which can be chemically modified using two orthogonal polymer-analogous reactions. With this method, a small library of fifteen functionalized alternating copolymers was prepared.

    7. Sulfur Atom Transfer

      Metal-Catalyzed “On-Demand” Production of Carbonyl Sulfide from Carbon Monoxide and Elemental Sulfur

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

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

      Thumbnail image of graphical abstract

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

    8. Synthetic Methods

      Copper-Catalyzed Intermolecular Carboetherification of Unactivated Alkenes by Alkyl Nitriles and Alcohols

      Claire Chatalova-Sazepin, Dr. Qian Wang, Prof. Dr. Glenn M. Sammis and Prof. Dr. Jieping Zhu

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201412357

      Thumbnail image of graphical abstract

      Three-component coupling of alkenes, alcohols, and alkyl nitriles catalyzed by copper triflate afforded 4-alkoxyalkyl nitriles in good to excellent yields. The reaction forms a C[BOND]C and a C[BOND]O bond with concomitant creation of a quaternary carbon center. The involvement of a radical intermediate was proven by a radical clock experiment.

    9. Para-Selective Liquid Sorption

      Separation of p-Divinylbenzene by Selective Room-Temperature Adsorption Inside Mg-CUK-1 Prepared by Aqueous Microwave Synthesis

      Beau Saccoccia, Alisha M. Bohnsack, Nolan W. Waggoner, Kyung Ho Cho, Ji Sun Lee, Dr. Do-Young Hong, Dr. Vincent M. Lynch, Dr. Jong-San Chang and Prof. Simon M. Humphrey

      Article first published online: 3 MAR 2015 | DOI: 10.1002/anie.201411862

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      From complex to simple: The porous material Mg-CUK-1 has been prepared using an aqueous microwave-assisted synthetic method. This material contains infinite one-dimensional pores that show highly selective, room-temperature adsorption of p-divinylbenzene (p-DVB) and other organic compounds from complex mixtures of isomers.

    10. Metal–Organic Frameworks | Hot Paper

      Photoinduced Postsynthetic Polymerization of a Metal–Organic Framework toward a Flexible Stand-Alone Membrane

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

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

      Thumbnail image of graphical abstract

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

    11. Mesoporous Materials | Hot Paper

      Polymeric Micelle Assembly with Inorganic Nanosheets for Construction of Mesoporous Architectures with Crystallized Walls

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

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

      Thumbnail image of graphical abstract

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

    12. Photonic Crystals

      Mechanochromic Photonic-Crystal Fibers Based on Continuous Sheets of Aligned Carbon Nanotubes

      Dr. Xuemei Sun, Jing Zhang, Xin Lu, Xin Fang and Prof. Huisheng Peng

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201412475

      Thumbnail image of graphical abstract

      Color play: A new family of mechanochromic photonic-crystal fibers exhibits tunable structural colors under stretching. These fibers maintain both a high sensitivity and stability even after more than 1000 deformation cycles. These elastic photonic-crystal fibers are woven into colorful patterns and fabrics for various applications in displays and sensing devices.

    13. Methane Activation | Very Important Paper

      On the Role of the Electronic Structure of the Heteronuclear Oxide Cluster [Ga2Mg2O5].+ in the Thermal Activation of Methane and Ethane: An Unusual Doping Effect

      Dr. Jilai Li, Dr. Xiao-Nan Wu, Dr. Maria Schlangen, Dr. Shaodong Zhou, Dr. Patricio González-Navarrete, Dr. Shiya Tang and Prof. Dr. Helmut Schwarz

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201412441

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      Bridging oxygen: A combination of mass spectrometry and quantum chemical calculations shows that [Ga2Mg2O5].+, bearing an unpaired electron at a bridging oxygen atom, is capable of activating the C[BOND]H bond of methane. The roles of spin density and charge distributions in hydrogen-atom transfer processes provide important guidance for the rational design of catalysts.

    14. Water Splitting

      Fast and Simple Preparation of Iron-Based Thin Films as Highly Efficient Water-Oxidation Catalysts in Neutral Aqueous Solution

      Yizhen Wu, Mingxing Chen, Yongzhen Han, Prof. Dr. Hongxia Luo, Xiaojun Su, Prof. Dr. Ming-Tian Zhang, Xiaohuan Lin, Prof. Dr. Junliang Sun, Lei Wang, Prof. Dr. Liang Deng, Prof. Dr. Wei Zhang and Prof. Dr. Rui Cao

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201412389

      Thumbnail image of graphical abstract

      A catalyst with iron strength: Iron-based films were deposited onto electrodes by cyclic voltammetry within a minute, thus minimizing the time and energy input for potential large-scale applications. The films, which had a very low iron loading, catalyzed water oxidation in neutral aqueous media with a high turnover frequency and showed remarkable catalytic stability (see picture; ITO=indium tin oxide).

    15. Self-Assembly

      Surface-Induced Selection During In Situ Photoswitching at the Solid/Liquid Interface

      Dr. Sara Bonacchi, Dr. Mohamed El Garah, Dr. Artur Ciesielski, Martin Herder, Simone Conti, Dr. Marco Cecchini, Prof. Dr. Stefan Hecht and Prof. Dr. Paolo Samorì

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201412215

      Thumbnail image of graphical abstract

      A diarylethene derivative exhibits pronounced affinity for the graphite surface in all its isomeric forms. The photoswitch between its two isomers, that is, the open and closed form, at the solid/liquid interface is investigated by submolecularly resolved scanning tunneling microscopy and atomistic modeling. Prolonged irradiation leads to the in situ irreversible formation of another isomer as by-product of the reaction.

    16. Polymers

      Highly Isoselective Coordination Polymerization of ortho-Methoxystyrene with β-Diketiminato Rare-Earth-Metal Precursors

      Dr. Dongtao Liu, Changguang Yao, Rong Wang, Dr. Meiyan Wang, Zichuan Wang, Dr. Chunji Wu, Fei Lin, Dr. Shihui Li, Prof. Xinhua Wan and Prof. Dongmei Cui

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201412166

      Thumbnail image of graphical abstract

      Name your poison: The title reaction has been achieved for the first time by using a β-diketiminato cationic rare-earth-metal species. High activity and excellent isoselectivity are observed. The Lewis-basic methoxy group does not poison the Lewis-acidic metal center but activates the polymerization through σ-π chelation to the active species.

    17. Molecularly Imprinted Polymer Nanomaterials and Nanocomposites: Atom-Transfer Radical Polymerization with Acidic Monomers

      Zeynep Adali-Kaya, Dr. Bernadette Tse Sum Bui, Dr. Aude Falcimaigne-Cordin and Prof. Karsten Haupt

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201412494

      Thumbnail image of graphical abstract

      Read the small (im)print: Molecularly imprinted polymers (MIPs) are artificial receptors which can be tailored to bind target molecules specifically. The title reaction is compatible with acidic monomers, for their synthesis as monoliths, thin films and nanoparticles. This paves the way for surface modification and lithographic patterning of MIPs and their postfunctionalization from living chain-ends. ppy=2-phenylpyridine.

    18. Asymmetric Catalysis

      Redox Tuning of a Direct Asymmetric Aldol Reaction

      Qiying Zhang, Prof. Dr. Xiuling Cui, Dr. Long Zhang, Prof. Dr. Sanzhong Luo, Hui Wang and Prof. Dr. Yangjie Wu

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201500070

      Thumbnail image of graphical abstract

      Stay tuned: A redox tuning strategy has been developed for asymmetric aminocatalysis using a chiral ferrocenophane. Under redox control, the catalyst catalyzes the asymmetric aldol reaction at room temperature with excellent yield and good stereoselectivity. Moreover, the catalyst is recyclable.

    19. Aggregation

      o-Carborane-Based Anthracene: A Variety of Emission Behaviors

      Hirofumi Naito, Prof. Yasuhiro Morisaki and Prof. Yoshiki Chujo

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201500129

      Thumbnail image of graphical abstract

      Multiple personalities: Single crystals of o-carborane-based anthracene were obtained. In the crystal, the anthracene ring is highly distorted because of the formation of a π-stacked dimer. The crystals exhibit a variety of emission behaviors such as aggregation-induced emission (AIE), crystallization-induced emission (CIE), aggregation-caused quenching (ACQ), vapochromism, thermochromism, and mechanochromism.

  4. News

  5. Highlights

    1. Genome Engineering

      CRISPR Craze Conquers the RNA World: Precise Manipulation of DNA and RNA Based on a Bacterial Defense System

      Prof. Dr. Andrea Rentmeister

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201500563

      Thumbnail image of graphical abstract

      It cuts both ways: The CRISPR/Cas9 genome engineering system has been extended from DNA to RNA. The sequence-specific targeting and cleavage of RNA can be achieved with S. pyogenes Cas9–gRNA if an appropriate short single-stranded oligonucleotide, the “PAMmer”, is added. This technique could lead to a general approach for sequence-specific RNA manipulation.

  6. Cover Pictures

    1. New Insights into the Hexaphenylethane Riddle: Formation of an α,o-Dimer

      Yasuto Uchimura, Dr. Takashi Takeda, Dr. Ryo Katoono, Prof. Dr. Kenshu Fujiwara and Prof. Dr. Takanori Suzuki

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201501649

      Thumbnail image of graphical abstract

      Since the discovery of triphenylmethyl by Gomberg in 1900, its dimerization has been extensively studied. However, the actual structure of the dimer (the α,p-adduct) was not identified until 1968 as it was believed to have the incorrectly assigned hexaphenylethane (α,α-adduct) structure. Hindered but stable α,α-adducts have since become available by the “arylenediyl” approach. In their Communication (DOI: 10.1002/anie.201500122), T. Suzuki et al. now report the first generation of the α,o-adduct.

    2. Mechanochromic Photonic-Crystal Fibers Based on Continuous Sheets of Aligned Carbon Nanotubes

      Dr. Xuemei Sun, Jing Zhang, Xin Lu, Xin Fang and Prof. Huisheng Peng

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201501646

      Thumbnail image of graphical abstract

      Mechanochromic photonic-crystal fibers with tunable structural colors are described by X. Sun, H. Peng, and co-workers in their Communication (DOI: 10.1002/anie.201412475). When subjected to mechanical strain, these fibers undergo reversible and rapid color changes, and their reflection peaks are shifted. These elastic photonic-crystal fibers can be woven into colorful patterns and fabrics for various applications in displays and sensing devices.

    3. Cycloparaphenylene-Based Ionic Donor–Acceptor Supramolecule: Isolation and Characterization of Li+@C60⊂[10]CPP

      Dr. Hiroshi Ueno, Dr. Taishi Nishihara, Prof.Dr. Yasutomo Segawa and Prof.Dr. Kenichiro Itami

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201501644

      Thumbnail image of graphical abstract

      A strong charge-transfer interaction between [10]cycloparaphenylene (CPP) and Li+@C60 in the first CPP-based ionic donor–acceptor supramolecule Li+@C60⊂[10]CPP⋅X is confirmed by electrochemical measurement and spectroscopic analyses. K. Itami and co-workers show in their Communication (10.1002/anie.201500544) that the cationic charge on the Li+ ion is delocalized not only onto the fullerene cage, but also further onto the outer CPP ring. Thus the whole compound is a well-structured, supramolecular cation.

  7. Communications

    1. Photochemistry

      Auger Ionization Beats Photo-Oxidation of Semiconductor Quantum Dots: Extended Stability of Single-Molecule Photoluminescence

      Shin-ichi Yamashita, Morihiko Hamada, Prof. Shunsuke Nakanishi, Hironobu Saito, Prof. Yoshio Nosaka, Dr. Shin-ichi Wakida and Dr. Vasudevanpillai Biju

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201501131

      Thumbnail image of graphical abstract

      Preventing oxidation: Single semiconductor quantum dots escape from photoluminescence (PL; see picture) loss, which is due to the self-sensitized oxidation by singlet oxygen, by the transient escape into the Auger-ionized state. The ultrafast non-radiative recombination processes of carriers in the trion state of such quantum dots shut down the energy transfer pathway to molecular oxygen.

    2. Asymmetric Catalysis

      Aromatic Amide-Derived Non-Biaryl Atropisomers as Highly Efficient Ligands in Silver-Catalyzed Asymmetric Cycloaddition Reactions

      Xing-Feng Bai, Tao Song, Dr. Zheng Xu, Prof. Chun-Gu Xia, Wei-Sheng Huang and Prof. Dr. Li-Wen Xu

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201501100

      Thumbnail image of graphical abstract

      New chiral ligands: Optically pure aromatic amide-derived atropisomers were shown to be powerful phosphine ligands in the enantioselective silver-catalyzed [3+2] cycloaddition. This method provides a highly efficient strategy for the synthesis of optically pure nitro-substituted pyrrolidines with multiple stereogenic centers.

    3. Group 13 Metal Catalysis | Hot Paper

      Cooperative Bond Activation and Catalytic Reduction of Carbon Dioxide at a Group 13 Metal Center

      Joseph A. B. Abdalla, Dr. Ian M. Riddlestone, Rémi Tirfoin and Prof. Simon Aldridge

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201500570

      Thumbnail image of graphical abstract

      A single-component ambiphilic Group 13 system has been developed, capable of the cooperative activation of protic, hydridic and apolar H[BOND]X bonds. The hydride complex derived from the activation of H2 catalyzes the selective transformation of CO2 to a methanol derivative, representing the first example of such a reduction process catalyzed by a molecular gallium complex.

    4. Cross-Coupling

      Copper/Palladium Synergistic Catalysis for the syn- and anti-Selective Carboboration of Alkenes

      Kaitlyn M. Logan, Kevin B. Smith and Prof. M. Kevin Brown

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201500396

      Thumbnail image of graphical abstract

      The diastereoselective carboboration of 1,2-disubstituted styrenes with aryl/vinyl bromides and (Bpin)2 proceeds with high diastereoselectivities and yields. The formation of either diastereomer of the product from a single alkene isomer is determined by the reaction conditions. The method thus provides access to a diverse range of structures from simple starting materials.

    5. Donor–Acceptor Systems

      Charge Separation in Graphene-Decorated Multimodular Tris(pyrene)–Subphthalocyanine–Fullerene Donor–Acceptor Hybrids

      Chandra B. KC, Gary N. Lim and Prof. Dr. Francis D'Souza

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201500156

      Thumbnail image of graphical abstract

      In a split second: Ultrafast photochemical charge separation in multimodular donor–acceptor systems, composed of three units of pyrene, a subphthalocyanine, and a fullerene hybridized on graphene through π–π stacking interactions, is demonstrated using femtosecond transient spectroscopy. The present hybrids may have use as materials for fast-responding optoelectronic devices and in light energy harvesting applications.

  8. Reviews

    1. Enantioselective Photocatalysis

      Enantioselective Catalysis of Photochemical Reactions

      Dr. Richard Brimioulle, M. Sc. Dominik Lenhart, M. Sc. Mark M. Maturi and Prof. Dr. Thorsten Bach

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201411409

      Thumbnail image of graphical abstract

      All good things come in threes: With catalysis, light, and chirality, three of the most important scientific phenomena merge in the field of the enantioselective catalysis of photochemical reactions. This Review introduces the main concepts and provides an overview of the key findings in this area.

  9. Communications

    1. Synthetic Methods

      Rhodium-Catalyzed [(3+2)+2] Carbocyclization of Alkynylidenecyclopropanes with Substituted Allenes: Stereoselective Construction of Tri- and Tetrasubstituted Exocyclic Olefins

      Prof. P. Andrew Evans, Daniela E. Negru and Dr. Deju Shang

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201410857

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      At a distance: The development of the title reaction demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. cod=1,5-cyclooctadiene, Ts=4-toluenesulfonyl.

    2. Knotted Polymers

      A Trefoil Knotted Polymer Produced through Ring Expansion

      Peng-Fei Cao, Joey Mangadlao and Prof. Rigoberto Advincula

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201411623

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      Knot a problem: A synthetic strategy is reported for the production of a trefoil knotted polymer from a CuI-templated helical knot precursor through ring expansion. The expected changes in the properties of the knotted polymer compared to a linear analogue, namely reduced hydrodynamic radius and lower intrinsic viscosity, together with atomic force microscopy images of individual molecular knots, confirmed the formation of a trefoil knotted polymer.

    3. Proton-Conducting Materials

      Superprotonic Conductivity of a UiO-66 Framework Functionalized with Sulfonic Acid Groups by Facile Postsynthetic Oxidation

      Dr. Won Ju Phang, Hyuna Jo, Woo Ram Lee, Jeong Hwa Song, Kicheon Yoo, Dr. BongSoo Kim and Prof. Chang Seop Hong

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201411703

      Thumbnail image of graphical abstract

      Decorated for honorable conductivity: The postsynthetic oxidation of a thiol-laced UiO-66-type framework generated sulfonic acid groups covalently linked to the backbone of the system (see picture; green circles are Zr[BOND]O nodes). The oxidized material exhibited stable superprotonic conductivity of 8.4×10−2 S cm−1 at 80 °C and 90 % relative humidity.

    4. Synthetic Methods

      A Concise Flow Synthesis of Efavirenz

      Dr. Camille A. Correia, Dr. Kerry Gilmore, Prof. Dr. D. Tyler McQuade and Prof. Dr. Peter H. Seeberger

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201411728

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      As fast as you can: Efavirenz is an essential medicine for the treatment of HIV, which is inaccessible to millions of people worldwide. A proof-of-principle, semi-continuous, three-step synthesis that is based on the intramolecular cyclization of an aryl isocyanate provides rac-Efavirenz in three steps and 45 % overall yield.

    5. Enantioselective Organocatalysis

      Enantioselective Desymmetrization of Prochiral Cyclohexanones by Organocatalytic Intramolecular Michael Additions to α,β-Unsaturated Esters

      Adam D. Gammack Yamagata, Dr. Swarup Datta, Kelvin E. Jackson, Linus Stegbauer, Dr. Robert S. Paton and Prof. Dr. Darren J. Dixon

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201411924

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      Enantioenriched derivatives of 2-azabicyclo[3.3.1]nonane, a key motif common to many alkaloids, are obtained by a catalytic asymmetric desymmetrization reaction with a cyclohexanediamine-derived primary-amine organocatalyst. A range of prochiral cyclohexanone derivatives with an α,β-unsaturated ester moiety linked to the 4-position afford the bicyclic products as single diastereoisomers in high enantioselectivity and good yields.

    6. Cyclization with CO

      Cyclization of a 1,4-Diborabutadiene Ligand with Both Atoms of CO

      Prof. Dr. Holger Braunschweig, Dr. Qing Ye, Dr. Mehmet Ali Celik, Dr. Rian D. Dewhurst and Dr. Krzysztof Radacki

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201411967

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      Ringing the changes: A 1,4-dibora-1,3-butadiene iron complex was successfully synthesized through the stoichiometric reaction of iron bis(borylene) with diphenylacetylene. This complex was treated with CO and PMe3, thereby leading to the formation of an unusual six-membered B2C3O ylidic ring bound to both the PMe3 group and zerovalent iron center. The reaction is a very rare example of the incorporation of both atoms of CO into a ring system.

    7. Chemical Probes

      A Potent, Selective and Cell-Active Allosteric Inhibitor of Protein Arginine Methyltransferase 3 (PRMT3)

      Dr. H. Ümit Kaniskan, Dr. Magdalena M. Szewczyk, Dr. Zhengtian Yu, Dr. Mohammad S. Eram, Dr. Xiaobao Yang, Keith Schmidt, Dr. Xiao Luo, Miao Dai, Dr. Feng He, Irene Zang, Dr. Ying Lin, Dr. Steven Kennedy, Dr. Fengling Li, Elena Dobrovetsky, Aiping Dong, Dr. David Smil, Dr. Sun-Joon Min, Dr. Melissa Landon, Dr. Jennifer Lin-Jones, Dr. Xi-Ping Huang, Prof. Dr. Bryan L. Roth, Prof. Dr. Matthieu Schapira, Dr. Peter Atadja, Dr. Dalia Barsyte-Lovejoy, Prof. Dr. Cheryl H. Arrowsmith, Dr. Peter J. Brown, Dr. Kehao Zhao, Prof. Dr. Jian Jin and Prof. Dr. Masoud Vedadi

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201412154

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      High selectivity: The first PRMT3 chemical probe, SGC707, was discovered by structure-based optimization. SGC707 is a potent PRMT3 inhibitor with outstanding selectivity. The mechanism of action studies and crystal structure of the PRMT3–SGC707 complex confirm the allosteric inhibition mode. SGC707 engages PRMT3 and potently inhibits its methyltransferase activity in cells. It is also bioavailable and suitable for animal studies.

  10. Essays

    1. Energy Industry

      The Revolution Continues: Energiewende 2.0

      Prof. Dr. Robert Schlögl

      Article first published online: 27 FEB 2015 | DOI: 10.1002/anie.201405876

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      You say you want a revolution: The “Energiewende”, the change in energy regimes in Germany, is presently not effective. The lack of integration of renewable and conventional power generation is seen as the critical factor. Chemistry and catalysis play a decisive role in solving this systemic challenge.

  11. Communications

    1. Heterogeneous Catalysis

      You have full text access to this OnlineOpen article
      Mild Deoxygenation of Aromatic Ketones and Aldehydes over Pd/C Using Polymethylhydrosiloxane as the Reducing Agent

      Alexey Volkov, Karl P. J. Gustafson, Dr. Cheuk-Wai Tai, Dr. Oscar Verho, Prof. Dr. Jan-E. Bäckvall and Prof. Dr. Hans Adolfsson

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201411059

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      O, Farewell! Heterogeneous Pd/C was found to be an efficient and recyclable catalyst for the title reaction. The robustness of the catalytic system was demonstrated by the high-yielding reduction of ethyl vanillin, which was conducted on a 30 mmol scale in an open-to-air set-up at room temperature.

    2. DNA Damage

      Discrimination Between 8-Oxo-2′-Deoxyguanosine and 2′-Deoxyguanosine in DNA by the Single Nucleotide Primer Extension Reaction with Adap Triphosphate

      Dr. Yosuke Taniguchi, Yoshiya Kikukawa and Prof. Dr. Shigeki Sasaki

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201412086

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      One is not like the other: The triphosphate of Adap (dAdapTP) was synthesized and used in single nucleotide primer extension reactions with the Klenow Fragment. Based on the extension efficiency, dAdapTP showed excellent discrimination between 8-oxo-dG and dG in the template ODNs. The sequence-specific detection of 8-oxo-dG in human telomeric DNA sequences extracted from H2O2-treated HeLa cells was also performed by an enzymatic incorporation reaction with dAdapTP.

    3. Drug Delivery

      Active Targeting of Tumors through Conformational Epitope Imprinting

      Yan Zhang, Chunyue Deng, Sha Liu, Jin Wu, Prof. Dr. Zhangbao Chen, Prof. Dr. Chong Li and Prof. Weiyue Lu

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201412114

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      Magic bullet: A peptide served as an “indirect” targeting ligand to mediate active tumor-targeted drug delivery. A disulfide-linked α-helix containing peptide, apamin, was used to mimic the extracellular, structured N-terminal part of the protein p32. The combination with surface molecular imprinting produced a nanocarrier that recognizes p32-positive tumors in vivo.

    4. Homogeneous catalysis | Hot Paper

      Lewis Acid Promoted Ruthenium(II)-Catalyzed Etherifications by Selective Hydrogenation of Carboxylic Acids/Esters

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

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201500062

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      An assist from Al: A bifunctional catalyst system consisting of a Ru/phosphine complex and aluminum triflate allows selective hydrogenation of esters to ethers. A variety of lactones were reduced to the desired products in good yields. The catalyst further provides a general method for the reduction of linear esters and reductive etherification of carboxylic acids with alcohols.

    5. Peptide Drugs

      Bioinspired Therapeutic Dendrimers as Efficient Peptide Drugs Based on Supramolecular Interactions for Tumor Inhibition

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

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

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

    6. Gold Chemistry | Very Important Paper

      Oxidative Addition of Carbon–Carbon Bonds to Gold

      Dr. Maximilian Joost, Dr. Laura Estévez, Dr. Karinne Miqueu, Dr. Abderrahmane Amgoune and Dr. Didier Bourissou

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201500458

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      Gold(I) complexes ([(DPCb)Au]+) readily insert into the four-membered rings of biphenylene and benzocyclobutenone. These transformations afforded well-defined cationic organogold(III) complexes that were isolated and fully characterized. [(DPCb)Au]+ is the only complex to cleave selectively either the C(aryl)[BOND]C(O) or the C(alkyl)[BOND]C(O) bond of benzocyclobutenone under kinetic/thermodynamic control. DPCb=diphosphinocarborane.

    7. Water Oxidation

      Cerium(IV)-Driven Water Oxidation Catalyzed by a Manganese(V)–Nitrido Complex

      Li Ma, Qian Wang, Dr. Wai-Lun Man, Dr. Hoi-Ki Kwong, Dr. Chi-Chiu Ko and Prof. Tai-Chu Lau

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201500507

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      High turnover: The study of manganese complexes as catalysts for the oxidation of water is of great interest as they can serve as models for the oxygen-evolving complex of photosystem II. The manganese(V)–nitrido complex [Mn(N)(CN)4]2− was now shown to catalyze the oxidation of water by cerium(IV) with a turnover number (TON) of higher than 180.

    8. Synthetic Methods

      Palladium-Catalyzed Vicinal Amino Alcohols Synthesis from Allyl Amines by in Situ Tether Formation and Carboetherification

      Ugo Orcel and Prof. Dr. Jerome Waser

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201500636

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      Just tether it! Vicinal amino alcohols are important structural motifs of bioactive compounds. Reported herein is an efficient method for their synthesis based on the palladium-catalyzed oxy-alkynylation, oxy-arylation, or oxy-vinylation of allyl amines. High regio- and stereoselectivity were ensured through the in situ formation of a hemiaminal tether using the commercially available trifluoroacetaldehyde in its hemiacetal form.

    9. In Situ Spectroscopy

      Microimaging of Transient Concentration Profiles of Reactant and Product Molecules during Catalytic Conversion in Nanoporous Materials

      Tobias Titze, Dr. Christian Chmelik, Jens Kullmann, Dr. Lutz Prager, Prof. Erich Miersemann, Prof. Roger Gläser, Prof. Dirk Enke, Prof. Jens Weitkamp and Prof. Jörg Kärger

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201409482

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      At a glance: Microimaging by IR microscopy is used to record the evolution of the concentration profiles of reactant and product molecules during catalytic reaction. It is thus shown to allow a one-shot determination of effectiveness factors.

    10. Biocatalysis

      Synthesis of D- and L-Phenylalanine Derivatives by Phenylalanine Ammonia Lyases: A Multienzymatic Cascade Process

      Dr. Fabio Parmeggiani, Dr. Sarah L. Lovelock, Nicholas J. Weise, Syed T. Ahmed and Prof. Nicholas J. Turner

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201410670

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      PAL around: The cascade coupling of phenylalanine ammonia lyase (PAL) with L-amino acid deaminase (LAAD) or D-amino acid oxidase (DAAO), led to the conversion of cheap and easily accessible cinnamic acids into both non-natural D- and L-phenylalanines by a chemoenzymatic process. PAL variants possessing higher D-activity were selected by using a novel solid-phase screening assay and employed to increase yield and ee values.

    11. Mesoporous Materials | Very Important Paper

      Interrupted Chalcogenide-Based Zeolite-Analog Semiconductor: Atomically Precise Doping for Tunable Electro-/Photoelectrochemical Properties

      Jian Lin, Youzhen Dong, Qian Zhang, Dandan Hu, Prof. Dr. Na Li, Dr. Le Wang, Prof. Dr. Yang Liu and Prof. Dr. Tao Wu

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201500659

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      Zeolitic architecture: An interrupted chalcogenide-based zeolite-analog semiconductor with an entirely new boracite-related framework and specific sites at the interrupted section is reported. The specific indium sites serving as effective electrocatalytic active centers for the oxygen reduction reaction proved to be atomically precisely doped by trivalent bismuth ions.

    12. Porphyrinoids

      Phenanthriporphyrin: An Antiaromatic Aceneporphyrinoid as a Ligand for a Hypervalent Organophosphorus(V) Moiety

      Dr. Bartosz Szyszko, Dr. Agata Białońska, Dr. Ludmiła Szterenberg and Prof. Dr. Lechosław Latos-Grażyński

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201500732

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      PAH–porphyrins: Phenanthriporphyrin, an antiaromatic hybrid macrocycle, merges structural facets of polycyclic aromatic hydrocarbons and porphyrins. The {CCNN} core of this aceneporphyrinoid involves phenanthrene carbon atoms which coordinate a hypervalent organophosphorus(V) center. Atom colors: C=gray; N=blue; O=red; H=white; P=purple.

    13. Nanostructures

      Cobalt Phosphide Nanowires: Efficient Nanostructures for Fluorescence Sensing of Biomolecules and Photocatalytic Evolution of Dihydrogen from Water under Visible Light

      Dr. Jingqi Tian, Ningyan Cheng, Qian Liu, Prof. Wei Xing and Prof. Xuping Sun

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201501237

      Thumbnail image of graphical abstract

      Quenched: The high fluorescence quenching ability of cobalt phosphide nanowires (CoP NWs) and their different affinity toward single-stranded and double-stranded DNA were used to develop a rapid fluorescence assay for nucleic acids and proteins. The attachment of dye-labelled oligonucleotide probes to its surfaceof the CoP semiconductor leads togreatly enhanced photocatalytic hydrogen evolution from H2O under visible light.

    14. Pentafluoroethylation | Very Important Paper

      Well-Defined CuC2F5 Complexes and Pentafluoroethylation of Acid Chlorides

      Liubov I. Panferova, Fedor M. Miloserdov, Dr. Anton Lishchynskyi, Dr. Marta Martínez Belmonte, Dr. Jordi Benet-Buchholz and Prof. Vladimir V. Grushin

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201500341

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      Four well-defined CuC2F5 complexes have been prepared and fully characterized, with [(phen)Cu(PPh3)C2F5] (phen=1,10-phenanthroline) proving to be a remarkably efficient fluoroalkylating agent for a broad variety of acid chlorides (see scheme). The developed procedure represents the first general method for the one-step conversion of RCOCl into valuable pentafluoroethyl ketones.

    15. Electrocatalysis

      High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts

      Dr. F. Sloan Roberts, Dr. Kendra P. Kuhl and Prof. Anders Nilsson

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201412214

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      Cubic nanostructures formed on a polycrystalline copper surface give high selectivity for ethylene formation from carbon dioxide electroreduction. The nanocubes are easily synthesized in situ, and online electrochemical mass spectrometry is used to compare the reactivity to other copper single-crystal surfaces.

    16. Biosynthesis

      Biosynthesis of the Carbamoylated D-Gulosamine Moiety of Streptothricins: Involvement of a Guanidino-N-glycosyltransferase and an N-Acetyl-D-gulosamine Deacetylase

      Dr. Zhengyan Guo, Dr. Jine Li, Dr. Hua Qin, Dr. Min Wang, Dr. Xun Lv, Prof. Xuebing Li and Prof. Yihua Chen

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201412190

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      The dynamic duo: Two novel enzymes, StnG and StnI, have been found to be involved in the biosynthetic pathway of the carbamoylated D-gulosamine moiety in streptothricins. StnG is a GT-A fold glycosyltransferase that catalyzes the unprecedented attachment of a sugar to the imine nitrogen atom of a guanidine group; StnI catalyzes the deacetylation of the N-acetyl-D-gulosamine moiety.

    17. Fluorescence

      The Design of Dual Emitting Cores for Green Thermally Activated Delayed Fluorescent Materials

      Yong Joo Cho, Sang Kyu Jeon, Prof. Byung Doo Chin, Dr. Eunsun Yu and Prof. Jun Yeob Lee

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201412107

      Thumbnail image of graphical abstract

      Coupled emitter units: The design of dual emitting cores for thermally activated delayed fluorescent (TADF) materials is reported. The strategy can be used to improve the quantum efficiency of TADF emitters (see picture; PLQY=photoluminescence quantum yield).

    18. Cancer Therapy

      A Smart DNAzyme–MnO2 Nanosystem for Efficient Gene Silencing

      Huanhuan Fan, Dr. Zilong Zhao, Guobei Yan, Prof. Xiaobing Zhang, Dr. Chao Yang, Hongmin Meng, Zhuo Chen, Hui Liu and Prof. Weihong Tan

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201411417

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      Multitasking: A smart carrier for DNAzymes has been developed in which MnO2 nanosheets are able to enhance cellular uptake of DNAzymes, protect them from endogenous nuclease digestion, and self-generate in situ cofactors (Mn2+ ions) in the cell cytoplasm to maintain the catalytic activity of 10–23 DNAzyme for RNA cleavage and gene silencing. Ce6–DNAzyme=chlorin e6-labelled DNAzyme.

    19. Synthetic Methods

      Electrolytic Macrocyclizations: Scalable Synthesis of a Diazonamide-Based Drug Development Candidate

      Dr. Hui Ding, Patrick L. DeRoy, Christian Perreault, Dr. Alexandre Larivée, Dr. Arshad Siddiqui, Dr. Charles G. Caldwell, Susan Harran and Prof. Dr. Patrick G. Harran

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201411663

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      Electrifying chemistry! The core macrolactam of diazonamides can be synthesized electrochemically. This large ring forming dehydrogenation has enabled a concise preparation of DZ-2384, a refined analog of diazonamide A slated for clinical development as a cancer therapeutic.

    20. Biosynthesis

      Enzymatic Basis of “Hybridity” in Thiomarinol Biosynthesis

      Zachary D. Dunn, Walter J. Wever, Dr. Nicoleta J. Economou, Prof. Albert A. Bowers and Prof. Bo Li

      Article first published online: 26 FEB 2015 | DOI: 10.1002/anie.201411667

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      The biosynthetic mechanism responsible for generating the antibiotic thiomarinol was elucidated. In contrast to previous hypotheses, TmlU acts as a CoA-ligase and works in tandem with a second enzyme, acyltransferase HolE, to link two antimicrobial warheads pseudomonic acid and holothin, creating a hybrid antibiotic (see scheme).

    21. Trifluoromethylthiolation

      Silver-Mediated Oxidative Aliphatic C[BOND]H Trifluoromethylthiolation

      Shuo Guo, Xiaofei Zhang and Prof. Dr. Pingping Tang

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201411807

      Thumbnail image of graphical abstract

      The silver-mediated trifluoromethylthiolation of unactivated aliphatic C[BOND]H bonds is reported. The reaction is operationally simple, amenable to gram-scale synthesis, and can be employed for the late-stage trifluoromethylthiolation of complex small molecules.

    22. Layered Structures | Very Important Paper

      Synthesis of Carbon/Sulfur Nanolaminates by Electrochemical Extraction of Titanium from Ti2SC

      Dr. Meng-Qiang Zhao, Morgane Sedran, Zheng Ling, Maria R. Lukatskaya, Olha Mashtalir, Michael Ghidiu, Boris Dyatkin, Darin J. Tallman, Prof. Thierry Djenizian, Prof. Michel W. Barsoum and Prof. Yury Gogotsi

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201500110

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      Carbon/sulfur nanolaminates composed of multi-layered C/S flakes with predominantly amorphous, and some graphene-like, structures were synthesized by electrochemical extraction of Ti from a Ti2SC MAX phase. This approach provides a novel method for the room-temperature synthesis of “AX” layered structures by the selective extraction of “M” from the MAX phases.

  12. Highlights

    1. Piezoelectricity

      Piezoelectricity in Two-Dimensional Materials

      Prof. Dr. Tom Wu and Prof. Dr. Hua Zhang

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201411335

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      Powering up 2D materials: Recent experimental studies confirmed the existence of piezoelectricity—the conversion of mechanical stress into electricity—in two-dimensional single-layer MoS2 nanosheets. The results represent a milestone towards embedding low-dimensional materials into future disruptive technologies.

  13. Communications

    1. Ammonia Coupling

      Nickel-Catalyzed Amination of Aryl Chlorides with Ammonia or Ammonium Salts

      Rebecca A. Green and Prof. John F. Hartwig

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201500404

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      Simple alternative: The title reaction, which results in primary arylamines, is catalyzed by well-defined single-component nickel(0) precatalysts containing a Josiphos ligand and an η2-bound benzonitrile ligand. This system also catalyzes the coupling of aryl chlorides with gaseous amines in the form of their hydrochloride salts.

    2. Total Synthesis

      A General and Scalable Synthesis of Aeruginosin Marine Natural Products Based on Two Strategic C(sp3)[BOND]H Activation Reactions

      David Dailler, Dr. Grégory Danoun and Prof. Dr. Olivier Baudoin

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201500066

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      Family ties: An efficient access to the aeruginosin family of marine natural products, which exhibit potent inhibitory activity against serine proteases, was achieved. The strategic use of two different C(sp3)[BOND]H activation reactions led to the synthesis of aeruginosins 98B and 298 A, with the latter being obtained on an unprecedentedly large scale.

    3. Biomedical Materials

      Highly Biocompatible Nanofibrous Microspheres Self-Assembled from Chitin in NaOH/Urea Aqueous Solution as Cell Carriers

      Bo Duan, Xing Zheng, Zhixiong Xia, Xiaoli Fan, Lin Guo, Prof. Jianfeng Liu, Prof. Yanfeng Wang, Prof. Qifa Ye and Prof. Lina Zhang

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201412129

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      Nimbly weaved: Chitin chains rapidly self-assembled into nanofibers in aqueous NaOH/urea solution by a thermally induced method. Subsequently, the nanofibers formed weaved chitin microspheres (NCM) having a uniform architecture throughout. Cells could adhere to the nanofibrous NCM, which indicates the great potential of the NCM for cell microcarriers.

    4. Polymer–Semiconductor Hybrids

      An Unconventional Route to Monodisperse and Intimately Contacted Semiconducting Organic–Inorganic Nanocomposites

      Hui Xu, Dr. Xinchang Pang, Yanjie He, Dr. Ming He, Jaehan Jung, Prof. Dr. Haiping Xia and Prof. Dr. Zhiqun Lin

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201500763

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      A robust strategy to produce spherically shaped organic–inorganic nanocomposites composed of PbTe nanoparticles tethered with poly(3,4-ethylenedioxythiophene) (PEDOT) chains was developed by using amphiphilic star-like diblock copolymer PAA-b-PEDOT as template. The PbTe–PEDOT nanohybrids show long-term stability and hold promise for use in thermoelectrics.

    5. Polymerization | Hot Paper

      Iron-Catalyzed Dehydropolymerization: A Convenient Route to Poly(phosphinoboranes) with Molecular-Weight Control

      Dr. André Schäfer, Dr. Titel Jurca, Joshua Turner, Dr. James R. Vance, Dr. Kajin Lee, Dr. Van An Du, Dr. Mairi F. Haddow, Dr. George R. Whittell and Prof. Dr. Ian Manners

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201411957

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      Loading matters: The catalyst loading is the key to control the molecular weight of the polymer in the iron-catalyzed dehydropolymerization of phosphine–borane adducts. Studies showed that the reaction proceeds through a chain-growth coordination–insertion mechanism.

    6. Paracyclophanes

      Cyclophanes Containing Bowl-Shaped Aromatic Chromophores: Three Isomers of anti-[2.2](1,4)Subphthalocyaninophane

      Dr. Quan Liu, Prof. Soji Shimizu and Prof. Nagao Kobayashi

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201411510

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      Bending the rules: A transannular interaction between two bowl-shaped π-conjugated systems was investigated in the designed subphthalocyaninophane (see scheme). The extension of π conjugation along the long axis of the molecule led to redshifting, broadening, and splitting of the Q band in the UV/Vis absorption spectrum. 1H NMR spectra showed significant differences between the endo and exo faces of the subphthalocyanine units.

    7. Bionanotechnology

      Photothermally Induced Local Dissociation of Collagens for Harvesting of Cell Sheets

      Jae Dong Kim, June Seok Heo, Teahoon Park, Chihyun Park, Prof. Hyun Ok Kim and Prof. Eunkyoung Kim

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201411386

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      A live cell sheet is harvested by the dissociation of adsorbed collagens on a poly(3,4-ethylenedioxythiophene) (PEDOT) surface by a photothermal method employing near-IR (NIR) radiation. Irradiation with NIR light induces unfolding of the collagen triple helices leading to the spatially controlled detachment of a patterned cell sheet with intact cell morphology.

    8. Tetracarbene Ligands

      Reversible Photochemical Modifications in Dicarbene-Derived Metallacycles with Coumarin Pendants

      Prof. Ying-Feng Han, Prof. Guo-Xin Jin, Constantin G. Daniliuc and Prof. F. Ekkehardt Hahn

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201411006

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      Tying up loose ends: The synthesis and characterization of a series of dinuclear molecular rectangles (1) containing CuI, AgI, or AuI ions and coumarin pendants is described. Photochemically induced [2+2] cycloaddition reactions were performed with these complexes to give new complexes (2) featuring a macrocyclic coordinated tetracarbene ligand and two cyclobutane rings.

    9. Biosynthesis

      Discovery and Reconstitution of the Cycloclavine Biosynthetic Pathway—Enzymatic Formation of a Cyclopropyl Group

      Dr. Dorota Jakubczyk, Dr. Lorenzo Caputi, Anaëlle Hatsch, Curt A. F. Nielsen, Melanie Diefenbacher, Jens Klein, Andrea Molt, Hartwig Schröder, Dr. Johnathan Z. Cheng, Dr. Michael Naesby and Prof. Sarah E. O'Connor

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201410002

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      Who’s responsible for the ring? The biosynthetic pathway of the ergot alkaloid cycloclavine (see scheme) was discovered and reconstituted in yeast at titers of >500 mg L−1. A yeast-based expression platform and in vitro biochemical experiments enabled the identification of the enzyme that catalyzes the unprecedented rearrangement of a biosynthetic intermediate to form the cyclopropyl moiety of cycloclavine.

    10. Cation–Cation Interactions

      Cation–Cation Pairing by N[BOND]C[BOND]H⋅⋅⋅O Hydrogen Bonds

      Waltraud Gamrad, Angelika Dreier, Dr. Richard Goddard and Prof. Dr. Klaus-Richard Pörschke

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201408278

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      Same-sex chemistry: A novel pairing of cations is reported. When 4-oxopiperidinium cations are combined with the weakly basic NTf2 anion, the cations link head-to-tail through N[BOND]H⋅⋅⋅O hydrogen bonds to form chains of cations, flanked by anions. With the larger and noncoordinating [Al{OC(CF3)3}4] counterion, centrosymmetric dicationic pairs of 4-oxopiperidinium ions form in the crystal through C[BOND]H⋅⋅⋅O hydrogen bonds.

  14. Book Reviews

    1. The Chemical Bond. Two Volume Set. Edited by Gernot Frenking and Sason Shaik.

      Gabriel Merino and Thomas Heine

      Article first published online: 25 FEB 2015 | DOI: 10.1002/anie.201412068

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      Wiley-VCH, Weinheim, 2014. 1004 pp., hardcover, € 229.00.—ISBN 978-3527333189

  15. Communications

    1. Photoelectrochemistry

      Electro-Assembly of a Chromophore–Catalyst Bilayer for Water Oxidation and Photocatalytic Water Splitting

      Dr. Dennis L. Ashford, Dr. Benjamin D. Sherman, Dr. Robert A. Binstead, Prof. Joseph L. Templeton and Prof. Thomas J. Meyer

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201410944

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      Electropolymerization is used to prepare electrocatalytically and photocatalytically active electrodes for water oxidation. The catalyst studied shows a change in the water oxidation mechanism in the polymerized film as compared to solution. This approach establishes a new method for forming a chromophore–catalyst structure on mesoporous TiO2 films for use in a water splitting dye-sensitized photoelectrosynthesis cells.

    2. Antitumor Agents | Hot Paper

      (−)-Englerin A is a Potent and Selective Activator of TRPC4 and TRPC5 Calcium Channels

      M. Sc. Yasemin Akbulut, Hannah J. Gaunt, Prof. Katsuhiko Muraki, Dr. Melanie J. Ludlow, Dr. Mohamed S. Amer, Dr. Alexander Bruns, Dr. Naveen S. Vasudev, Dr. Lea Radtke, Dr. Matthieu Willot, M. Sc. Sven Hahn, M. Sc. Tobias Seitz, Dr. Slava Ziegler, Prof. Dr. Mathias Christmann, Prof. Dr. David J. Beech and Prof. Dr. Herbert Waldmann

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201411511

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      Natural born killer: The sesquiterpene (−)-englerin A rapidly and selectively kills renal cancer cells through activation of calcium-permeable nonselective transient receptor potential canonical (TRPC) calcium channels. It is a highly efficient, fast-acting, potent, selective, and direct stimulator of TRPC4 and TRPC5 channels (PM=plasma membrane).

    3. C[BOND]H Activation

      Direct Trifluoromethylthiolation of Unactivated C(sp3)[BOND]H Using Silver(I) Trifluoromethanethiolate and Potassium Persulfate

      Hao Wu, Zhiwei Xiao, Junhui Wu, Prof. Dr. Yong Guo, Prof. Dr. Ji-Chang Xiao, Prof. Dr. Chao Liu and Prof. Dr. Qing-Yun Chen

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201411953

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      Direct and mild: A variety of alkyltrifluoromethylthioethers were efficiently synthesized by direct trifluoromethylthiolation of unactivated C(sp3)[BOND]H bonds under mild reaction conditions. The reagent system comprises AgSCF3 and K2S2O8, the latter of which both activates the C(sp3)[BOND]H bond and oxidizes AgSCF3. The reaction has a broad substrate scope with good functional-group tolerance and good selectivity.

    4. Asymmetric Catalysis | Hot Paper

      Temperature-Controlled Bidirectional Enantioselectivity in a Dynamic Catalyst for Asymmetric Hydrogenation

      M. Sc. Golo Storch and Prof. Dr. Oliver Trapp

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201412098

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      Temperature switches enantioselectivity! A stereochemically flexible diastereomeric rhodium(I) catalyst has been designed for the asymmetric hydrogenation of prochiral (Z)-α-acetamidocinnamates and α-substituted acrylates. The catalyst changes its enantioselectivity depending on the temperature to produce each single enantiomer in high yield and a constant high enantioselectivity.

    5. Stereocontrol

      Unique Stereocontrol in Carborane Chemistry: Skeletal Alkylcarbonation (SAC) versus Exoskeletal Alkylmethylation (EAM) Reactions

      Dr. Mario Bakardjiev, Dr. Josef Holub, Dr. Jan Macháček, Dr. Drahomír Hnyk, Prof. Dr. Bohumil Štíbr, Dr. Zdeňka Růžičková and Prof. Dr. Aleš Růžička

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201500824

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      Demand and deliver: Reactions between arachno-6,9-C2B8H14 and acyl chlorides are uniquely stereocontrolled. Sterically undemanding chlorides give tricarbollides 8-R-nido-7,8,9-C3B8H11 (skeletal alkylcarbonation=SAC products), while bulky chlorides produce entirely different 1-R-2-CH3-closo-1,6-C2B8H8 dicarbaboranes (exoskeletal alkylmethylation=EAM products).

    6. Asymmetric Catalysis

      Enantioselective Synthesis of Macrocyclic Heterobiaryl Derivatives of Molecular Asymmetry by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis

      Yoichi Okayama, Satoru Tsuji, Yuka Toyomori, Prof. Dr. Atsunori Mori, Dr. Sachie Arae, Dr. Wei-Yi Wu, Prof. Dr. Tamotsu Takahashi and Prof. Dr. Masamichi Ogasawara

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201500459

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      Winding-vine-shaped molecular asymmetry is induced by enantioselective ring-closing metathesis with a chiral molybdenum catalyst. The reaction proceeds under mild reaction conditions through an E-selective ring-closing metathesis leading to macrocyclic bisazoles with enantioselectivities of up to 96 % ee.

    7. Conducting Membranes

      A Mixed Ionic and Electronic Conducting Dual-Phase Membrane with High Oxygen Permeability

      Wei Fang, Dr. Fangyi Liang, Dr. Zhengwen Cao, Frank Steinbach and Prof. Dr. Armin Feldhoff

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201411963

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      A dual-phase membrane made of two different mixed ionic–electronic conductors (MIEC) is presented. This composite mechanism enhances the rate of surface exchange and bulk diffusion for oxygen permeation at the same time. TPB=triple phase boundary.

    8. Metal Nanocrystals

      Direct Conversion of Bulk Metals to Size-Tailored, Monodisperse Spherical Non-Coinage-Metal Nanocrystals

      Rui-Chun Luo, Chao Li, Prof. Xi-Wen Du and Prof. Jing Yang

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201411322

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      A robust conversion strategy that is free of reducing agents and precursors is developed. This method transforms bulk non-noble metals directly into ligand-protected, size-tailored, highly crystalline monodisperse spherical colloidal metal nanocrystals (NCs). The technique is based on near-IR laser-induced size-selective layer-by-layer surface vaporization. The monodisperse Cd NCs exhibit pronounced deep-UV localized surface plasmon resonance.

    9. Biocatalysis

      Individual Surface-Engineered Microorganisms as Robust Pickering Interfacial Biocatalysts for Resistance-Minimized Phase-Transfer Bioconversion

      Zhaowei Chen, Haiwei Ji, Chuanqi Zhao, Enguo Ju, Prof. Dr. Jinsong Ren and Prof. Dr. Xiaogang Qu

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201412049

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      Whole-cell biocatalysis in biphasic systems was achieved by using individually encapsulated bacteria as robust recyclable Pickering interfacial biocatalysts. By minimizing diffusional resistance, enhanced bioconversion efficiencies were obtained, for example for the conversion of hydrophobic (R,S)-mandelonitrile into hydrophilic (R)-(−)-mandelic acid.

    10. Heterogeneous Catalysis

      Probing the Coordinative Unsaturation and Local Environment of Ti3+ Sites in an Activated High-Yield Ziegler–Natta Catalyst

      Elena Morra, Prof. Elio Giamello, Prof. Sabine Van Doorslaer, Giuseppe Antinucci, Dr. Maddalena D'Amore, Prof. Vincenzo Busico and Prof. Mario Chiesa

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201412052

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      Advanced EPR experiments reveal the coordination environment and chemical accessibility of Ti3+ sites in an activated MgCl2-supported industrial Ziegler–Natta (ZN) catalyst. These results provide the first detailed characterization of potential catalytically active sites in industrial ZN catalysts. Sphere colors: green=Cl, yellow=Mg2+.

    11. C[BOND]H Activation

      OH-Directed Alkynylation of 2-Vinylphenols with Ethynyl Benziodoxolones: A Fast Access to Terminal 1,3-Enynes

      Peter Finkbeiner, Ulrich Kloeckner and Jun.-Prof. Dr. Boris J. Nachtsheim

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201412148

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      TIPS and tricks for alkynylation: The first direct alkynylation of 2-vinylphenols was developed. The rationally optimized hypervalent iodine reagent TIPS-EBX* (see scheme)in combination with [(Cp*RhCl2)2] as a C[BOND]H-activating transition metal catalyst enables the construction of a variety of highly substituted 1,3-enynes in high yield under mild conditions and with excellent chemo- and stereoselectivity.

    12. Natural Product Synthesis | Hot Paper

      A Concise and Scalable Strategy for the Total Synthesis of Dictyodendrin B Based on Sequential C[BOND]H Functionalization

      Andrew K. Pitts, Dr. Fionn O'Hara, Dr. Robert H. Snell and Prof. Matthew J. Gaunt

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201500067

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      One by one: A sequential C[BOND]H functionalization strategy for the synthesis of the marine alkaloid dictyodendrin B is reported. The synthetic route begins from commercially available 4-bromoindole and involves six direct functionalizations around the heteroarene core as part of a gram-scale strategy towards the natural product.

    13. Molecular Switches | Hot Paper

      Visible-Light-Triggered Molecular Photoswitch Based on Reversible E/Z Isomerization of a 1,2-Dicyanoethene Derivative

      Dr. Xin Guo, Jiawang Zhou, Dr. Maxime A. Siegler, Prof. Dr. Arthur E. Bragg and Prof. Dr. Howard E. Katz

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201410945

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      Light switch: A dicyanoethene-based molecular photoswitch operates only through E/Z photoisomerization that is triggered by visible light (100 % E[RIGHTWARDS ARROW]Z conversion within minutes). The combination of favorable properties in a single photochromic switch makes it an attractive alternative to the frequently used azobenzenes in numerous photoswitching applications.

    14. Organosuperelasticity

      Superelastic Shape Recovery of Mechanically Twinned 3,5-Difluorobenzoic Acid Crystals

      Prof. Dr. Satoshi Takamizawa and Yuichi Takasaki

      Article first published online: 23 FEB 2015 | DOI: 10.1002/anie.201411447

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      Organosuperelasticity is observed in single crystals of 3,5-difluorobenzoic acid. This elasticity is due to the molecular distortion on the twinning interface, suggesting a new mechanism for superelasticity in molecular materials.

    15. Metastable Materials

      Sulfates-Based Nanothermites: An Expanding Horizon for Metastable Interstitial Composites

      Dr. Marc Comet, Dr. Geoffrey Vidick, Fabien Schnell, Yves Suma, Bernard Baps and Dr. Denis Spitzer

      Article first published online: 20 FEB 2015 | DOI: 10.1002/anie.201410634

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      Big bang theory (and practice): Metal sulfates are used as oxidizers in reactive compositions with aluminum nanopowder (n-Al), leading to energetic materials with high reaction heats (4–6 kJ g−1), fast combustion velocities (200–840 m s−1), and extremely low sensitivity to friction. Compositions prepared from other sulfur oxygenates (SO32−, S2O32−, S2O82−) and n-Al have analogous properties.

    16. Self-Assembly

      When Molecular Probes Meet Self-Assembly: An Enhanced Quenching Effect

      Chunhua Ren, Huaimin Wang, Duo Mao, Xiaoli Zhang, Qianqi Fengzhao, Yang Shi, Dr. Dan Ding, Prof. Deling Kong, Dr. Ling Wang and Prof. Zhimou Yang

      Article first published online: 20 FEB 2015 | DOI: 10.1002/anie.201411833

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      The incorporation of one or two fluoro phenylalanine groups (fFs) in conventional quenched probes can lead to the production of self-assembled probes with enhanced quenching effects. The self-assembled probes possess similar enzyme recognition and fluorescence recovery properties. This provides a useful strategy for the design of molecular probes with good fluorescence turn-on properties.

    17. Cluster Compounds

      A Functionalized Ag2S Molecular Architecture: Facile Assembly of the Atomically Precise Ferrocene-Decorated Nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18]

      Yiyi Liu, Bahareh Khalili Najafabadi, Mahmood Azizpoor Fard and Prof. Dr. John F. Corrigan

      Article first published online: 20 FEB 2015 | DOI: 10.1002/anie.201411944

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      All wrapped up! A ferrocenyl-based dithiol reagent has been employed as a precursor for the preparation of a surface-functionalized Ag74S55 nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18] (dppp=1,3-bis(diphenylphosphino)propane, fc=[Fe(η5-C5H4)2]). The electrochemical properties and single-crystal X-ray structure of the cluster are reported (atom colors: Ag=blue, S=yellow, P=green, O=red, Fe=orange, C=gray).

    18. Zinc Finger Proteins

      113Cd NMR Experiments Reveal an Unusual Metal Cluster in the Solution Structure of the Yeast Splicing Protein Bud31p

      Dr. Anne-Marie M. van Roon, Dr. Ji-Chun Yang, Dr. Daniel Mathieu, Dr. Wolfgang Bermel, Dr. Kiyoshi Nagai and Dr. David Neuhaus

      Article first published online: 20 FEB 2015 | DOI: 10.1002/anie.201412210

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      Cadmium finds the links: Replacing zinc with the spin equation image isotope cadmium-113 makes it possible to trace metal–ligand bonding networks in zinc finger proteins using NMR spectroscopy. Previously this approach was restricted to very small domains, but the structure determination of Bud31p, a 157-residue splicing protein from yeast, shows that recently introduced hardware advances have turned this into a widely useful method.