Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 36

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, Zeitschrift für Chemie

  1. Communications

    1. Wet Adhesion

      Intrinsic Surface-Drying Properties of Bioadhesive Proteins

      Dr. Yasar Akdogan, Dr. Wei Wei, Dr. Kuo-Ying Huang, Dr. Yoshiyuki Kageyama, Eric W. Danner, Dusty R. Miller, Nadine R. Martinez Rodriguez, Prof. Dr. J. Herbert Waite and Prof. Dr. Songi Han

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406858

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      Home and dry underwater: Repulsive hydration forces hinder wet adhesion in the absence of applied external forces. The direct measurement of hydration-water dynamics by NMR relaxometry at 10 GHz revealed that the most hydrophobic mussel adhesive protein, and not the most enriched with 3,4-dihydroxyphenylalanine, effectively dries the surface and overcomes repulsive hydration forces to adsorb spontaneously to surfaces in preparation for adhesion.

  2. Book Reviews

    1. The Last Alchemist in Paris. & other curious tales from chemistry. By Lars Öhrström.

      Gerald Linti

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201407853

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      Oxford University Press, Oxford, 2013. 272 pp., hardcover, £ 16.99.—ISBN 978-0199661091

  3. News

  4. Communications

    1. Asymmetric Catalysis

      Palladium-Catalyzed Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with Michael Acceptors: Construction of Vicinal Quaternary Stereocenters

      Ajmal Khan, Lei Yang, Jing Xu, Prof. Dr. Long Yi Jin and Prof. Dr. Yong Jian Zhang

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201407013

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      Vicinal all-carbon quaternary stereocenters are constructed through a Pd-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates 1 with Michael acceptors 2 (see Scheme). By using a palladium complex generated in situ from [Pd2(dab)3]⋅CHCl3 and phosphoramidite L, the process provides multifunctionalized tetrahydrofurans 3 in high yields with high levels of diastereo- and enantioselectivities.

    2. Carbodicarbenes

      Synthesis and Isolation of an Acyclic Tridentate Bis(pyridine)carbodicarbene and Studies on Its Structural Implications and Reactivities

      Yu-Chen Hsu, Jiun-Shian Shen, Dr. Bo-Chao Lin, Dr. Wen-Ching Chen, Prof. Yi-Tsu Chan, Dr. Wei-Min Ching, Prof. Glenn P. A. Yap, Dr. Chao-Ping Hsu and Dr. Tiow-Gan Ong

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406481

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      The acyclic pincer ligand bis(pyridine)carbodicarbene was synthesized, isolated, and characterized. It features a C-C-C angle of 143°, which is larger than that in the monodentate framework. Palladium complexes supported by this ligand are active catalysts in Heck–Mizoroki and Suzuki–Miyaura coupling reactions.

    3. Fischer–Tropsch Kinetics | Hot Paper

      The optimally performing Fischer–Tropsch catalyst

      Ivo A. W. Filot, Prof. Dr. Rutger A. van Santen and Prof. Dr. Emiel J. M. Hensen

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406521

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      State-of-the-art quantum-chemical reaction data were used in a microkinetics simulations study to elucidate the different fundamental kinetic regimes underlying Fischer–Tropsch activity and selectivity. Based on the nature of the rate-controlling steps, three regimes were identified: I) monomer formation, II) chain-growth termination, and III) water formation.

    4. Triboelectrification | Very Important Paper

      Bipolar Tribocharging Signal During Friction Force Fluctuations at Metal–Insulator Interfaces

      Dr. Thiago A. L. Burgo and Dr. Ali Erdemir

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406541

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      Friction force fluctuation and tribocurrent generation at metal–insulator interfaces show a strong correlation during sliding contacts. The reported results suggest that these two phenomena have a common origin that must be associated with the occurrence of strong electrostatic interactions at the interface.

    5. Cyclic Peptides

      Racemic and Quasi-Racemic X-ray Structures of Cyclic Disulfide-Rich Peptide Drug Scaffolds

      Conan K. Wang, Gordon J. King, Susan E. Northfield, Paola G. Ojeda and Prof. Dr. David J. Craik

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406563

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      Looking into the mirror: Cyclic disulfide-rich peptides are exceptionally stable and thus promising frameworks for drug design, however, disulfide-rich peptides are notoriously difficult to crystallize. To overcome this limitation, L- and D-forms of three prototypic cyclic disulfide-rich peptides were synthesized for crystallization studies on the racemic mixtures.

    6. Lithium-Ion Batteries | Very Important Paper

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

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

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406719

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      A new aspect: When titanate-based nanotubes are used to fabricate electrode materials, the aspect ratio of the nanostructures correlates with the electrochemical performance in lithium-ion batteries. These insights should be useful in the development of efficient energy devices based on nanomaterials.

    7. Cancer Vaccines

      A Cancer Therapeutic Vaccine based on Clustered Tn-Antigen Mimetics Induces Strong Antibody-Mediated Protective Immunity

      Dr. Barbara Richichi, Baptiste Thomas, Dr. Michele Fiore, Dr. Rosa Bosco, Dr. Huma Qureshi, Prof. Dr. Cristina Nativi, Prof. Dr. Olivier Renaudet and Dr. Lbachir BenMohamed

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406897

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      Fantastic four: Four clustered mimetics of the tumor-associated carbohydrate antigen Tn (red) and a T-helper-cell peptide epitope (blue) conjugated to a cyclopeptide carrier (RAFT) are the chemical components of a new improved vaccine prototype. This fully synthetic vaccine elicits a robust and long-lasting IgG/IgM antibody response and induces tumor protection in mice through a B-cell-mediated mechanism.

    8. Supramolecular Chemistry

      Self-Assembly of a Giant Molecular Solomon Link from 30 Subcomponents

      Dr. Clément Schouwey, Dr. Julian J. Holstein, Dr. Rosario Scopelliti, Konstantin O. Zhurov, Dr. Konstantin O. Nagornov, Prof. Yury O. Tsybin, Dr. Oliver S. Smart, Dr. Gérard Bricogne and Prof. Kay Severin

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201407144

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      Linking with sticks: A molecular Solomon link is formed by assembly of twelve cis-blocked Pt2+ complexes, six Cu+ ions, and twelve rigid N-donor ligands. The complex represents a molecular version of a “stick link”.

    9. π Interactions | Hot Paper

      Anion–π and Cation–π Interactions on the Same Surface

      Dr. Kaori Fujisawa, Dr. César Beuchat, Marie Humbert-Droz, Dr. Adam Wilson, Prof. Tomasz A. Wesolowski, Dr. Jiri Mareda, Dr. Naomi Sakai and Prof. Stefan Matile

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201407161

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      It takes two to tango: Theoretical and experimental evidence shows that anion–π and cation–π interactions can occur simultaneously on the same aromatic surface. The resulting ion pair–π interactions shift the absorption of push–pull chromophores to the red.

  5. Highlights

    1. Carbon(IV) Nitrides

      gt-C3N4—The First Stable Binary Carbon(IV) Nitride

      Prof. Dr. Edwin Kroke

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406427

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      Twenty-five years ago a diamondlike C3N4 phase was postulated. After many unsuccessful attempts the synthesis of an s-triazine-based modification was accomplished, which is reported to show interesting semiconducting and catalytic properties similar to that of graphene and related graphitic C/N/H phases.

  6. Communications

    1. Supramolecular Chemistry

      Self-Assembly of Molecular Borromean Rings from Bimetallic Coordination Rectangles

      Sheng-Li Huang, Yue-Jian Lin, Zhen-Hua Li and Prof. Guo-Xin Jin

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406193

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      A (Borro)mean business: For chemists, molecular Borromean rings represent a formidable synthetic challenge. Different from their stepwise synthesis with the aid of a well-known driving force, a self-assembly method associated with the formation of molecular rectangles is described. DFT calculations were used to provide theoretical support for the formation of these species.

    2. Actinide Chemistry

      Experimental and Computational Studies on the Reactivity of a Terminal Thorium Imidometallocene towards Organic Azides and Diazoalkanes

      Dr. Wenshan Ren, Enwei Zhou, Bo Fang, Dr. Guohua Hou, Prof. Guofu Zi, Prof. De-Cai Fang and Dr. Marc D. Walter

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406191

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      A hard act(inide) to follow: The reaction of a thorium imido complex with 9-diazofluorene was found to proceed through a [2+2] cycloaddition reaction to yield a η2-diazenido iminato complex (see scheme). In contrast, an organic azide reacted with the same thorium imido complex by [2+3] cycloaddition to give a tetraazametallacyclopentene.

    3. Microreactor Imaging

      Lab-on-a-Chip Reactor Imaging with Unprecedented Chemical Resolution by Hadamard-Encoded Remote Detection NMR

      Dr. Ville-Veikko Telkki, Dr. Vladimir V. Zhivonitko, M. Sc. Anne Selent, Dr. Gianmario Scotti, M. Sc. Jarmo Leppäniemi, Prof. Sami Franssila and Prof. Igor V. Koptyug

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201405681

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      Increased NMR sensitivity: Remote detection exchange NMR spectroscopy (RD-EXSY), along with indirect spatial information extracted from time-of-flight data, provides unique information about the active regions, reaction pathways, and intermediates in a lab-on-a-chip reactor. Direct spatial resolution can be added to RD-EXSY by applying the principles of Hadamard spectroscopy.

    4. Metal–Organic Frameworks

      Introduction of an Ionic Liquid into the Micropores of a Metal–Organic Framework and Its Anomalous Phase Behavior

      Kazuyuki Fujie, Dr. Teppei Yamada, Prof. Ryuichi Ikeda and Prof. Hiroshi Kitagawa

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406011

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      Hosting ionic guests: An ionic liquid (IL) was incorporated within the micropores of a metal–organic framework (MOF). The phase behavior of the IL inside the MOF micropores was studied by differential scanning calorimetry and solid-state NMR measurements. The IL inside the micropores demonstrated no marked freezing transition down to low temperature, where the bulk IL was frozen.

    5. Hot-Electron Transfer | Hot Paper

      Hot-Electron-Transfer Enhancement for the Efficient Energy Conversion of Visible Light

      Sungju Yu, Yong Hwa Kim, Su Young Lee, Hyeon Don Song and Prof. Jongheop Yi

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201405598

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      A core–shell nanostructure with three distinct components enables the efficient production of H2 from water and significant electron harvesting under visible-light irradiation because of enhanced hot-electron injection, the formation of a Schottky junction, and high-performance electron filtering. The electron transfer pathway is elucidated through steady-state and time-resolved photoluminescence spectroscopy.

    6. Formic Acid Dehydrogenation | Hot Paper

      Hydrogen from Formic Acid through Its Selective Disproportionation over Sodium Germanate—A Non-Transition-Metal Catalysis System

      Dr. Ruth I. J. Amos, Dr. Falk Heinroth, Dr. Bun Chan, Sisi Zheng, Prof. Brian S. Haynes, Prof. Christopher J. Easton, Prof. Anthony F. Masters, Prof. Leo Radom and Prof. Thomas Maschmeyer

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201405360

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      From models to reality: A robust catalyst for the selective dehydrogenation of formic acid to liberate hydrogen gas has been designed computationally, and also demonstrated experimentally. This catalyst represents an important step towards the use of renewable formic acid as a hydrogen-storage and transport vector in fuel and energy applications.

    7. Metal Ion Cluster

      A Tray-Shaped, PdII-Clipped Au3 Complex as a Scaffold for the Modular Assembly of [3×n] Au Ion Clusters

      Takafumi Osuga, Dr. Takashi Murase, Dr. Manabu Hoshino and Prof. Dr. Makoto Fujita

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201404892

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      Pile up gold: A PdII3AuI3 shallow concave complex was prepared by connecting peripheral pyridyl groups of a planar AuI3 complex with each other through PdII coordination. The tray-shaped host accommodated the AuI3 planes to form three-dimensional AuI arrays. The number of AuI3 stacks (n) was systematically tuned by the solvent conditions and the addition of AgI ions.

    8. Heterogeneous Catalysis

      Remarkable Enhancement of O2 Activation on Yttrium-Stabilized Zirconia Surface in a Dual Catalyst Bed

      Mélissandre Richard, Dr. Fabien Can, Dr. Daniel Duprez, Dr. Sonia Gil, Prof. Dr. Anne Giroir-Fendler and Dr. Nicolas Bion

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201403921

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      A double bed is better: The exchange of O2 across an LaMnO3 catalytic bed leads to an enhancement of its activation on an yttrium-stabilized zirconia (YSZ) surface. The O atoms of the YSZ lattice, which are unable to exchange with gas-phase O2 below 823 K, become exchangeable from 533 K in a dual LaMnO3-YSZ bed. This property makes the dual LaMnO3-Pd/YSZ catalytic system highly active for CH4 combustion and partial oxidation at moderate temperatures.

    9. RNA Imaging

      Brightness through Local Constraint—LNA-Enhanced FIT Hybridization Probes for In Vivo Ribonucleotide Particle Tracking

      Felix Hövelmann, Dr. Imre Gaspar, Simon Loibl, Dr. Eugeny A. Ermilov, Prof. Dr. Beate Röder, Prof. Dr. Jesper Wengel, Dr. Anne Ephrussi and Prof. Dr. Oliver Seitz

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201406022

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      …And there was light: Local constraint of the DNA structure through the introduction of a locked nucleic acid (LNA) closes fluorescence decay channels of an environment-sensitive thiazole orange dye in DNA hybridization probes. Two singly labeled LNA-enhanced forced-intercalation (FIT) probes were sufficient for tracking ribonucleotide particles in living tissue.

    10. Systems Catalysis

      Transient Substrate-Induced Catalyst Formation in a Dynamic Molecular Network

      Hugo Fanlo-Virgós, Dr. Andrea-Nekane R. Alba, Saleh Hamieh, Mathieu Colomb-Delsuc and Prof. Dr. Sijbren Otto

      Article first published online: 28 AUG 2014 | DOI: 10.1002/anie.201403480

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      Substrate-induced catalyst formation was achieved which is similar to the continuous regulation of enzymes in biology. A dynamic molecular network responds to the substrate by transiently producing the catalyst required for its transformation. As soon as the substrate is consumed, the network disassembles the catalyst again. These results open up new opportunities for controlling catalysis in synthetic chemical systems.

    11. Ruthenium Pincer Complexes | Hot Paper

      Direct Catalytic Olefination of Alcohols with Sulfones

      Dr. Dipankar Srimani, Dr. Gregory Leitus, Yehoshoa Ben-David and Prof. Dr. David Milstein

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201407281

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      The one-step olefination of alcohols with sulfones for the direct synthesis of terminal and internal olefins is catalyzed by ruthenium pincer complexes. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressure provides a one-step method for the replacement of alcohol hydroxy groups by methyl groups.

    12. Synthetic Methods

      An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

      Chinta Nagaraju and Prof. Dr. Kavirayani R. Prasad

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201407680

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      In sync: An unusual rearrangement involving a ring contraction and subsequent intramolecular trapping of the incipient oxocarbenium ion with an alkene is observed. The rearrangement offers a new route to structurally complex diquinanes (see scheme). The sequence was extended to the synthesis of an oxymethano-bridged triquinane framework.

    13. Biocatalysis

      Oxygenase-Catalyzed Desymmetrization of N,N-Dialkyl-piperidine-4-carboxylic Acids

      Anna M. Rydzik, Ivanhoe K. H. Leung, Grazyna T. Kochan, Michael A. McDonough, Timothy D. W. Claridge and Prof. Christopher J. Schofield

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406125

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      Thinking outside the BBOX: γ-Butyrobetaine hydroxylase (BBOX) is a 2-oxoglutarate (2OG)-dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N-dialkyl piperidine-4-carboxylates to give products with two or three stereogenic centers.

    14. Li-Ion Batteries | Very Important Paper

      Sustainable Electrical Energy Storage through the Ferrocene/Ferrocenium Redox Reaction in Aprotic Electrolyte

      Dr. Yu Zhao, Yu Ding, Dr. Jie Song, Dr. Gang Li, Prof. Guangbin Dong, Prof. John B. Goodenough and Prof. Guihua Yu

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406135

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      The redox couple ferrocene/ferrocenium is applied for the construction of a liquid cathode Li-ion redox battery for electrical energy storage. The redox reaction is highly reversible and efficient. Even after 250 full charge/discharge cycles the capacity maintains ca. 90 % of the initial value and the Coulombic efficiency reaches 98–100 %.

  7. Reviews

    1. Natural Products

      Reactivity and Stability of Glucosinolates and their Breakdown Products in Foods

      Dr. Franziska S. Hanschen, Dr. Evelyn Lamy, Prof. Dr. Monika Schreiner and Prof. Dr. Sascha Rohn

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201402639

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      Vegetables such as broccoli contain a variety of cancer-preventing agents, among them glucosinolates. These sulfur-containing compounds are precursors to a variety of enzymatically or chemically formed breakdown products that affect the quality of food with regard to nutritional value, flavor, and beneficial health effects. This review provides an overview over the reactivity of glucosinolates and their breakdown products.

  8. Author Profiles

    1. Dongyuan Zhao

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406195

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      My biggest inspiration is nature. My favorite time of day is the evening.

  9. Communications

    1. Nanoparticle Imaging Agents

      You have full text access to this OnlineOpen article
      A “Schizophotonic” All-In-One Nanoparticle Coating for Multiplexed SE(R)RS Biomedical Imaging

      Dr. Pasquale Iacono, Dr. Hazem Karabeber and Prof. Dr. Moritz F. Kircher

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201403835

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      Split personality: A biocompatible polymeric surface coating gives rise to dual emissive SERS/NIRF behavior when bound to gold nanoparticles of varying sizes. These polymers allow the first synthesis of SERS nanoprobes with gold cores smaller than 20 nm. These nanoprobes are shown to be capable of multiplexed lymph-node imaging.

    2. 1,2-Oxaphosphetane Complexes

      Synthesis and Reaction of the First 1,2-Oxaphosphetane Complexes

      Andreas Wolfgang Kyri, Dr. Vitaly Nesterov, Dr. Gregor Schnakenburg and Prof. Dr. Rainer Streubel

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201404877

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      O-PIIIeration successful: The first 1,2-oxaphosphetane complexes II were synthesized by a formal P1 insertion into the C[BOND]O bond of different epoxides using the Li/Cl phosphinidenoid complex I (see scheme; R=CH(SiMe3)2, solv=solvent). The reaction of a mixture of II and trifluoromethane sulfonic acid/benzonitrile/triethylamine led to a ring expansion formation of the 1,3,4-oxazaphosphacyclohex-2-ene complex III.

    3. Photoelectrodes

      Switchable Charge-Transfer in the Photoelectrochemical Energy-Conversion Process of Ferroelectric BiFeO3 Photoelectrodes

      Dr. Dawei Cao, Dr. Zhijie Wang, Nasori, Liaoyong Wen, Yan Mi and Prof. Yong Lei

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406044

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      Poling station: The orientation of the BiFeO3 (BFO) band bending at the BFO/electrolyte in polycrystalline BFO photoelectrodes can be switched from upwards to downwards by poling pretreatments of +8 V or −8 V, respectively. It is thus possible to manipulate photoelectrochemical reactions on a single ferroelectric photoelectrode.

    4. Bioorthogonal Chemistry | Hot Paper

      Super-Resolution Imaging of Plasma Membrane Glycans

      Sebastian Letschert, Dr. Antonia Göhler, Christian Franke, Nadja Bertleff-Zieschang, Elisabeth Memmel, Priv.-Doz. Dr. Sören Doose, Prof. Dr. Jürgen Seibel and Prof. Dr. Markus Sauer

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406045

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      Glycan spotting: Click chemistry and super-resolution imaging was used to visualize and quantify ManNAc-, GalNAc-, and O-GlcNAc-modified glycans in the plasma membrane of mammalian cells with single-molecule sensitivity (see image). The data demonstrate that a single cell may easily contain more than ten million glycans, which are homogeneously distributed and do not form clusters or nanodomains.

    5. Bioconjugation | Hot Paper

      Dialdehydes Lead to Exceptionally Fast Bioconjugations at Neutral pH by Virtue of a Cyclic Intermediate

      Pascal Schmidt, Dr. Linna Zhou, Kiril Tishinov, Kaspar Zimmermann and Prof. Dr. Dennis Gillingham

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406132

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      For aldehydes, 1+1=500: Dialdehydes react with O-alkylhydroxylamines at rates of 500 M−1 s−1 at neutral pH values in the absence of catalysts. The key to these conjugations is an unusually stable cyclic intermediate, which ultimately undergoes dehydration to yield an oxime. The application of this method in bioconjugations and a mechanistic interpretation are outlined.

    6. RNA Targeting

      A Toxic RNA Catalyzes the In Cellulo Synthesis of Its Own Inhibitor

      Dr. Suzanne G. Rzuczek, Dr. HaJeung Park and Prof. Dr. Matthew D. Disney

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406465

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      Potent modulators of RNA function can be assembled in cellulo by using the cell as the reaction vessel and a disease-causing RNA as the catalyst. In particular, a Huisgen 1,3-dipolar cycloaddition reaction was used to template the synthesis of an RNA inhibitor in disease-affected cells.

    7. Receptor Targeting

      A Multivalent Ligand for the Mannose-6-Phosphate Receptor for Endolysosomal Targeting of an Activity-Based Probe

      Dr. Sascha Hoogendoorn, Dr. Gijs H. M. van Puijvelde, Prof. Dr. Johan Kuiper, Prof. Dr. Gijs A. van der Marel and Prof. Dr. Herman S. Overkleeft

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406842

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      On target: A synthetic glycopeptide (P) that contains six mannose-6-phosphate residues was covalently attached to a fluorescent activity-based probe for cathepsins. The construct was internalized in live cells through binding to the mannose-6-phosphate receptor (MPR), thus validating the cluster as an MPR-targeting ligand that can be used to deliver cargo into the endolysosomal pathway.

    8. C[BOND]H Oxidation

      Enantioselective Allylic Hydroxylation of ω-Alkenoic Acids and Esters by P450 BM3 Monooxygenase

      B.Sc. Katharina Neufeld, Birgit Henßen and Prof. Dr. Jörg Pietruszka

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201403537

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      Modern biocatalysts on the rise: The P450 BM3 monooxygenase mutant A74G/L188Q catalyzes the enantioselective allylic hydroxylation of ω-alkenoic acids and esters under mild conditions using O2 as an oxidant. This reaction offers access to important chiral building blocks for the synthesis of biologically active compounds and demonstrates the highest chemo- and enantioselectivity observed to date for the C[BOND]H oxidation of acyclic terminal olefins.

    9. Natural Products

      Total Synthesis of Myceliothermophins C, D, and E

      Prof. Dr. K. C. Nicolaou, Dr. Lei Shi, Dr. Min Lu, Dr. Manas R. Pattanayak, Dr. Akshay A. Shah, Dr. Heraklidia A. Ioannidou and Dr. Manjunath Lamani

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406815

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      Cascades: The total synthesis of the cytotoxic myceliothermophins C, D, and E have been achieved through a sequence involving a cascade bis(cyclization) of epoxide or aldehyde substrates to forge a trans-fused decalin precursor of the natural products.

  10. Book Reviews

    1. Symmetry of Crystals & Molecules. By Mark Ladd.

      Werner Kaminsky

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201407286

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      Oxford University Press, 2014. 464 pp., hardcover, £ 55.00.—ISBN 978-0199670888

  11. Cover Pictures

    1. Mononuclear and Terminal Zirconium and Hafnium Methylidenes

      Dr. Masahiro Kamitani, Balazs Pinter, Dr. Chun-Hsing Chen, Dr. Maren Pink and Prof. Dr. Daniel J. Mindiola

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408379

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      Kinetically stable methylidene complexes of zirconium and hafnium were prepared through photolysis-induced α-H abstraction from the corresponding complexes with aryloxide and two methyl ligands. In their Communication (DOI: 10.1002/anie.201405042), D. J. Mindiola and co-workers describe their quest for a kinetically more resistant system (structure on top of the compass) by taking advantage of prior systems (old map with drawings), thus finding the target molecule (inside the treasure chest).

  12. Communications

    1. Sythetic Methods

      Regioselective Radical Aminofluorination of Styrenes

      Hongwei Zhang, Yongcheng Song, Dr. Jinbo Zhao, Prof. Jingping Zhang and Prof. Qian Zhang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406797

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      Double agent: The copper-catalyzed radical aminofluorination of styrenes with N-fluorobenzenesulfonimide (NFSI) is realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite to those of the palladium-catalyzed and noncatalyzed processes. NFSI reacts under N[BOND]F bond homolysis and is utilized as both a radical nitrogen source and radical fluorine source.

    2. [4+2] Cycloaddition

      Cobalt-Catalyzed Formal [4+2] Cycloaddition of α,α′-Dichloro-ortho-Xylenes with Alkynes

      Prof. Dr. Kimihiro Komeyama, Yuji Okamoto and Prof. Dr. Ken Takaki

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406807

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      Simple, but powerful: The title reaction leads to 1,4-dihydronaphthalenes with a wide substrate scope and high functional-group tolerance. Mechanistic investigation supports a benzyl cobaltation of alkyne, not the classical Diels–Alder reaction of ortho-quinodimethanes. This methodology provides a straightforward access to linearly expanded π-conjugated aromatics.

    3. Radical Chemistry

      Trans-Selective Radical Silylzincation of Ynamides

      Elise Romain, Carolin Fopp, Prof. Dr. Fabrice Chemla, Dr. Franck Ferreira, Dr. Olivier Jackowski, Prof. Dr. Martin Oestreich and Dr. Alejandro Perez-Luna

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201407002

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      A radical­ transformation:­ Z-configured α,β-disubstituted enamides are obtained through a regio- and stereoselective silylzincation of terminal ynamides and subsequent sequential functionalization of the resulting Cinline image[BOND]Zn and Cinline image[BOND]Si bonds (see Scheme). The trans-selective silylzincation proceeds through a radical process combining organosilyl radical and radical Zn-atom transfer chemistry.

  13. Cover Pictures

    1. Tailoring Intermolecular Interactions for Efficient Room-Temperature Phosphorescence from Purely Organic Materials in Amorphous Polymer Matrices

      Dr. Min Sang Kwon, Dongwook Lee, Sungbaek Seo, Jaehun Jung and Prof. Dr. Jinsang Kim

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408162

      Thumbnail image of graphical abstract

      Rationally designed strong intermolecular hydrogen and halogen bonds between a novel phosphor and a poly(vinyl alcohol) (PVA) matrix led to bright room-temperature phosphorescence with a quantum yield of 24 %. J. Kim and co-workers show in their Communication (10.1002/anie.201404490) that modulation of the strength of halogen and hydrogen bonding in the purely organic phosphor–PVA system by water enabled reversible switching between phosphorescence (green) and fluorescence (blue).

    2. Fluxionally Chiral DMAP Catalysts: Kinetic Resolution of Axially Chiral Biaryl Compounds

      Gaoyuan Ma, Dr. Jun Deng and Prof. Dr. Mukund P. Sibi

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408268

      Thumbnail image of graphical abstract

      Place a pair of enantiomers in a box, wave a magic wand (a chiral catalyst), and two enantioenriched compounds pop out because of their differential interaction with the catalyst. In their Communication (DOI: 10.1002/anie.201406684), M. P. Sibi et al. demonstrate that a novel 4-dimethylaminopyridine catalyst having fluxional chirality is efficient in promoting acylative kinetic resolution of axially chiral biaryl compounds with selectivities of up to 51:1.

    3. Surface Polarization Matters: Enhancing the Hydrogen-Evolution Reaction by Shrinking Pt Shells in Pt–Pd–Graphene Stack Structures

      Song Bai, Dr. Chengming Wang, Dr. Mingsen Deng, Prof. Ming Gong, Yu Bai, Prof. Jun Jiang and Prof. Yujie Xiong

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408163

      Thumbnail image of graphical abstract

      Surface charge states play an important role in tuning the catalytic performance of nanocrystals in various reactions. In their Communication (DOI: 10.1002/anie.201406468), Y. Xiong and co-workers demonstrate that the surface polarization effect can be induced on Pt surfaces in Pt–Pd–graphene stack structures as long as the Pt surface thickness is shrunk to a few layers. The surface polarization boosts the hydrogen evolution reaction activity as the thickness of the Pt layer decreases, opening the possibility to decrease the amount of Pt used.

  14. Communications

    1. Luminescent Frameworks

      Cluster Linker Approach: Preparation of a Luminescent Porous Framework with NbO Topology by Linking Silver Ions with Gold(I) Clusters

      Zhen Lei, Xiao-Li Pei, Zhan-Guo Jiang and Prof. Dr. Quan-Ming Wang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406761

      Thumbnail image of graphical abstract

      Cluster linker: A luminescent gold(I) cluster prefunctionalized with pyrazinyl groups (left) was used as a cluster linker, similar to an organic linker, to connect silver ions in order to form a 3D framework. The intrinsic luminescence of the cluster was thus introduced into a bifunctional porous framework, which is characterized by an NbO topology and features 1D channels with a diameter of 1.1 nm.

    2. Mössbauer Spectroscopy

      Re-Appearance of Cooperativity in Ultra-Small Spin-Crossover [Fe(pz){Ni(CN)4}] Nanoparticles

      Haonan Peng, Dr. Simon Tricard, Gautier Félix, Dr. Gábor Molnár, Dr. William Nicolazzi, Dr. Lionel Salmon and Dr. Azzedine Bousseksou

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406710

      Thumbnail image of graphical abstract

      Spin-crossover nanoparticles: Mössbauer spectroscopy was used to determine the variation of the Debye temperature (θD) for [Fe(pz){Ni(CN)4}] (py=pyrazine) spin-crossover nanoparticles ranging from 2 to 110 nm (see picture). The investigations explain the re-appearance of cooperativity in the smallest nanoparticles.

    3. Polyketide Biosynthesis

      An Unusual Dehydratase Acting on Glycerate and a Ketoreducatse Stereoselectively Reducing α-Ketone in Polyketide Starter Unit Biosynthesis

      Dr. Hai-Yan He, Dr. Hua Yuan, Dr. Man-Cheng Tang and Prof. Dr. Gong-Li Tang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406602

      Thumbnail image of graphical abstract

      Biochemical characterization of a dehydratase and a ketoreductase-like domain (DH*-KR*) in the loading module of FR901464 polyketide synthase revealed that DH* catalyzes the dehydration of an acyl carrier protein (ACP)-tethered glycerate to an ACP-linked pyruvate. The KR* domain then carries out α-ketone reduction to yield L-lactyl-S-ACP, which serves as a starter unit for polyketide biosynthesis.

    4. DNA Demethylation

      Pyrene-Based Quantitative Detection of the 5-Formylcytosine Loci Symmetry in the CpG Duplex Content during TET-Dependent Demethylation

      Dr. Liang Xu, Ying-Chu Chen, Jenny Chong, Dr. Andrea Fin, Dr. Lisa S. McCoy, Dr. Jun Xu, Prof. Dr. Chao Zhang and Prof. Dr. Dong Wang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406220

      Thumbnail image of graphical abstract

      Employing the unique fluorescence properties of the pyrene group, a sensitive fluorescence-based probe was designed and synthesized not only to target 5-formylcytosine (5fC) sites, but also to distinguish symmetric from asymmetric 5fC sites in the double-stranded DNA context during the TET-dependent 5mC oxidation process. Dominant levels of symmetric 5fC were revealed among total 5fC sites during in vitro TET-dependent 5mC oxidation.

    5. C[BOND]H Functionalization

      Combining Rhodium and Photoredox Catalysis for C[BOND]H Functionalizations of Arenes: Oxidative Heck Reactions with Visible Light

      M. Sc. David C. Fabry, Dipl.-Chem. Jochen Zoller, Dr. Sadiya Raja and Prof. Dr. Magnus Rueping

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201400560

      Thumbnail image of graphical abstract

      Much milder and environmentally friendly reaction conditions can be used for oxidative Heck reactions through the combined use of rhodium and redox catalysis. This allows the rhodium complex to be catalytically regenerated. A broad range of substrates was tolerated in the reaction and afforded different amides in good to very good yields.

  15. Minireviews

    1. Natural Product Synthesis

      The Total Synthesis of Isodon Diterpenes

      Dr. Kiel E. Lazarski, Dr. Benjamin J. Moritz and Prof. Regan J. Thomson

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201404482

      Thumbnail image of graphical abstract

      An interesting family: Complex polycyclic diterpenes can be isolated from the plants of the Isodon genus. This Minireview gives a concise summary of recent synthetic efforts that have culminated in the successful total synthesis of these diterpenes.

  16. Communications

    1. Total Synthesis

      A Biomimetic Synthesis of (±)-Basiliolide B

      Long Min, Yang Zhang, Xuefeng Liang, Junrong Huang, Wenli Bao and Dr. Chi-Sing Lee

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201405770

      Thumbnail image of graphical abstract

      O-Acylation or O-methylation? The biosynthetic origin of the C ring of the basiliolide/transtaganolide framework has been elucidated by studying the proposed biosynthetic pathways, namely O-acylation and O-methylation. The intramolecular O-acylation of the seco acid derivative gave (±)-basiliolide B in 92 % yield. This indicates that the seco acid derivative is likely a biosynthetic precursor of basiliolide B instead of a biosynthetic dead end.

    2. Enzymatic Activity

      Multiple Stable Conformations Account for Reversible Concentration-Dependent Oligomerization and Autoinhibition of a Metamorphic Metallopeptidase

      Mar López-Pelegrín, Dr. Núria Cerdà-Costa, Dr. Anna Cintas-Pedrola, Fátima Herranz-Trillo, Pau Bernadó, Dr. Juan R. Peinado, Dr. Joan L. Arolas and Prof. Dr. F. Xavier Gomis-Rüth

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201405727

      Thumbnail image of graphical abstract

      Shape shifting: A minimal metamorphic, selective, and specific caseinolytic metallopeptidase, selecase, reversibly transits between several different states of defined three-dimensional structure (monomer and tetramer represented in picture). The competent conformation is sequestered in incompetent but structured dimers, tetramers, and octamers, which are associated with loss of enzymatic activity due to autoinhibition.

    3. Luminescence

      A Phosphorescent Molecular “Butterfly” that undergoes a Photoinduced Structural Change allowing Temperature Sensing and White Emission

      Dr. Mingu Han, Yu Tian, Dr. Zhao Yuan, Prof. Lei Zhu and Prof. Biwu Ma

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201405293

      Thumbnail image of graphical abstract

      The white brothers: A molecular “butterfly”, that is, a phosphorescent PtII binuclear complex, can flap its “wings” and generate dual (white) emission upon photoexcitation. This photoinduced molecular structure change results from the shorterning of the Pt–Pt distance in the excited state and is phase-dependent allowing application of the complex as a self-referenced luminescent sensor for phase change, temperature, and viscosity.

    4. Flavin Redox Bifurcation

      Flavin Redox Bifurcation as a Mechanism for Controlling the Direction of Electron Flow during Extracellular Electron Transfer

      Dr. Akihiro Okamoto, Prof. Dr. Kazuhito Hashimoto and Prof. Dr. Kenneth H. Nealson

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201407004

      Thumbnail image of graphical abstract

      The iron-reducing bacterium­ Shewanella oneidensis MR-1 has a dual directional electronic conduit involving 40 heme redox centers in flavin-binding outer-membrane c-type cytochromes (OM c-Cyts). The redox bifurcation of the cell-secreted riboflavin cofactor in OM c-Cyts switches the direction of electron conduction in the biological conduit at the cell–electrode interface to drive either bacterial electrode reduction or oxidation reactions. Sq=semiquinone, Hq=hydroquinone.

    5. Wearable Solar Cells | Very Important Paper

      A Lightweight Polymer Solar Cell Textile that Functions when Illuminated from Either Side

      Zhitao Zhang, Xueyi Li, Guozhen Guan, Shaowu Pan, Zhengju Zhu, Dayong Ren and Prof. Huisheng Peng

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201407688

      Thumbnail image of graphical abstract

      A polymer solar cell textile has been developed by sandwiching a metal textile electrode between two ultrathin, transparent, and conducting carbon nanotube sheets. Because of its unique structure, the resulting solar cell textile shows the same energy conversion efficiency regardless of which side it is irradiated from. Furthermore, its energy conversion efficiencies were maintained even after 200 bending cycles.

  17. News

  18. Communications

    1. Nanoparticle Catalysts

      Palladium Nanoparticles Embedded in the Inner Surfaces of Carbon Nanotubes: Synthesis, Catalytic Activity, and Sinter Resistance

      Prof. Dr. Hongyang Liu, Dr. Liyun Zhang, Prof. Dr. Ning Wang and Prof. Dr. Dang Sheng Su

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406490

      Thumbnail image of graphical abstract

      Inside out: A facile and versatile synthesis using a template-based procedure gives Pd nanoparticles uniformly embedded in the inner surfaces of carbon nanotubes (see picture). The nanocomposite is catalytically more active and sinter-resistant, than traditional carbon-nanotube-supported Pd catalysts.

    2. Nanostructures

      Surface Polarization Matters: Enhancing the Hydrogen-Evolution Reaction by Shrinking Pt Shells in Pt–Pd–Graphene Stack Structures

      Song Bai, Dr. Chengming Wang, Dr. Mingsen Deng, Prof. Ming Gong, Yu Bai, Prof. Jun Jiang and Prof. Yujie Xiong

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406468

      Thumbnail image of graphical abstract

      Less is more: Pt–Pd–graphene stack structures (see picture) are prepared by a new method that allows control of the thickness of the Pt shell. This thickness correlates with performance in the hydrogen-evolution reaction (HER). As a result of surface polarization, the HER activity actually increases with decreasing Pt thickness, opening possibilities of using less Pt.

    3. Radicals

      An Amphoteric Switch to Aromatic and Antiaromatic States of a Neutral Air-Stable 25π Radical

      Tullimilli Y. Gopalakrishna, Dr. J. Sreedhar Reddy and Prof. Dr. Venkataramanarao G. Anand

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406893

      Thumbnail image of graphical abstract

      Super stable: A 25π radical of an expanded isophlorin undergoes reversible one-electron oxidation to form 24π antiaromatic species and one-electron reduction to form 26π aromatic species, confirming its amphoteric behavior. All of the three oxidation states of the macrocycle have been characterized in solution and solid state to confirm their stability under ambient conditions.

  19. Reviews

    1. Nanostructures

      Formation of Nanoparticles and Nanostructures—An Industrial Perspective on CaCO3, Cement, and Polymers

      Dr. Jens Rieger, Dr. Matthias Kellermeier and Dr. Luc Nicoleau

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201402890

      Thumbnail image of graphical abstract

      Intermediate nanostructures occurring during crystallization reactions play an important role in understanding and controlling the formation of particles and hybrid materials. The use of polymers allows the range of achievable properties to be broadened through their specific effects at the nanoscale—as is exemplified in this Review with calcium carbonate, zinc oxide, and cementitious systems.

  20. Communications

    1. Electrocatalysis | Very Important Paper

      Core/Shell Au/MnO Nanoparticles Prepared Through Controlled Oxidation of AuMn as an Electrocatalyst for Sensitive H2O2 Detection

      Huiyuan Zhu, Aruna Sigdel, Dr. Sen Zhang, Dr. Dong Su, Zheng Xi, Dr. Qing Li and Prof. Shouheng Sun

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406281

      Thumbnail image of graphical abstract

      Cell sensing: AuMn alloy nanoparticles were synthesized through hydride reduction of manganese acetylacetonate in the presence of Au nanoparticles and were subsequently converted into Au/MnO nanoparticles through air annealing. The Au/MnO nanoparticles are active catalysts for the electrochemical reduction of H2O2 and can be used to measure the H2O2 levels from different types of cells for cancer detection.

    2. Isotopic Labeling

      A Universal Procedure for the [18F]Trifluoromethylation of Aryl Iodides and Aryl Boronic Acids with Highly Improved Specific Activity

      Dion van der Born, Claudia Sewing, Dr. J. (Koos) D. M. Herscheid, Prof. Dr. Albert D. Windhorst, Prof. Dr. Romano V. A. Orru and Dr. Danielle J. Vugts

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406221

      Thumbnail image of graphical abstract

      A quality label: Tracers for positron emission tomography (PET) with a [18F]CF3 group directly attached to an arene were synthesized with improved specific activity by the trifluoromethylation of aryl iodides and aryl boronic acids with [18F]trifluoromethane (see scheme). In particular, the trifluoromethylation of aryl boronic acids proceeded rapidly under mild reaction conditions, thus making this method highly suitable for PET-tracer production.

    3. C[BOND]H Activation | Hot Paper

      Aldehyde-Assisted Ruthenium(II)-Catalyzed C[BOND]H Oxygenations

      M. Sc. Fanzhi Yang, Karsten Rauch, M. Sc. Katharina Kettelhoit and Prof. Dr. Lutz Ackermann

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201405647

      Thumbnail image of graphical abstract

      The weakest link: Challenging aryl C[BOND]H oxygenations with very weakly coordinating aldehydes proceed chemoselectively in the presence of versatile ruthenium(II) catalysts under mild reaction conditions. This transformation features an ample substrate scope and excellent positional selectivity.

    4. Protein Design

      Optogenetic Engineering: Light-Directed Cell Motility

      Prof. Dr. Robert M. Hughes and Prof. Dr. David S. Lawrence

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201404198

      Thumbnail image of graphical abstract

      Shine a light: A straightforward strategy for the acquisition of genetically encoded, light-activatable proteins is based upon the principles set forth in the 100 year old Michaelis–Menten equation. Photoactivation of a light-responsive cofilin mediates cytoskeleton remodelling, lamellipodia and filopodia formation, and directed cell motility.

    5. Collective Tunneling | Very Important Paper

      Exceptional Isotopic-Substitution Effect: Breakdown of Collective Proton Tunneling in Hexagonal Ice due to Partial Deuteration

      Dr. Christof Drechsel-Grau and Prof. Dr. Dominik Marx

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201405989

      Thumbnail image of graphical abstract

      Ab initio simulations clarify the effects of H/D isotopic substitution on the mechanism of the collective tunneling of six protons within proton-ordered cyclic water hexamers that are contained in proton-disordered ice. At the transition state, isotopic substitution leads to a Zundel-like [HO⋅⋅⋅D⋅⋅⋅OH] complex with localized ionic defects and thus inhibits perfectly correlated proton tunneling.

    6. Electrocatalysis | Hot Paper

      Controlling Selectivity in the Chlorine Evolution Reaction over RuO2-Based Catalysts

      Kai S. Exner, Josef Anton, Timo Jacob and Herbert Over

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406112

      Thumbnail image of graphical abstract

      Being selective: The selectivity in the industrially important Chlor-Alkali process has been elucidated on the microscopic level through a combination of DFT calculations and volcano plots. A single layer of TiO2(110) grown on RuO2(110) increases the selectivity between the chlorine and oxygen evolution reactions (CER and OER, respectively) by several orders of magnitude, while keeping the high activity for CER practically constant.

    7. Cycloadditions

      The Trapping of Phenyldiazenes in Cycloaddition Reactions

      M. Sc. Stefanie K. Fehler, Dr. Gerald Pratsch and Prof. Dr. Markus R. Heinrich

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406175

      Thumbnail image of graphical abstract

      Catch me if you can! Phenyldiazenes were intensively investigated in the late 1960s. But only recently was it possible to finally trap these reactive intermediates in cycloaddition reactions leading to pyridazinium salts (see scheme).

    8. Photocatalysis

      Photocatalytic Synthesis of Dihydrobenzofurans by Oxidative [3+2] Cycloaddition of Phenols

      Travis R. Blum, Dr. Ye Zhu, Sarah A. Nordeen and Prof. Tehshik P. Yoon

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406393

      Thumbnail image of graphical abstract

      In a good light: The versatile photoredox properties of RuII chromophores offer a strategy to couple powerful oxidative transformations to benign inorganic peroxysulfate oxidants. In this example, the photocatalytic [3+2] cycloaddition of phenols and electron-rich styrenes for the synthesis of diverse dihydrobenzofurans is presented.

    9. Controlled Drug Delivery

      Molecularly Precise Dendrimer–Drug Conjugates with Tunable Drug Release for Cancer Therapy

      Dr. Zhuxian Zhou, Dr. Xinpeng Ma, Dr. Caitlin J. Murphy, Dr. Erlei Jin, Dr. Qihang Sun, Prof. Youqing Shen, Edward A. Van Kirk and Prof. William J. Murdoch

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406442

      Thumbnail image of graphical abstract

      Camptothecine core: Polylysine dendrimers with the conjugated drug in the core were synthesized for cancer therapy. The release rates of the camptothecine conjugates were easily tunable by adjusting the dendrimer generation and the peripheral functional groups as well as the pH. Conjugates showing a fast drug release also exhibited a high anticancer activity against intraperitoneal and subcutaneous tumors.

    10. Photochemistry

      Metal-Free C[BOND]H Bond Activation of Branched Aldehydes with Hypervalent Iodine(III) Catalyst under Visible-Light Photolysis: Successful Trapping with Electron-Deficient Olefins

      Dr. Shin A. Moteki, Asuka Usui, Dr. Sermadurai Selvakumar, Dr. Tiexin Zhang and Prof. Dr. Keiji Maruoka

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406513

      Thumbnail image of graphical abstract

      A radical approach: The mild photocatalyzed activation of the C(O)[BOND]H bond in branched aldehydes offers easy access to acyl radicals and, without decarbonylation, allowed the efficient synthesis of unsymmetrical ketones by trapping with electrophilic olefins. A characteristic feature of this approach is the catalytic use of a hypervalent iodine(III) reagent to generation of radicals.

    11. Cross-Coupling

      Gold(I)-Catalyzed Diazo Coupling: Strategy towards Alkene Formation and Tandem Benzannulation

      Daming Zhang, Guangyang Xu, Dong Ding, Chenghao Zhu, Dr. Jian Li and Prof. Dr. Jiangtao Sun

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406712

      Thumbnail image of graphical abstract

      Crossing paths: A gold(I)-catalyzed cross-coupling of diazo compounds to afford tetrasubstituted alkenes has been developed. In addition, a gold(I)-initiated benzannulation has been achieved in a tandem reaction involving cross-coupling of the vinyldiazoacetates, sequential 6π electrocyclization, and oxidative aromatization.

    12. Metal–Organic Supercontainers

      pH-Modulated Molecular Assemblies and Surface Properties of Metal–Organic Supercontainers at the Air–Water Interface

      Nathan L. Netzer, Dr. Feng-Rong Dai, Prof. Zhenqiang Wang and Prof. Chaoyang Jiang

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406733

      Thumbnail image of graphical abstract

      MOSC thin films: The molecular assemblies of metal–organic supercontainers (MOSCs) were studied at the air–water interface. Variation in the pH values of the subphases causes significant changes in the molecular orientation in the Langmuir films. The uniform MOSC structures in Langmuir–Blodgett films show tunable surface properties that can be precisely controlled by fabricating conditions.

    13. Cyclization

      Mild ArI-Catalyzed C(sp2)[BOND]H or C(sp3)[BOND]H Functionalization/C[BOND]O Formation: An Intriguing Catalyst-Controlled Selectivity Switch

      Xueqiang Wang, Joan Gallardo-Donaire and Prof. Ruben Martin

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407011

      Thumbnail image of graphical abstract

      Who controls the switch? I! A tandem C(sp2)[BOND]H or C(sp3)[BOND]H functionalization/C[BOND]O bond-forming reaction catalyzed by IIII reagents generated in situ has been developed. The transformation shows broad scope under mild conditions and exhibits an unprecedented selectivity profile that can be switched depending on the nature of the iodine catalyst employed (see scheme; HFIP=1,1,1,3,3,3-hexafluoro-2-propanol).

    14. Cross-Coupling

      Synthesis of Direct β-to-β Linked Porphyrin Arrays with Large Electronic Interactions: Branched and Cyclic Oligomers

      Hao Cai, Keisuke Fujimoto, Dr. Jong Min Lim, Chaojie Wang, Weiming Huang, Yutao Rao, Senmiao Zhang, Hui Shi, Dr. Bangshao Yin, Prof. Dr. Bo Chen, Prof. Dr. Ming Ma, Prof. Dr. Jianxin Song, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407032

      Thumbnail image of graphical abstract

      Molecular twine: The title porphyrin trimers and pentamers have been synthesized by Suzuki–Miyaura coupling of β-boryl-porphyrins and β-bromoporphyrins. The cyclic porphyrin trimer, the smallest directly linked cyclic porphyrin, and its twined pentamer exhibit small HOMO–LUMO gaps, broad nonsplit Soret bands, red-shifted Q-bands, and efficient excitation-energy hopping.

    15. Synthetic Methods | Very Important Paper

      Highly Diastereoselective and Enantiospecific Allylation of Ketones and Imines Using Borinic Esters: Contiguous Quaternary Stereogenic Centers

      Dr. Jack L.-Y. Chen and Prof. Dr. Varinder K. Aggarwal

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407127

      Thumbnail image of graphical abstract

      Goldilocks reactivity: 3,3-Disubstituted allylic borinic esters possess the perfect balance between reactivity and configurational stability to react with both ketones and ketimines, allowing facile access to adjacent quaternary stereocenters with full stereocontrol. Synthesis of all possible stereoisomers of a quaternary-quaternary motif is demonstrated. TFAA=trifluoroacetic anhydride.

  21. Minireviews

    1. Chiral-at-Metal Complexes

      Asymmetric Catalysis Mediated by the Ligand Sphere of Octahedral Chiral-at-Metal Complexes

      Dr. Lei Gong, B.Sc. Liang-An Chen and Prof. Dr. Eric Meggers

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201404305

      Thumbnail image of graphical abstract

      “Organocatalysis” with metal complexes: Inert octahedral metal complexes are an emerging class of catalysts for asymmetric synthesis. In these compounds the globular, rigid nature and stereochemical options of octahedral compounds are exploited. Complexes like those shown promise new opportunities in the field of catalysis.

  22. Communications

    1. Drug Delivery

      Cell-Mediated Assembly of Phototherapeutics

      Weston J. Smith, Nathan P. Oien, Dr. Robert M. Hughes, Christina M. Marvin, Zachary L. Rodgers, Junghyun Lee and Prof. David S. Lawrence

      Article first published online: 22 AUG 2014 | DOI: 10.1002/anie.201406216

      Thumbnail image of graphical abstract

      Window of opportunity: A wavelength-encoded drug-delivery strategy operates within the optical window of tissue. The photoresponsive system is acquired by the assembly of lipid-cobalamin-drug and lipid-fluorophore constructs on the surface of erythrocytes. The desired wavelength of cobalamin-drug photocleavage is “dialed-in” by simply choosing the appropriate lipid-fluorophore “antenna”.

    2. Analytical Methods

      Lysosomal pH Rise during Heat Shock Monitored by a Lysosome-Targeting Near-Infrared Ratiometric Fluorescent Probe

      Dr. Qiongqiong Wan, Prof. Dr. Suming Chen, Prof. Dr. Wen Shi, Lihong Li and Prof. Dr. Huimin Ma

      Article first published online: 22 AUG 2014 | DOI: 10.1002/anie.201405742

      Thumbnail image of graphical abstract

      Feeling hot, hot, hot: A near-infrared ratiometric pH probe with a stable semicyanine skeleton is developed for lysosomal pH measurements. The readily preparable probe shows an excellent lysosome-targeting ability and high photostability. The probe is used to investigate the change of lysosomal pH with temperature, revealing for the first time that lysosomal pH values rise during heat shock and the process is irreversible.

  23. Highlights

    1. Arenes

      Organocatalytic Enantioselective Construction of Polyaromatic Architectures

      Ophélie Quinonero, Dr. Cyril Bressy and Dr. Xavier Bugaut

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406263

      Thumbnail image of graphical abstract

      Aromatics in 3D. Organocatalysis is now reaching beyond the control of stereogenic centers and opens new possibilities for the construction of complex polyaromatic structures with either helical or axial chirality.

  24. Communications

    1. Organic Photovoltaics

      Polymerization of Tellurophene Derivatives by Microwave-Assisted Palladium-Catalyzed ipso-Arylative Polymerization

      Dr. Young S. Park, Dr. Qin Wu, Dr. Chang-Yong Nam and Prof. Robert B. Grubbs

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406068

      Thumbnail image of graphical abstract

      Telluric rings: The tellurophene-containing low-bandgap polymer PDPPTe2T, prepared by microwave-assisted ipso-arylative polymerization, exhibited red-shifted absorption spectra compared to the thiophene analogue. Bulk heterojunction solar-cell devices from PDPPTe2T and PC71BM reach a power conversion efficiency of 4.4 % and produce photocurrent at wavelengths up to 1 µm.

    2. Drug Delivery

      An Aptamer Intrinsically Comprising 5-Fluoro-2′-deoxyuridine for Targeted Chemotherapy

      Dipl.-Chem. Sven Kruspe and Prof. Dr. Ulrich Hahn

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405778

      Thumbnail image of graphical abstract

      A trojan chemotherapeutic: An aptamer intrinsically comprising multiple units of the nucleoside analogue 5-fluoro-2′-deoxyuridine can exert a direct cytostatic effect on certain cells. The aptamer, which can be synthesized in a single enzymatic step, binds to a cell surface receptor that is conveyed into the lysosome. Upon lysosomal degradation of the aptamer by intracellular nucleases, the active drug is released within the targeted cells exclusively.

    3. Natural Product Synthesis

      A Multitasking Vanadium-Dependent Chloroperoxidase as an Inspiration for the Chemical Synthesis of the Merochlorins

      Dr. Stefan Diethelm, Dr. Robin Teufel, Dr. Leonard Kaysser and Prof. Dr. Bradley S. Moore

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405696

      Thumbnail image of graphical abstract

      Naturally inspiring: The vanadium- dependent chloroperoxidase Mcl24 was found to mediate a complex series of transformations in the biosynthesis of the merochlorins, in particular, a site-selective naphthol chlorination and an oxidative dearomatization/terpene cyclization sequence to build up the stereochemically complex carbon framework. Inspired by the enzyme reactivity, a chemical chlorination protocol paralleling the biocatalytic process was developed.

    4. Halogenation

      You have full text access to this OnlineOpen article
      Regioselective Dihalohydration Reactions of Propargylic Alcohols: Gold-Catalyzed and Non-Catalyzed Reactions

      Jarryl M. D'Oyley, Dr. Abil E. Aliev and Dr. Tom D. Sheppard

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405348

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      With or without gold: Propargylic alcohols were converted into α,α-diiodo-β-hydroxyketones by treatment with N-iodosuccinimide in the presence of a gold catalyst. α,α-Dichloro-β-hydroxyketones were prepared without a catalyst by reaction of propargylic alcohols with trichloroisocyanuric acid. Mechanistic studies suggest that both of these reactions proceed via the formation of 5-halooxazines, formed by participation of the acetonitrile solvent.

    5. Microwave Spectroscopy

      Tautomerism in Neutral Histidine

      Celina Bermúdez, Santiago Mata, Dr. Carlos Cabezas and Prof. José L. Alonso

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405347

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      Conformational analysis: Neutral histidine has been generated in the gas phase by laser ablation of solid samples and its NεH tautomeric form has been unraveled through its rotational spectrum (see picture). The quadrupole hyperfine structure, arising from the existing three 14N nuclei, constituted a site-specific probe for revealing the tautomeric form as well as the side-chain configuration of this proteogenic amino acid.

  25. Book Reviews

    1. Bioinorganic Chemistry. By Dieter Rehder.

      Felix Zelder

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406318

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      Oxford University Press, Oxford, 2014. 240 pp., hardcover, £ 34.99.—ISBN 978-0199655199

  26. Communications

    1. Carbenoids

      C[BOND]H Functionalization/Asymmetric Michael Addition Cascade Enabled by Relay Catalysis: Metal Carbenoid used for C[BOND]C Bond Formation

      Dr. Dian-Feng Chen, Feng Zhao, Yue Hu and Prof. Dr. Liu-Zhu Gong

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406098

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      Square deal: A combination of either ruthenium(II) or rhodium(II) complexes and quinine-derived squaramide enables 3-diazooxindoles, indole, and nitroalkenes to undergo a highly efficient asymmetric three-component reaction. Based on this metal/organo relay catalysis, a total synthesis of (−)-folicanthine was accomplished in seven steps with 14.5 % overall yield.

    2. Trifluoromethylation | Hot Paper

      Vanadium-Catalyzed Solvent-Free Synthesis of Quaternary α-Trifluoromethyl Nitriles by Electrophilic Trifluoromethylation

      Natalja Früh and Prof. Dr. Antonio Togni

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406181

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      Not only copper! Oxovanadium(IV) complexes catalyze the trifluoromethylation of silyl ketene imines with hypervalent iodine reagents to form quaternary α-trifluoromethyl nitriles under solvent-free conditions. The products, formed in up to 93 % yield, may be further transformed into useful synthetic building blocks for organofluorine chemistry.

    3. Asymmetric Catalysis

      Kinetic Resolution of 1,1′-Biaryl-2,2′-Diols and Amino Alcohols through NHC-Catalyzed Atroposelective Acylation

      Dr. Shenci Lu, Si Bei Poh and Prof. Yu Zhao

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406192

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      BINOL and NOBIN derivatives are obtained in high enantioselectivities of ≥99 % ee through NHC-catalyzed kinetic resolution. This method presents the first highly enantioselective catalytic acylation of axially chiral alcohols.

  27. Cover Pictures

    1. Opposite-Face Sensitivity of Cerium(IV) Oxide in Hydrogenation and Oxidation Catalysis

      Gianvito Vilé, Dr. Sara Colussi, Dr. Frank Krumeich, Prof. Alessandro Trovarelli and Prof. Javier Pérez-Ramírez

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201408165

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      Structure–performance relationships of ceria in heterogeneous reactions are revealed by J. Pérez-Ramírez, A. Trovarelli, et al. in their Communication (DOI: 10.1002/anie.201406637). The (111) surface prevalent in conventional polyhedral CeO2 particles outperforms in hydrogenation, while the (100) surface that is exposed in nanocubes dominates in oxidation. Artwork: Amalia Gallardo (ArteLi) and Marcel Reich.

    2. An All-Halogen Bonding Rotaxane for Selective Sensing of Halides in Aqueous Media

      Benjamin R. Mullaney, Dr. Amber L. Thompson and Prof. Paul D. Beer

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201408031

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      Combining halogen bonding with an optical probe in an interlocked host design leads to a potent anion sensory system. As P. D. Beer et al. show in their Communication (DOI: 10.1002/anie.201403659), an all-halogen bonding rotaxane host with a photoactive rhenium(I) bipyridyl center in the macrocyclic component can optically sense halide anions by luminescence, with a high binding affinity and selectivity for iodide ions. Image: Dr. Karl Harrison.

    3. Long-Lived Trifluoromethide Anion: A Key Intermediate in Nucleophilic Trifluoromethylations

      Prof. Dr. G. K. Surya Prakash, Dr. Fang Wang, Zhe Zhang, Prof. Dr. Ralf Haiges, Dr. Martin Rahm, Prof. Dr. Karl O. Christe, Dr. Thomas Mathew and Prof. Dr. George A. Olah

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201407930

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      CF3 is a long-lived species! For more than six decades, CF3 was believed to exist only as a short-lived and kinetically unstable species in the condensed phase. In their Communication (DOI: 10.1002/anie.201406505), G. K. S. Prakash et al. have obtained the first direct evidence for the persistence of the trifluoromethide anion in THF by NMR spectroscopy. The experiments explicitly show that CF3 with the [K(18-crown-6)]+ counterion is quite stable at low temperatures.

  28. Communications

    1. Energy Conversion

      Platinum-Free Binary Co-Ni Alloy Counter Electrodes for Efficient Dye-Sensitized Solar Cells

      Xiaoxu Chen, Prof. Qunwei Tang, Dr. Benlin He, Dr. Lin Lin and Prof. Liangmin Yu

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406982

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      A mild hydrothermal reduction strategy has been used to generate Pt-free binary Co-Ni alloys for use as counter electrode (CE) materials in dye-sensitized solar cells (DSSCs). These materials offer high electrocatalytic activity toward I3, good electron-conduction, as well as cost-effectiveness. A conversion efficiency of 8.39 % was measured under one sun irradiation, which is much higher than the 6.96 % from platinum-based DSSCs.

    2. Crystal Morphology

      Opposite Face Sensitivity of CeO2 in Hydrogenation and Oxidation Catalysis

      Gianvito Vilé, Dr. Sara Colussi, Dr. Frank Krumeich, Prof. Alessandro Trovarelli and Prof. Javier Pérez-Ramírez

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406637

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      Shape and face matter: The design of ceria catalysts for oxidation and hydrogenation reactions is governed by opposite criteria. Whereas oxygen vacancies, maximized on (100) nanocubes, promote oxidation, hydrogenation is favored by their minimization, requiring (111) face-enclosed polyhedral particles.

    3. Reactive Intermediates | Very Important Paper

      Long-Lived Trifluoromethanide Anion: A Key Intermediate in Nucleophilic Trifluoromethylations

      Prof. Dr. G. K. Surya Prakash, Dr. Fang Wang, Zhe Zhang, Prof. Dr. Ralf Haiges, Dr. Martin Rahm, Prof. Dr. Karl O. Christe, Dr. Thomas Mathew and Prof. Dr. George A. Olah

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406505

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      Rather persistent: For more than 60 years, the trifluoromethanide anion has been widely believed to exist only as an extremely transient species in the condensed phase, and to undergo swift decomposition to difluorocarbene and fluoride. The trifluoromethanide anion has now been successfully prepared, observed, and characterized for the first time in solution. Contrary to previous assumptions, the anion possesses considerable lifetime at subambient temperatures.

    4. Boride Magnets | Hot Paper

      Unexpected Synergy between Magnetic Iron Chains and Stacked B6 Rings in Nb6Fe1−xIr6+xB8

      Dipl.-Chem. Mohammed Mbarki, M.Sc. Rachid St. Touzani and Priv.-Doz. Dr. Boniface P. T. Fokwa

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406397

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      A mutual dependency between ferromagnetic iron chains and stacked B6 rings (see picture) is found in the new ferromagnetic material, Nb6Fe1−xIr6+xB8 (TC=350 K) by combining experiment and density functional theory (DFT). The strong magnetic Fe–Fe interactions found in the iron chains induce an unexpected strengthening of the B–B interactions in the B6 rings.

    5. Nanostructure Assembly

      Recrystallization-Induced Self-Assembly for the Growth of Cu2O Superstructures

      Yang Shang, Yi-Ming Shao, Prof. Dr. Dong-Feng Zhang and Prof. Dr. Lin Guo

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406331

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      A recrystallization-induced self-assembly (RISA) strategy was proposed for the growth of 3D Cu2O superstructures and employs Cu2O mesoporous spheres (diameters ca. 300 nm) as the building blocks. Balancing the hydrolysis and recrystallization rates of the CuCl precursors is key to the successful assembly. Furthermore, the shape of the superstructures can be tuned to obtain either cubes or tetrahedra.

    6. Heterocycle Synthesis

      Dearomative Indole [5+2] Cycloaddition Reactions: Stereoselective Synthesis of Highly Functionalized Cyclohepta[b]indoles

      Guangjian Mei, Hao Yuan, Yueqing Gu, Wei Chen, Prof. Dr. Lung Wa Chung and Prof. Dr. Chuang-chuang Li

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406278

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      Bridge construction: The title reaction with an oxidopyrylium ylide resulted in efficient and diastereoselective construction of highly functionalized oxacyclohepta[b]indoles. The protocol proceeded under very mild reaction conditions, thus enabling high functional-group tolerance and endo selectivity. TBS=tert-butyldimethylsilyl, Tf=trifluoromethanesulfonyl.

    7. Dinuclear Metal Complexes

      Facile C[BOND]H Bond Formation by Reductive Elimination at a Dinuclear Metal Site

      Dr. Richard D. Adams, Dr. Vitaly Rassolov and Yuen Onn Wong

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406219

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      The electronically unsaturated dirhenium complex [Re2(CO)8(µ-AuPPh3)(µ-Ph)] was obtained from the reaction of [Re2(CO)8{µ-η2-C(H)[DOUBLE BOND]C(H)nBu}(µ-H)] with [Au(PPh3)Ph] and by reaction with HSnPh3 was converted into [Re2(CO)8(µ-H)(µ-Ph)] (see picture). This hydrido-bridged complex reductively eliminates benzene upon addition of NCMe.

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