Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 52

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. Layered Compounds

      β-CuN3: The Overlooked Ground-State Polymorph of Copper Azide with Heterographene-Like Layers

      Dr. Xiaohui Liu, Janine George, M. Sc. Dipl.-Chem. Stefan Maintz and Prof. Dr. Richard Dronskowski

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410987

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      Are there others azide from me? A new CuN3 polymorph with a heterographene-like motif was synthesized and characterized. Experimental and theoretical investigations give insight to its thermochemistry and its electronic and vibrational properties. Not only is β-CuN3 identified as the ground-state structure, the compound exhibits negative thermal expansion in the ab plane, similar to, but more pronounced, than in graphite.

    2. Flexible Electrodes | Hot Paper

      Phosphorus-Doped Graphitic Carbon Nitrides Grown in Situ on Carbon-Fiber Paper: Flexible and Reversible Oxygen Electrodes

      Dr. Tian Yi Ma, Jingrun Ran, Prof. Sheng Dai, Prof. Mietek Jaroniec and Prof. Shi Zhang Qiao

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201411125

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      Electrodes, on a roll: Flexible and reversible oxygen electrodes composed of nanostructured P-doped graphitic carbon nitrides grown on carbon-fiber paper exhibit outstanding catalytic activity and stability towards both oxygen reduction (ORR) and oxygen evolution reactions (OER) in different folded and rolled-up forms. They can be used as efficient air cathodes in Zn–air batteries.

  2. Cover Pictures

    1. You have free access to this content
      Metal Dendrimers: Synthesis of Hierarchically Stellated Nanocrystals by Sequential Seed-Directed Overgrowth

      Rebecca G. Weiner and Prof. Sara E. Skrabalak

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201411677

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      Nature seeds pathways to hierarchical structures, which scientists strive to emulate through the synthesis of advanced nanostructures. In their Communication (DOI: 10.1002/anie.201409966), R. G. Weiner and S. E. Skrabalak describe the synthesis of hierarchically stellated nanocrystals by sequential seed-directed overgrowth. These structures are analogous to organic dendrimers, but seed symmetry, rather than molecular connectivity, directs the multi-level branching (Image designed by Ella Marushchenko, Scientific Illustrations).

    2. You have free access to this content
      Quantitative Trace Analysis of Complex Mixtures Using SABRE Hyperpolarization

      Nan Eshuis, Bram J. A. van Weerdenburg, Dr. Martin C. Feiters, Prof. Dr. Floris P. J. T. Rutjes, Prof. Dr. Sybren S. Wijmenga and Dr. Marco Tessari

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201411678

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      Quantitative trace analysis by NMR spectroscopy is feasible with a nuclear spin hyperpolarization method, namely signal amplification by reversible exchange (SABRE), as described by M. Tessari and co-workers in their Communication (DOI: 10.1002/anie.201409795). SABRE was combined with the standard-addition method to determine concentrations of dilute analytes in complex mixtures.

    3. You have free access to this content
      Interception of Cobalt-Based Carbene Radicals with α-Aminoalkyl Radicals: A Tandem Reaction for the Construction of β-Ester-γ-amino Ketones

      Jie Zhang, Jiewen Jiang, Dongmei Xu, Qiang Luo, Hongxiang Wang, Jijun Chen, Huihuang Li, Yaxiong Wang and Prof. Dr. Xiaobing Wan

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201411683

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      A tandem reaction for the construction of β-ester-γ-amino ketones combines a carbene radical, an organoradical, and an ionic Kornblum–DeLaMare reaction into a single catalytic cycle. In their Communication (DOI: 10.1002/anie.201408874), X. Wan and co-workers show that once the cobalt-based carbene radical intermediate has been generated, it can be intercepted with α-aminoalkyl radicals instead of simply adding to an olefin.

  3. Communications

    1. Peptide Catalysis

      Histidine-Containing Peptide Catalysts Developed by a Facile Library Screening Method

      Dr. Kengo Akagawa, Nobutaka Sakai and Prof. Dr. Kazuaki Kudo

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410268

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      Catalytically active peptides were identified from a peptide library by a facile screening method. Reactive amino catalysts can be visualized by anchoring a dye-labeled product. Histidine-containing peptides were found to be efficient catalysts for the enantioselective Michael addition of malonates and enals.

    2. Hydrogen Splitting

      Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H2 Addition and Kinetic Analysis

      Dr. Konstantin Chernichenko, Bianka Kótai, Dr. Imre Pápai, Dr. Vladimir Zhivonitko, Dr. Martin Nieger, Prof. Markku Leskelä and Prof. Timo Repo

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410141

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      As simple as that: An intramolecular frustrated Lewis pair that consists of a very simple acidic boryl site (BH2) and a bulky amino group is found to split dihydrogen in a fast and reversible process. Spin-saturation transfer NMR techniques were used to measure the reaction rates and to obtain accurate kinetic parameters.

    3. Microreactor Synthesis

      Integrated One-Flow Synthesis of Heterocyclic Thioquinazolinones through Serial Microreactions with Two Organolithium Intermediates

      Dr. Heejin Kim, Hyune-Jea Lee and Prof. Dr. Dong-Pyo Kim

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410062

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      High yield and productivity is achieved for the synthesis of heterocyclic thioquinazolinones by sequential reaction in a one-flow microreactor. This methodology allows control of the residence time of reactive intermediates and significantly speeds up reaction times.

    4. Protein Delivery

      Covalent Attachment of Cyclic TAT Peptides to GFP Results in Protein Delivery into Live Cells with Immediate Bioavailability

      Nicole Nischan, Dr. Henry D. Herce, Dr. Francesco Natale, Nina Bohlke, Prof. Nediljko Budisa, Prof. M. Cristina Cardoso and Prof. Christian P. R. Hackenberger

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410006

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      Cycle trip: The conjugation of cyclic cell penetrating peptides (CPPs) to full-length GFP enables direct protein transport into the cell. The cyclic-CPP–GFP conjugates are internalized into live cells with immediate bioavailability, whereas linear CPP analogues are not efficient for GFP transduction. This technology expands the application of cyclic CPPs to the efficient transport of functional full-length proteins into live cells.

    5. Heterocycle Synthesis

      From Anilines to Isatins: Oxidative Palladium-Catalyzed Double Carbonylation of C[BOND]H Bonds

      Wu Li, Zhengli Duan, Xueye Zhang, Heng Zhang, Mengfan Wang, Ru Jiang, Dr. Hongyao Zeng, Dr. Chao Liu and Prof. Aiwen Lei

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410321

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      Two at once: A novel palladium-catalyzed C[BOND]H double carbonylation introduces two adjacent carbonyl groups for the synthesis of isatins from readily available anilines. The reaction proceeds under atmospheric pressure of CO with high regioselectivity and without any additives. Density functional theory investigations indicate that the palladium-catalyzed double carbonylation catalytic cycle is plausible.

    6. Hydrodeoxygenation | Hot Paper

      Hydrodeoxygenation of Vicinal OH Groups over Heterogeneous Rhenium Catalyst Promoted by Palladium and Ceria Support

      Nobuhiko Ota, Dr. Masazumi Tamura, Dr. Yoshinao Nakagawa, Prof. Kazu Okumura and Prof. Keiichi Tomishige

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410352

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      Ultra-fast double cutting: High yields (>99 %), turnover frequencies (TOF, 300 h−1), and turnover numbers (TON, 10 000) are achieved in the simultaneous hydrodeoxygenation of 1,4-anhydroerythritol to tetrahydrofuran over heterogeneous ReOx–Pd/CeO2 catalyst. This catalyst can be applied to sugar alcohols; mono-alcohols and diols are obtained in high yields (≥85 %).

    7. EPR-Based Trilateration

      EPR-Based Approach for the Localization of Paramagnetic Metal Ions in Biomolecules

      Dinar Abdullin, Nicole Florin, Dr. Gregor Hagelueken and Prof. Dr. Olav Schiemann

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410396

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      A trilateration approach for the localization of metal ions within biomolecular structures is presented. Such metal ions are important in the catalysis and folding of biomolecules. The approach utilizes EPR-based long-range distance measurements, and was tested on the Cu2+ center of azurin. Factors affecting the precision of the method are discussed.

    8. Renewable Carbon Sources | Hot Paper

      Cyclic Alkyl Amino Carbene (CAAC) Ruthenium Complexes as Remarkably Active Catalysts for Ethenolysis

      Dr. Vanessa M. Marx, Alexandra H. Sullivan, Dr. Mohand Melaimi, Dr. Scott C. Virgil, Dr. Benjamin K. Keitz, Dr. David S. Weinberger, Prof. Guy Bertrand and Prof. Robert H. Grubbs

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201410797

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      A new series of olefin-metathesis catalysts containing cyclic alkyl amino carbene (CAAC) ligands exhibit unprecedented activity in the ethenolysis of methyl oleate. This work advances the state-of-the-art of the ethenolysis reaction and is expected to find particular use in large-scale industrial applications.

    9. Molecular Structure

      An Accurate Molecular Structure of Phenyl, the Simplest Aryl Radical

      Dr. Oscar Martinez Jr., Prof. Kyle N. Crabtree, Dr. Carl A. Gottlieb, Prof. John F. Stanton and Dr. Michael C. McCarthy

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201409896

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      Radical structure: Using a combination of rotational spectroscopy and vibrational corrections calculated theoretically, an extremely accurate molecular structure of the phenyl radical has been determined. Relative to benzene, the phenyl radical has a substantially larger C-Cipso-C bond angle (125.8(3)° vs. 120°), and a shorter distance (2.713(3) Å vs. 2.783(2) Å) between the ipso and para carbon atoms.

    10. siRNA Delivery

      Cell-Penetrating and Neurotargeting Dendritic siRNA Nanostructures

      M. Sc. Korbinian Brunner, Dr. Johannes Harder, M. Sc. Tobias Halbach, Dr. Julian Willibald, Dr. Fabio Spada, M. Sc. Felix Gnerlich, Dr. Konstantin Sparrer, M. Sc. Andreas Beil, M. Sc. Leonhard Möckl, Prof. Dr. Christoph Bräuchle, Prof. Dr. Karl-Klaus Conzelmann and Prof. Dr. Thomas Carell

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201409803

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      siRNA dendrimers with an anandamide receptor ligand are accessible through a click-chemistry approach, and are taken up even by sensitive neural cells. Silencing of two key proteins of the rabies virus was achieved, allowing the suppression of the viral titer in infected neurons below the detection limit.

    11. Mixed Metal Oxides

      Self-Templated Formation of Uniform NiCo2O4 Hollow Spheres with Complex Interior Structures for Lithium-Ion Batteries and Supercapacitors

      Laifa Shen, Le Yu, Dr. Xin-Yao Yu, Prof. Xiaogang Zhang and Prof. Xiong Wen (David) Lou

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201409776

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      Complex Hollow Spheres: Metal oxide hollow spheres with complex interior structures were obtained by a strategy involving the solution synthesis of metal glycerate solid spheres and subsequent thermal annealing in air. The image shows NiCo2O4 core-in-double-shell hollow spheres. Their structural features give rise to an outstanding electrochemical performance as advanced electrode materials for both lithium-ion batteries and supercapacitors.

    12. Layered Compounds | Hot Paper

      Synthesis of Inorganic Structural Isomers By Diffusion-Constrained Self-Assembly of Designed Precursors: A Novel Type of Isomerism

      Marco Esters, Matti B. Alemayehu, Zachary Jones, Dr. N. T. Nguyen, Dr. Michael D. Anderson, Corinna Grosse, Prof. Saskia F. Fischer and Prof. David C. Johnson

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201409714

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      Just as organic molecules have isomers resulting from different interconnectivity (as shown for C4H8), layered compounds have similar structural isomers. The six possible structural isomers containing four Se-Nb-Se trilayers and four bilayers of PbSe were synthesized from designed precursors. Thus, thousands of new compounds may be selectively prepared from fragments of known compounds.

    13. Porous Carbon | Hot Paper

      Unusual Ultra-Hydrophilic, Porous Carbon Cuboids for Atmospheric-Water Capture

      Dr. Guang-Ping Hao, Giovanni Mondin, Dr. Zhikun Zheng, Tim Biemelt, Stefan Klosz, René Schubel, Prof. Alexander Eychmüller and Prof. Stefan Kaskel

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201409439

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      Thirsty materials: A new class of ultra-hydrophilic porous carbon cuboids shows the best performance for atmospheric-water capture among porous carbons to date. It may serve as a model material for research on carbon chemistry, a new material for water capture, and find use in applications requiring highly hydrophilic surfaces, porosity, and stability.

    14. Molecular Set Screws

      Scanning-Tunneling-Spectroscopy-Directed Design of Tailored Deep-Blue Emitters

      Dipl.-Chem. Jan Sanning, M. Sc. Pascal R. Ewen, M. Sc. Linda Stegemann, Judith Schmidt, Dr. Constantin G. Daniliuc, B. Sc. Tobias Koch, Prof. Dr. Nikos L. Doltsinis, Dr. Daniel Wegner and Dr. Cristian A. Strassert

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201407439

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      Seeing is believing: Frontier orbitals of PtII complexes have been visualized and measured by scanning tunneling spectroscopy. Moreover, they have been tuned with the aid of targeted synthetic strategies to yield a deep-blue triplet emitter. This approach of finding and tuning the right electronic set screws at the molecular level constitutes a new strategy to design and to realize tailored optoelectronic materials.

    15. Metal–Organic Frameworks

      You have full text access to this OnlineOpen article
      Chemical and Structural Stability of Zirconium-based Metal–Organic Frameworks with Large Three-Dimensional Pores by Linker Engineering

      Dr. Suresh B. Kalidindi, Dr. Sanjit Nayak, Dr. Michael E. Briggs, Dr. Susanna Jansat, Dr. Alexandros P. Katsoulidis, Dr. Gary J. Miller, Dr. John E. Warren, Dr. Dmytro Antypov, Dr. Furio Corà, Dr. Ben Slater, Dr. Mark R. Prestly, Dr. Carlos Martí-Gastaldo and Prof. Matthew J. Rosseinsky

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201406501

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      Two linkers of equivalent connectivity but quite distinct torsional flexibility are used to produce [Zr6O4(OH)4(L1)2.6(L2)0.4]⋅(solvent)x that combines both structural and chemical stability in a metal–organic framework. Such a combination is not accessible for the single-linker isostructural phases. The resulting Zr-based MOF has three-dimensional channels and a high surface area of 4184 m2 g−1.

  4. Reviews

    1. Liquid-Crystal Templates

      Functional Materials from Cellulose-Derived Liquid-Crystal Templates

      Dr. Michael Giese, Dr. Lina K. Blusch, Dr. Mostofa K. Khan and Prof. Mark J. MacLachlan

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201407141

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      Out of the woods: Novel mesoporous and nanostructured materials can be generated by templating approaches based on cellulose-based liquid crystals derived from trees. This Review focuses on materials templated by cellulose nanocrystals, since their chiral nematic order allows their use in various optical applications such as optical filters, sensors, and optoelectronics.

    2. DNA Nanotechnology

      DNA Switches: From Principles to Applications

      Dr. Fuan Wang, Dr. Xiaoqing Liu and Prof. Itamar Willner

      Article first published online: 17 DEC 2014 | DOI: 10.1002/anie.201404652

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      Switched on: The stimuli-triggered reversible reconfiguration of i-motifs, G-quadruplexes, and duplex DNA structures, and of DNA devices, such as tweezers, nanosprings or walkers, are the basis for DNA switches that can be triggered by changes in pH values, metal ions/ligands, and photonic or electrochemical signals. Applications of DNA switches include controlled drug delivery, opening/closure of pores, and switchable catalysis.

  5. Communications

    1. Glycans

      Tracking Surface Glycans on Live Cancer Cells with Single-Molecule Sensitivity

      Dr. Hao Jiang, Dr. Brian P. English, Prof. Rachel B. Hazan, Prof. Peng Wu and Prof. Ben Ovryn

      Article first published online: 16 DEC 2014 | DOI: 10.1002/anie.201407976

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      The dynamic single-molecule tracking and super-resolution imaging of N-linked sialic acids and O-linked N-acetyl galactosamine (GalNAc) on the membrane of live cells was achieved by using a combination of metabolically labeled glycans and a bioorthogonal copper(I)-catalyzed azide–alkyne cycloaddition. Analysis of the trajectories of the dye-labeled glycans in mammary cancer cells revealed constrained diffusion of both N- and O-linked glycans.

    2. Organocatalysis

      Asymmetric Dual-Reagent Catalysis: Mannich-type Reactions Catalyzed by Ion Pair

      Hong-Yu Wang, Kai Zhang, Dr. Chang-Wu Zheng, Dr. Zhuo Chai, Dong-Dong Cao, Jia-Xing Zhang and Prof. Gang Zhao

      Article first published online: 16 DEC 2014 | DOI: 10.1002/anie.201409342

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      Paired off: A new strategy, which combines a chiral phosphine with methyl acrylate to form a homogeneous ion pair, is introduced. This activation mode has been successfully applied to Mannich-type reactions, thus generating a variety of fluorinated amino acid derivatives in high yields and with high ee values.

    3. Nanostructures

      Compact Coupled Graphene and Porous Polyaryltriazine-Derived Frameworks as High Performance Cathodes for Lithium-Ion Batteries

      Prof. Yuezeng Su, Yuxin Liu, Dr. Ping Liu, Dr. Dongqing Wu, Dr. Xiaodong Zhuang, Prof. Fan Zhang and Prof. Xinliang Feng

      Article first published online: 16 DEC 2014 | DOI: 10.1002/anie.201410154

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      Designer sheets: Designed compact two-dimensional (2D) coupled graphene and porous polyaryltriazine-derived frameworks (G-PPFs) with tailormade porosities are fabricated by employing various dicyanobenzenes in molten ZnCl2 at different temperatures. The 2D porous nanosheets exhibit cycle stability of 395 mA h g−1 at 5 A g−1 for more than 5100 cycles and a rate capability of 135 mAh g−1 at a current density of 15 A g−1.

    4. Surface Chemistry

      Acquired Superoxide-Scavenging Ability of Ceria Nanoparticles

      Yuanyuan Li, Dr. Xiao He, Prof. Jun-Jie Yin, Dr. Yuhui Ma, Dr. Peng Zhang, Dr. Jingyuan Li, Dr. Yayun Ding, Dr. Jing Zhang, Prof. Yuliang Zhao, Prof. Zhifang Chai and Prof. Zhiyong Zhang

      Article first published online: 16 DEC 2014 | DOI: 10.1002/anie.201410398

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      Shaping up: Ceria nanoparticles (nanoceria) with negligible superoxide dismutase mimetic activity have been identified, and they exert antioxidant effects that are much stronger than expected in human bronchial epithelial cells. The underlying mechanism provides a strategy by which nanoceria of custom size, shape, and surface chemistry can acquire remarkable superoxide-scavenging abilities.

  6. Highlights

    1. Oxidation States

      The Formal Oxidation States of Iridium Now Run from −III to +IX

      Prof. Dr. Pekka Pyykkö and Dr. Wen-Hua Xu

      Article first published online: 16 DEC 2014 | DOI: 10.1002/anie.201410615

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      Rarer than a new element: Recently Wang et al. produced the [(Ir+IX)O4]+ ion by a pulsed laser vaporization/thermal expansion method and studied it by IR photodissociation spectroscopy. The oxidation state of +IX had been unknown previously. The picture shows the mass spectra for the argon-tagged iridium oxide species.

  7. Communications

    1. Synthetic Methods

      Highly Regio- and Enantioselective Synthesis of γ,δ-Unsaturated Amido Esters by Catalytic Hydrogenation of Conjugated Enamides

      Min Gao, Dr. Jing-jing Meng, Dr. Hui Lv and Prof. Dr. Xumu Zhang

      Article first published online: 15 DEC 2014 | DOI: 10.1002/anie.201410213

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      A bit tangy: The Rh/TangPhos-catalyzed asymmetric hydrogenation of α,γ-dienamido esters has been developed and affords γ,δ-unsaturated amido esters with both high regioselectivities and enantioselectivities. This protocol furnishes products using a high substrate to catalyst ratio (S/C) and with greater than 99 % ee. This strategy had been applied in the asymmetric synthesis of key a precursor to Ramipril, an ACE inhibitor. cod=1,5-cyclooctadiene.

    2. Colloidal Crystals

      Tuning the Colloidal Crystal Structure of Magnetic Particles by External Field

      Dr. Antara Pal, Dr. Vikash Malik, Dr. Le He, Dr. Ben H. Erné, Prof. Dr. Yadong Yin, Prof. Dr. Willem K. Kegel and Dr. Andrei V. Petukhov

      Article first published online: 15 DEC 2014 | DOI: 10.1002/anie.201409878

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      An external magnetic field stimulates core–shell magnetite/silica nanoparticles to self-assemble to a body-centered tetragonal crystalline structure. In the absence of magnetic field, the self-organization is governed by the hard-sphere repulsion between the particles and a combination of electrostatic repulsion and van der Waals attraction, leading to the formation of a random hexagonal close-packed structure.

    3. Gold Catalysis | Very Important Paper

      CO-Extrusion in Homogeneous Gold Catalysis: Reactivity of Gold Acyl Species Generated through Water Addition to Gold Vinylidenes

      M. Sc. Janina Bucher, B. Sc. Tim Stößer, Dr. Matthias Rudolph, Dr. Frank Rominger and Prof. Dr. A. Stephen K. Hashmi

      Article first published online: 15 DEC 2014 | DOI: 10.1002/anie.201409859

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      Gold acyl intermediates are generated through the addition of water to gold vinylidene intermediates. The hitherto barely known gold acyl species are shown to undergo an extrusion of CO, an elementary step so far unknown in homogeneous gold catalysis. The reaction sequence constitutes a new gold-catalyzed decarbonylative indene synthesis.

    4. Total Synthesis

      Total Synthesis of Ramonanins A–D

      Ross S. Harvey, Emily G. Mackay, Lukas Roger, Prof. Michael N. Paddon-Row, Prof. Michael S. Sherburn and Dr. Andrew L. Lawrence

      Article first published online: 15 DEC 2014 | DOI: 10.1002/anie.201409818

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      Dimers of dimers: The first total synthesis of the ramonanin family of natural products has been achieved in short order. These natural phenylpropanoid tetramers were assembled in seven steps from the starting materials vanillin, ethylene, and the ethynyl Grignard reagent. Computational studies shed light on a surprisingly facile Diels–Alder dimerization.

    5. Natural Product Synthesis

      Total Synthesis of the Tiacumicin B (Lipiarmycin A3/Fidaxomicin) Aglycone

      M. Sc. Florian Glaus and Prof. Karl-Heinz Altmann

      Article first published online: 15 DEC 2014 | DOI: 10.1002/anie.201409510

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      The crucial ring closure in the title total synthesis is effected by an intramolecular Suzuki cross-coupling. Key steps in in the assembly of the linear macrocyclization precursor are a highly selective one-pot Corey–Peterson olefination, which is based on a new thiophenol-mediated Z[RIGHTWARDS ARROW]E isomerization of an α,β-unsaturated aldimine, and an ene–diene cross-metathesis reaction.

    6. Heterocycles

      Rhodium(III)-Catalyzed Cyclative Capture Approach to Diverse 1-Aminoindoline Derivatives at Room Temperature

      Dr. Dongbing Zhao, Suhelen Vásquez-Céspedes and Prof. Dr. Frank Glorius

      Article first published online: 15 DEC 2014 | DOI: 10.1002/anie.201410342

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      Buckle up! The nucleophilic addition of C(sp3)–Rh species to polarized double bonds is the key step in a RhIII-catalyzed C–H activation/cyclative capture reaction. This constitutes the first intermolecular catalytic method to directly access the 1-aminoindoline core with a broad substituent scope under mild conditions (Boc=tert-butoxycarbonyl, DG=directing group).

    7. Polymerization

      Cationic RAFT Polymerization Using ppm Concentrations of Organic Acid

      Mineto Uchiyama, Prof. Dr. Kotaro Satoh and Prof. Dr. Masami Kamigaito

      Article first published online: 15 DEC 2014 | DOI: 10.1002/anie.201410858

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      Cationic RAFTing: A cationic reversible addition–fragmentation chain-transfer (RAFT) polymerization with thiocarbonylthio compounds proceeds in the presence of a small amount of CF3SO3H. Various monomers including vinyl ethers as well as alkoxy- and hydroxystyrene can be used. A transformation from cationic to radical RAFT polymerization enables the synthesis of block copolymers between cationically and radically polymerizable monomers.

  8. Cover Pictures

    1. You have free access to this content
      The Reactivities of Iminoboranes with Carbenes: BN Isosteres of Carbene–Alkyne Adducts

      Prof. Dr. Holger Braunschweig, Dr. William C. Ewing, Dr. K. Geetharani and Marius Schäfer

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201411644

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      The reactions of iminoboranes and singlet carbenes display expected as well as unexpected rectivity patterns. In their Communication (DOI: 10.1002/anie.201409699) H. Braunschweig and co-workers report the formation of an iminoborane–carbene Lewis acid–base adduct, an aminoborane-functionalized carbene, and a bicyclic azaborolidine from the reactions of three different carbenes with the same iminoborane.

    2. You have free access to this content
      Porous Liquids: A Promising Class of Media for Gas Separation

      Dr. Jinshui Zhang, Dr. Song-Hai Chai, Dr. Zhen-An Qiao, Dr. Shannon M. Mahurin, Dr. Jihua Chen, Dr. Youxing Fang, Dr. Shun Wan, Kimberly Nelson, Dr. Pengfei Zhang and Prof. Sheng Dai

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201411640

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      A porous liquid derived from the surface functionalization of hollow silica spheres with an organosilane corona and a poly(ethylene glycol)-tailed sulfonate canopy is reported by S. Dai and co-workers in their Communication (10.1002/anie.201409420). Taking advantage of the liquid-like polymeric matrix as a selective separation medium and the empty cavities as a pathway for enhanced gas transport, this porous liquid demonstrates promising performance for gas separation.

    3. You have free access to this content
      Impact of Pore Connectivity on the Design of Long-Lived Zeolite Catalysts

      Maria Milina, Dr. Sharon Mitchell, Dr. David Cooke, Dr. Paolo Crivelli and Prof. Javier Pérez-Ramírez

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201411639

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      The unique sensitivity of positron annihilation lifetime spectroscopy to subtleties in the pore connectivity of hierachically structured MFI zeolites reveals the direct correlation with the catalyst longevity in the conversion of methanol to hydrocarbons, as shown by J. Pérez-Ramírez et al. in their Communication (DOI: 10.1002/anie.201410016). Artwork: concept A. Gallardo, illustration M. Reich.

    4. You have free access to this content
      Cofactor-Free Light-Driven Whole-Cell Cytochrome P450 Catalysis

      Jong Hyun Park, Dr. Sahng Ha Lee, Gun Su Cha, Da Som Choi, Dong Heon Nam, Jae Hyung Lee, Prof. Dr. Jung-Kul Lee, Prof. Dr. Chul-Ho Yun, Prof. Dr. Ki Jun Jeong and Prof. Dr. Chan Beum Park

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201411638

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      A light-driven platform for cofactor-free, whole-cell P450 biocatalysis is described by C.-H. Yun, K. J. Jeong, C. B. Park, and co-workers in their Communication (DOI: 10.1002/anie.201410059). This novel platform does not require any labor-intensive and time-consuming pretreatments and is applicable to any type of bacterial and human cytochrome P450s. Instead of expensive cofactors, the use of inexpensive photosensitizer, visible light, and whole-cell system allows cost-effective, scalable, and sustainable process for P450-catalyzed reactions.

  9. Communications

    1. Solid-State Structures

      A Robust Microfluidic Device for the Synthesis and Crystal Growth of Organometallic Polymers with Highly Organized Structures

      Xiao Liu, Qiaolian Yi, Yongzhen Han, Zhenning Liang, Chaohua Shen, Zhengyang Zhou, Prof. Dr. Jun-liang Sun, Prof. Dr. Yizhi Li, Prof. Dr. Wenbin Du and Prof. Dr. Rui Cao

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201411008

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      SlowMo flow: A glass microfluidic device was developed for the synthesis and crystallization of organic, inorganic, and polymeric coordination complexes, whose single crystals cannot be obtained using traditional methods. This device is remarkable for its compatibility with organic solvents, the convenience for crystal harvest, the controlled reaction and crystal growth, and the simplicity of fabrication and usage.

  10. News

  11. Communications

    1. Microreactors

      Reactions of Difunctional Electrophiles with Functionalized Aryllithium Compounds: Remarkable Chemoselectivity by Flash Chemistry

      Dr. Aiichiro Nagaki, Keita Imai, Satoshi Ishiuchi and Prof. Jun-ichi Yoshida

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201410717

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      Microreactors: Flash chemistry using flow microreactors enables highly chemoselective reactions of difunctional electrophiles with functionalized aryllithium compounds by virtue of extremely fast micromixing. The approach serves as a powerful method for protecting-group-free synthesis using organolithium compounds.

    2. Heterogeneous Catalysis | Hot Paper

      High-Resolution Single-Molecule Fluorescence Imaging of Zeolite Aggregates within Real-Life Fluid Catalytic Cracking Particles

      Zoran Ristanović, Dr. Marleen M. Kerssens, Alexey V. Kubarev, Frank C. Hendriks, Dr. Peter Dedecker, Prof. Dr. Johan Hofkens, Prof. Dr. Maarten B. J. Roeffaers and Prof. Dr. Bert M. Weckhuysen

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201410236

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      Real-life fluid catalytic cracking (FCC) catalyst particles have been studied with a combination of single-molecule fluorescence nanoscopy and stochastic optical fluctuation imaging methods. Zeolite ZSM-5 aggregates and their reactivity could be mapped with unprecedented spatiotemporal resolution and sensitivity, revealing significant differences in turnover frequencies of the embedded individual zeolite particulates.

    3. Asymmetric Catalysis

      Highly Regio- and Enantioselective Synthesis of N-Substituted 2-Pyridones: Iridium-Catalyzed Intermolecular Asymmetric Allylic Amination

      Xiao Zhang, Ze-Peng Yang, Lin Huang and Prof. Dr. Shu-Li You

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201409976

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      Readily available 2-hydroxypyridines are converted into enantioenriched N-substituted 2-pyridone derivatives by means of a highly efficient protocol. The title reaction features a good tolerance of functional groups in both the allylic carbonates and 2-hydroxypyridines, thus delivering multifunctionalized heterocyclic products with up to 98 % yield and 99 % ee. cod=1,5-cyclooctadiene.

    4. Natural Product Synthesis | Very Important Paper

      Total Synthesis of Albicidin: A Lead Structure from Xanthomonas albilineans for Potent Antibacterial Gyrase Inhibitors

      Julian Kretz, Dennis Kerwat, Vivien Schubert, Stefan Grätz, Alexander Pesic, Siamak Semsary, Stéphane Cociancich, Monique Royer and Prof. Dr. Roderich D. Süssmuth

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201409584

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      New antibiotics are urgently needed in view of bacterial resistance to established drugs. Albicidin shows activity against various Gram-negative and Gram-positive bacteria, thus making it a promising lead candidate for drug development. The first total synthesis of albicidin was achieved through a convergent synthetic approach that is applicable to the production of derivatives for structure–activity studies.

    5. Protein Phosporylation | Hot Paper

      Screening for Protein Phosphorylation Using Nanoscale Reactions on Microdroplet Arrays

      Simon K. Küster, Dr. Martin Pabst, Prof. Renato Zenobi and Prof. Petra S. Dittrich

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201409440

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      Phosphopeptide screening: A mass spectrometry-based screening method detects protein phosphorylation in complex protein mixtures without extensive MS/MS experiments. The method employs droplet microfluidics to integrate nanoliter phosphatase reactions in a nano-LC-MALDI-MS workflow. The selective dephosphorylation of every second LC fraction induces characteristic peak fluctuations that can be used to identify even low-abundant phosphopeptides.

    6. Phosphorescent Complexes

      Near-IR Phosphorescent Ruthenium(II) and Iridium(III) Perylene Bisimide Metal Complexes

      Marcus Schulze, Dr. Andreas Steffen and Prof. Dr. Frank Würthner

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201410437

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      The attachment of a ruthenium(II) or iridium(III) metal complex to the perylene core of an azabenzannulated perylene bisimide (ab-PBI) leads to strong phosphorescence out of the PBI triplet state after visible-light absorption. The near-IR phosphorescence of the ruthenium complex has a quantum yield (Φp) of 11 %, which is remarkably high in comparison to other NIR emitters.

    7. Covalent Inhibitors

      Covalent Modification of a Cysteine Residue in the XPB Subunit of the General Transcription Factor TFIIH Through Single Epoxide Cleavage of the Transcription Inhibitor Triptolide

      Dr. Qing-Li He, Dr. Denis V. Titov, Dr. Jing Li, Prof. Minjia Tan, Prof. Zhaohui Ye, Prof. Yingming Zhao, Prof. Daniel Romo and Prof. Jun O. Liu

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201408817

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      Power trip: Triptolide, a plant secondary metabolite with potent anticancer and immunosuppressive activities, acts by irreversibly inhibiting eukaryotic transcription by RNA polymerase II (Pol II). XPB, a subunit of the general transcription factor TFIIH, was identified as the primary cellular target and the mechanism of action was shown to be the covalent modification of Cys342 of XPB by the 12,13-epoxide group of triptolide.

  12. Reviews

    1. Micro- and Nanomotors

      Chemically Powered Micro- and Nanomotors

      Dr. Samuel Sánchez, Dr. Lluís Soler and Jaideep Katuri

      Article first published online: 12 DEC 2014 | DOI: 10.1002/anie.201406096

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      Moving down in the world: Chemically powered micro- and nanomotors are small devices that are self-propelled by catalytic reactions in fluids. Remotely guided nanomotors can transport cargo to desired targets, drill into biomaterials, sense their environment, mix or pump fluids, and clean polluted water.

  13. Editorials

    1. You have free access to this content
      The Impact Factor of Angewandte Chemie

      Dr. Peter Gölitz

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201411579

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      What does the Impact Factor tell us? This question is addressed by Peter Gölitz in his Editorial, particularly in light of the surprising drop in the 2013 Impact Factor of Angewandte Chemie. An explanation is sought and found. Most importantly the influence of the individual variables that determine the Impact Factor needs to be understood.

  14. Communications

    1. Drug Discovery

      Multitarget Drug Discovery for Alzheimer's Disease: Triazinones as BACE-1 and GSK-3β Inhibitors

      Federica Prati, Dr. Angela De Simone, Dr. Paola Bisignano, Dr. Andrea Armirotti, Dr. Maria Summa, Dr. Daniela Pizzirani, Dr. Rita Scarpelli, Dr. Daniel I. Perez, Prof. Dr. Vincenza Andrisano, Dr. Ana Perez-Castillo, Prof. Dr. Barbara Monti, Francesca Massenzio, Dr. Letizia Polito, Prof. Dr. Marco Racchi, Dr. Angelo D. Favia, Dr. Giovanni Bottegoni, Prof. Dr. Ana Martinez, Prof. Dr. Maria Laura Bolognesi and Prof. Dr. Andrea Cavalli

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201410456

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      Two for one: Alzheimer's disease is a complex multifactorial syndrome which calls for the development of multitarget drugs. Accordingly, triazinones are reported here as the first molecule class which is able to simultaneously modulate BACE-1 and GSK-3β activity. Such dual-target inhibitors, by acting against two crucial enzymes in the neurotoxic pathways, might represent a breakthrough in the quest for disease-modifying drugs.

    2. Catalytic Metallodrug

      Toward the Design of a Catalytic Metallodrug: Selective Cleavage of G-Quadruplex Telomeric DNA by an Anticancer Copper–Acridine–ATCUN Complex

      Zhen Yu, Menglu Han and Dr. James A. Cowan

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201410434

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      A copper–acridine–ATCUN complex selectively binds and cleaves the G-quadruplex telomere sequence of DNA. The cleavage pathway has been mapped by MALDI-TOF MS experiments. The complex promotes significant inhibition of cancer cell proliferation and telomere shortening, inducing both senescence and apoptosis in the MCF7 cancer cell line.

    3. Hypervalent Reagents

      Hypervalent Iodine Reagents Enable Chemoselective Deboronative/Decarboxylative Alkenylation by Photoredox Catalysis

      Hanchu Huang, Kunfang Jia and Prof. Dr. Yiyun Chen

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201410176

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      Good visibility: A visible-light-induced chemoselective deboronative/decarboxylative alkenylation is reported. This novel hypervalent-iodine-enabled radical reaction proceeds through a benziodoxole vinyl carboxylic acid intermediate (right). Aryl-and acyl-substituted alkenes containing sensitive functional groups are constructed in good yields. Alkyl = 1’-, 2’-, 3’-alkyl, R = aryl, acyl.

    4. Diradicals

      Nitrogen Analogues of Thiele’s Hydrocarbon

      Yuanting Su, Dr. Xingyong Wang, Yuantao Li, Prof. You Song, Yunxia Sui and Prof. Xinping Wang

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201410256

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      Dications: A series of bis[N,N-di-(4-methoxylphenyl)amino]arene dications have been synthesized and characterized. It was found that they are singlets in the ground state and that their diradical character is dependent on the bridging moiety. The work provides a nitrogen analogue of Thiele’s hydrocarbon with a considerable diradical character.

    5. Natural Product Synthesis

      Total Synthesis and Biological Evaluation of the Antibiotic Lysocin E and Its Enantiomeric, Epimeric, and N-Demethylated Analogues

      Dr. Motoki Murai, Takuya Kaji, Dr. Takefumi Kuranaga, Dr. Hiroshi Hamamoto, Prof. Dr. Kazuhisa Sekimizu and Prof. Dr. Masayuki Inoue

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201410270

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      The antibacterial macrocyclic peptide lysocin E and its enantiomeric, epimeric, and N-demethylated analogues were synthesized by a full solid-phase strategy. Significantly, the antibacterial activity of the unnatural enantiomer was comparable to that of the natural isomer, suggesting the absence of chiral recognition in its mode of action.

    6. Fluorescent Probes

      Multiplex Detection of Enzymatic Activity with Responsive Lanthanide-Based Luminescent Probes

      Elias Pershagen and Dr. K. Eszter Borbas

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201408560

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      Getting real: The simultaneous, real-time detection of two enzymes or an enzyme and a small molecule by time-resolved luminescence spectroscopy has been demonstrated using lanthanide-based responsive probes. The use of two different lanthanide emitters results in well-separated output signals (see picture), while three-color analyte detection without spectral overlap can be achieved by combination with an organic fluorophore-based probe.

    7. Schottky Disorder

      Self-Regulation Mechanism for Charged Point Defects in Hybrid Halide Perovskites

      Prof. Aron Walsh, Dr. David O. Scanlon, Prof. Shiyou Chen, Prof. X. G. Gong and Dr. Su-Huai Wei

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201409740

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      Missing ion action: Schottky defects are found to be a dominant mode of equilibrium stoichiometric disorder in the photovoltaic material CH3NH3PbI3. This behavior can explain the previous finding that “the compounds show intense color, but there is no significant conductivity”.

    8. Iron Clusters

      Dinitrogen Activation Upon Reduction of a Triiron(II) Complex

      Yousoon Lee, Forrest T. Sloane, Dr. Geneviève Blondin, Dr. Khalil A. Abboud, Dr. Ricardo García-Serres and Prof. Dr. Leslie J. Murray

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201409676

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      A trinuclear iron(II) complex, Fe3Br3L in which L is a cyclophane bridged by three β-diketiminate arms, reacts with KC8 under dinitrogen atmosphere to form complex Fe3(NH)3L among other products. Reactions with 14N2 and 15N2 confirm atmospheric N2 reduction, and ammonia was detected by the indophenol assay. IR and Mössbauer spectroscopy as well as elemental analysis support the assignment that the reduction product contains protonated N-atom bridges.

    9. Noble Gas Clathrates

      Extreme Confinement of Xenon by Cryptophane-111 in the Solid State

      Akil I. Joseph, Dr. Saul H. Lapidus, Christopher M. Kane and Prof. K. Travis Holman

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201409415

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      Imprisoning a noble: Xenon gas is effectively imprisoned, at temperatures of up to 300 °C, by a trigonal crystalline phase of the discrete container molecule (±)-cryptophane-111. The seemingly unprecedented kinetic stability of the gas clathrate can be attributed in part to its crystal packing.

    10. Fluorescent Biological Probes

      Specific Light-Up Bioprobe with Aggregation-Induced Emission and Activatable Photoactivity for the Targeted and Image-Guided Photodynamic Ablation of Cancer Cells

      Dr. Youyong Yuan, Dr. Chong-Jing Zhang, Dr. Meng Gao, Ruoyu Zhang, Prof. Dr. Ben Zhong Tang and Prof. Dr. Bin Liu

      Article first published online: 11 DEC 2014 | DOI: 10.1002/anie.201408476

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      Target and kill: A dual-targeted enzyme-activatable bioprobe based on a photosensitizer was developed with the characteristics of aggregation-induced emission and aggregation-enhanced phototoxicity (see picture; ROS=reactive oxygen species). The probe enables simultaneous light-up fluorescence imaging and photodynamic ablation of specific cancer cells and shows a high signal-to-noise ratio without the need for a quencher or energy acceptor.

    11. Colloid Chemistry | Very Important Paper

      Emulsion Ripening through Molecular Exchange at Droplet Contacts

      Dr. Kevin Roger, Prof. Dr. Ulf Olsson, Dr. Ralf Schweins and Dr. Bernard Cabane

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201407858

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      Another pathway for coarsening of emulsion is uncovered, besides coalescence and Ostwald ripening, that is termed contact ripening (top). Its mechanism consists in an exchange of oil molecules during collisions of droplets (middle). The key step is the synchronous thinning of each surfactant layer, through which oil molecules can cross the interface (bottom).

    12. Bioconjugation

      Targeted Antithrombotic Protein Micelles

      Dr. Wookhyun Kim, Dr. Carolyn Haller, Dr. Erbin Dai, Xiowei Wang, Dr. Christoph E. Hagemeyer, Prof. David R. Liu, Prof. Karlheinz Peter and Prof. Elliot L. Chaikof

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201408529

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      Site-specific: An activated platelet-specific antibody and antithrombotic protein were site-specifically conjugated to the corona of protein nanomicelles for efficient detection and inhibition of thrombus formation. These multifunctional protein micelles provide a promising approach to the site-specific delivery of a potent antithrombotic agent, thus reducing the dose and bleeding risk. aPC=activated protein C, Th=thrombin.

    13. Synthetic Methods

      Metal-Free, Room-Temperature, Radical Alkoxycarbonylation of Aryldiazonium Salts through Visible-Light Photoredox Catalysis

      Wei Guo, Dr. Liang-Qiu Lu, Yue Wang, Ya-Ni Wang, Jia-Rong Chen and Prof. Dr. Wen-Jing Xiao

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201408837

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      All lit up: The radical alkoxycarboxylation of aryldiazonium salts using CO gas was accomplished through visible-light-induced photoredox catalysis. The reaction is metal-free, and proceeds at room temperature with a low loading of organic photocatalyst. A wide range of esters were conveniently synthesized in moderate to good yields. Importantly, this strategy can be further applied to other carboxylation reactions.

    14. Asymmetric Catalysis

      Highly Diastereo- and Enantioselective Palladium-Catalyzed [3+2] Cycloaddition of Vinyl Aziridines and α,β-Unsaturated Ketones

      Chao-Fan Xu, Bao-Hui Zheng, Jia-Jia Suo, Dr. Chang-Hua Ding and Prof. Dr. Xue-Long Hou

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201409467

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      Ring to ring: The title reaction of vinyl aziridines and alkenes with a single activator was realized. The presence of the substituent on the vinyl group of the vinyl aziridine plays a key role in determining the stereochemical outcome of the reaction. dba=dibenzylidene acetone, Ts=4-toluenesulfonyl.

    15. Lithium-Ion Batteries | Hot Paper

      A Hierarchical Tin/Carbon Composite as an Anode for Lithium-Ion Batteries with a Long Cycle Life

      Dr. Xingkang Huang, Dr. Shumao Cui, Dr. Jingbo Chang, Peter B. Hallac, Christopher R. Fell, Yanting Luo, Bernhard Metz, Junwei Jiang, Patrick T. Hurley and Prof. Junhong Chen

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201409530

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      High capacity anodes: A tin/carbon hierarchical structure was designed, in which some of the nanosized Sn particles are anchored on the tips of carbon nanotubes that are rooted on the surfaces of microsized hollow carbon cubes while other Sn nanoparticles are encapsulated in the hollow carbon cubes. Such a unique structure allows the Sn particles to accommodate the volume change upon lithiation.

    16. Heterogeneous Catalysis

      Ionic Liquids as Precursors for Efficient Mesoporous Iron-Nitrogen-Doped Oxygen Reduction Electrocatalyst

      Dr. Zelong Li, Dr. Guanglan Li, Prof. Luhua Jiang, Jinlei Li, Prof. Gongquan Sun, Prof. Chungu Xia and Prof. Fuwei Li

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201409579

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      N-enriched and Fe-embedded ordered mesoporous carbon electrocatalysts were fabricated from an ionic liquid precursor by hard template synthesis. This strategy provides a high surface area and populated Fe-N active sites with synergetic interaction for an optimized Fe10@NOMC catalyst. The catalyst shows excellent electrocatalytic efficiency and durability for the oxygen reduction in alkaline media.

    17. Synthetic Methods

      Redox-Neutral α-Allylation of Amines by Combining Palladium Catalysis and Visible-Light Photoredox Catalysis

      Jun Xuan, Ting-Ting Zeng, Zhu-Jia Feng, Qiao-Hui Deng, Prof. Dr. Jia-Rong Chen, Dr. Liang-Qiu Lu, Prof. Dr. Wen-Jing Xiao and Prof. Dr. Howard Alper

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201409999

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      Double up: The title reaction was accomplished by merging palladium catalysis and visible-light photoredox catalysis. The catalytic generation of an allyl radical from the corresponding π-allylpalladium intermediate was realized without additional metal reducing reagents for the first time. Various α-allylation products of amines were achieved in high yields by radical cross-coupling under mild reaction conditions. SET=single-electron transfer.

    18. Hybrid Materials

      Synergetic Spin Crossover and Fluorescence in One-Dimensional Hybrid Complexes

      Chun-Feng Wang, Dr. Ren-Fu Li, Prof. Dr. Xue-Yuan Chen, Dr. Rong-Jia Wei, Prof. Dr. Lan-Sun Zheng and Prof. Dr. Jun Tao

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201410454

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      Two hybrid materials assembled from a 1D spin-crossover structure and the fluorophores 1-pyrenecarboxaldehyde and Rhodamine B were prepared. A synergetic effect between spin crossover and fluorescence was proposed.

    19. Cycloaddition

      Type II Intramolecular [5+2] Cycloaddition: Facile Synthesis of Highly Functionalized Bridged Ring Systems

      Guangjian Mei, Xin Liu, Chuang Qiao, Wei Chen and Prof. Dr. Chuang-chuang Li

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201410806

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      Bridged: The title reaction proceeds via an oxidopyrylium ylide and allows the efficient diastereoselective formation of various synthetically challenging bridged 7-membered ring systems. This direct transformation has a broad substrate scope with high functional-group tolerance and unique endo selectivity and gives the bridged ring systems, including the highly strained tricyclic cores of ingenol and cyclocitrinol, in high yields. TMP=2,2,6,6-tetramethylpiperidine.

    20. Binding Modes in Peptides

      Multi-Frequency, Multi-Technique Pulsed EPR Investigation of the Copper Binding Site of Murine Amyloid β Peptide

      Donghun Kim, Dr. Jeong Kyu Bang and Dr. Sun Hee Kim

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201410389

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      Pulsed EPR spectroscopy in conjunction with specific isotope labeling was employed to investigate the structure of copper- murine amyloid peptides. This first detailed structural characterization shows that Ala2, Glu3, His6, and His14 are directly coordinated with the copper ion in murine amyloid β peptides at pH 8.5.

    21. Gas-Phase Ion Chemistry

      Nuclear Magnetic Resonance Structure Elucidation of Peptide b2 Ions

      Pengyuan Liu, Prof. Dr. R. Graham Cooks and Prof. Dr. Hao Chen

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201410250

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      Fragmentation of peptide ions: Atmospheric pressure thermal dissociation- (APTD) based preparative mass spectrometry was used to collect gas-phase peptide b2 fragments for structural elucidation by NMR spectroscopy. This strategy will be applicable to the elucidation of many difficult fragment ion structures in both fundamental ion chemistry studies and in applied proteomics research.

    22. Solid-State NMR Spectroscopy

      A Method for Dynamic Nuclear Polarization Enhancement of Membrane Proteins

      Adam N. Smith, Dr. Marc A. Caporini, Prof. Gail E. Fanucci and Prof. Joanna R. Long

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201410249

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      Large signal enhancements were observed for a membrane-embedded peptide throughout the lipid bilayer in dynamic nuclear polarization (DNP) magic-angle spinning solid-state NMR experiments when spin-labeled lipids were used as polarizing agent. The enhancement gradient typically observed with the use of water-soluble biradicals was diminished.

    23. Organoiron Complexes

      Elementary Steps of Iron Catalysis: Exploring the Links between Iron Alkyl and Iron Olefin Complexes for their Relevance in C[BOND]H Activation and C[BOND]C Bond Formation

      Dr. Alicia Casitas, Helga Krause, Dr. Richard Goddard and Prof. Alois Fürstner

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201410069

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      Trio con brio: Several unorthodox complexes of high relevance for the understanding of iron-catalyzed C–H activation and C–C bond formation have been obtained. These include a surrogate of an intermediate in [2+2+2] cycloaddition reactions, a 14 e [L2Fe(X)R] species that is (meta)stable despite its potential for β-H elimination, and an iron allyl hydride complex formed by two consecutive C–H activation events mediated by a single iron center.

    24. Radical Reactions | Hot Paper

      Decarbonylative Radical Coupling of α-Aminoacyl Tellurides: Single-Step Preparation of γ-Amino and α,β-Diamino Acids and Rapid Synthesis of Gabapentin and Manzacidin A

      Dr. Masanori Nagatomo, Hayato Nishiyama, Haruka Fujino and Prof. Dr. Masayuki Inoue

      Article first published online: 10 DEC 2014 | DOI: 10.1002/anie.201410186

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      Upon activation by Et3B and O2 at ambient temperature, α-aminoacyl tellurides were readily converted into α-amino carbon radicals through facile decarbonylation, which then reacted intermolecularly with acrylates or glyoxylic oxime ethers to generate various γ-amino and α,β-diamino acids. This mild and powerful coupling method was also applied to the synthesis of gabapentin and the natural product (−)-manzacidin A.

    25. Asymmetric Catalysis

      PyBidine–Cu(OTf)2-Catalyzed Asymmetric [3+2] Cycloaddition with Imino Esters: Harmony of Cu–Lewis Acid and Imidazolidine-NH Hydrogen Bonding in Concerto Catalysis

      Prof. Dr. Takayoshi Arai, Hiroki Ogawa, Dr. Atsuko Awata, Dr. Makoto Sato, Megumi Watabe and Prof. Dr. Masahiro Yamanaka

      Article first published online: 9 DEC 2014 | DOI: 10.1002/anie.201410782

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      Dual activation system: A bis(imidazolidine)pyridine (PyBidine)–Cu(OTf)2 complex catalyzes the endo-selective [3+2] cycloaddition of methyleneindolinones with imino esters to afford spiro[pyrrolidin-3,3′-oxindole]s in up to 98 % ee. X-ray analysis and DFT calculations suggest that an intermediate Cu enolate of the imino ester reacts with the methyleneindolinone, which is activated by NH-hydrogen bonding with the PyBidine–Cu(OTf)2 catalyst.

    26. Rhodium-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic Dibenzosiloles by Enantioselective [2+2+2] Cycloaddition

      Dr. Ryo Shintani, Chihiro Takagi, Tomoaki Ito, Dr. Masanobu Naito and Prof. Dr. Kyoko Nozaki

      Article first published online: 9 DEC 2014 | DOI: 10.1002/anie.201409733

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      Silicon cycles: An axially chiral monophosphine ligand is employed in the Rh-catalyzed reaction between siliconcontaining prochiral triynes and internal alkynes to form silicon-stereogenic dibenzosiloles with high yields and enantioselectivities. A germaniumstereogenic dibenzogermole is also prepared by this method.

    27. Rauhut–Currier Reaction

      Highly Enantioselective Intermolecular Cross Rauhut–Currier Reaction Catalyzed by a Multifunctional Lewis Base Catalyst

      Xuelin Dong, Ling Liang, Erqing Li and Prof. Dr. You Huang

      Article first published online: 9 DEC 2014 | DOI: 10.1002/anie.201409744

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      A cat. with handles: A multifunctional chiral Lewis base catalyst mediates the highly enantioselective intermolecular cross Rauhut–Currier reaction of different active olefins. The RC products were obtained in excellent yields and high chemo- and enantioselectivity. The reaction could be performed on a gram scale with a catalyst loading of 1 mol %.

    28. RNA Modification

      High-Resolution N6-Methyladenosine (m6A) Map Using Photo-Crosslinking-Assisted m6A Sequencing

      Kai Chen, Zhike Lu, Xiao Wang, Dr. Ye Fu, Dr. Guan-Zheng Luo, Nian Liu, Dr. Dali Han, Dr. Dan Dominissini, Dr. Qing Dai, Prof. Tao Pan and Prof. Chuan He

      Article first published online: 9 DEC 2014 | DOI: 10.1002/anie.201410647

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      Modification sites at N6-methyladenosine (m6A) can be more accurately defined with a photo-crosslinking-assisted m6A sequencing strategy. It was used to obtain a high-resolution map of m6A in a human transcriptome. 4SU=4-thiouridine, IP=immunoprecipitation.

    29. Molecular Dynamics

      Water-Mediated Recognition of Simple Alkyl Chains by Heart-Type Fatty-Acid-Binding Protein

      Dr. Shigeru Matsuoka, Dr. Shigeru Sugiyama, Dr. Daisuke Matsuoka, Mika Hirose, Dr. Sébastien Lethu, Hikaru Ano, Dr. Toshiaki Hara, Dr. Osamu Ichihara, Dr. S. Roy Kimura, Dr. Satoshi Murakami, Hanako Ishida, Dr. Eiichi Mizohata, Dr. Tsuyoshi Inoue and Dr. Michio Murata

      Article first published online: 9 DEC 2014 | DOI: 10.1002/anie.201409830

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      Distinguishing fatty acids: The heart-type fatty-acid-binding protein was shown to preferentially incorporate U-shaped fatty acids of C10–C18 by using a chain-length limiting water cluster. This mechanism was uncovered by ultrahigh-resolution X-ray crystallography as well as energy calculations of the coexisting water molecules with the WaterMap program.

    30. C[BOND]H Activation

      Synthesis of Annelated Phospholes through Intramolecular C[BOND]H Activation by Monovalent Phosphorus

      Xinda Wei, Zongming Lu, Xu Zhao, Prof. Dr. Zheng Duan and Prof. Dr. Francois Mathey

      Article first published online: 9 DEC 2014 | DOI: 10.1002/anie.201410603

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      Proximity matters: Electrophilic terminal phosphinidene complexes (left, with Ar-Ar being biaryl or an analogue thereof) undergo a spontaneous insertion of the P atom into the vicinal C[BOND]H bond to give annelated phospholes. The latter compounds are valuable precursors for the preparation of a variety of optoelectronic devices.

    31. Synthetic Methods

      Hydrogen-Borrowing and Interrupted-Hydrogen-Borrowing Reactions of Ketones and Methanol Catalyzed by Iridium

      Di Shen, Darren L. Poole, Camilla C. Shotton, Anne F. Kornahrens, Dr. Mark P. Healy and Prof. Timothy J. Donohoe

      Article first published online: 9 DEC 2014 | DOI: 10.1002/anie.201410391

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      On loan: [{Ir(cod)Cl}2] facilitates hydrogen-borrowing reactions of ketone enolates with methanol at 65 °C as described. Performing the reaction under an oxygen atmosphere aids the process, and when combined with a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. The addition of pro-nucleophiles to the reaction mixture completes a one-pot methylenation/conjugate addition protocol.

  15. Reviews

    1. Terpene Cyclases

      Terpenoid Biosynthesis Off the Beaten Track: Unconventional Cyclases and their Impact on Biomimetic Synthesis

      Martin Baunach, Jakob Franke and Prof. Dr. Christian Hertweck

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201407883

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      Terpene and terpenoid cyclizations are counted among the most complex chemical reactions occurring in nature and contribute crucially to the tremendous structural diversity of this largest family of natural products. This Review outlines novel terpenoid cyclases (TCs) beyond typical class I and II TCs, and showcases how their intriguing reaction mechanisms can inspire synthetic chemistry.

  16. Communications

    1. Liquid–Liquid Interfaces

      Particle-Stabilized Water Droplets that Sprout Millimeter-Scale Tubes

      Miglė Graužinytė, Joe Forth, Katherine A. Rumble and Dr. Paul S. Clegg

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201408365

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      Sprouting droplets: With increasing time, tubes are observed to sprout from water droplets with rigid membranes formed from colloidal particles trapped on the liquid–liquid interface. This is driven by an internal over-pressure which arises as a result of a minority constituent on the outside of the droplet that preferentially partitions into the water inside the membrane.

  17. Highlights

    1. Synthetic Methods

      Cooperation between Transition Metals and Lewis Acids: A Way To Activate H2 and H[BOND]E bonds

      Marc Devillard, Dr. Ghenwa Bouhadir and Dr. Didier Bourissou

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201410781

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      The presence of a Lewis acid, typically a borane, in the coordination sphere of transition metals (Ni, Fe, Pt) offers a new way to activate H2 and strong H[BOND]E (E=Si, C) bonds.

  18. Communications

    1. Reflection Colors

      Light-Directing Omnidirectional Circularly Polarized Reflection from Liquid-Crystal Droplets

      Dr. Jing Fan, Dr. Yannian Li, Dr. Hari Krishna Bisoyi, Prof. Rafael S. Zola, Prof. Deng-ke Yang, Dr. Timothy J. Bunning, Prof. David A. Weitz and Prof. Quan Li

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201410788

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      Blue rays: Photoirradiation of self-organized, phototunable 3D photonic superstructures of monodisperse droplets of a cholesteric liquid crystal (CLC) containing a photosensitive chiral molecular switch gives dynamic reflection colors. The colors can be tuned reversibly upon light irradiation, and in groups of droplets blue-ray patterns arise from photonic cross-communication between neighboring droplets.

    2. Microporous Materials

      Turn-On Luminescence Sensing and Real-Time Detection of Traces of Water in Organic Solvents by a Flexible Metal–Organic Framework

      Antigoni Douvali, Dr. Athanassios C. Tsipis, Dr. Svetlana V. Eliseeva, Prof. Stéphane Petoud, Dr. Giannis S. Papaefstathiou, Dr. Christos D. Malliakas, Dr. Ioannis Papadas, Dr. Gerasimos S. Armatas, Dr. Irene Margiolaki, Prof. Mercouri G. Kanatzidis, Dr. Theodore Lazarides and Dr. Manolis J. Manos

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201410612

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      Testing the water: A Mg2+ metal–organic framework (MOF) is reported. It has the extraordinary capability to detect, in real time, trace water concentrations (0.05–5 %) in various organic solvents through an unusual turn-on luminescence sensing mechanism. The sensitivity and fast response of this MOF for water, and its reusability make it one of the most powerful water sensors known.

    3. Single-Molecule Magnets

      Magnetic Memory in an Isotopically Enriched and Magnetically Isolated Mononuclear Dysprosium Complex

      Dr. Fabrice Pointillart, Dr. Kevin Bernot, Dr. Stéphane Golhen, Dr. Boris Le Guennic, Thierry Guizouarn, Dr. Lahcène Ouahab and Dr. Olivier Cador

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201409887

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      DIY magnetism: The quantum tunneling in a mononuclear Dy-based complex, which already behaves as a single-molecule magnet (SMM), can be drastically reduced, improving the capability of the molecule to store magnetic information. This improvement is brought about by using isotopes of DyIII without a nuclear magnetic moment, thus suppressing the hyperfine interaction, and by dilution of the SMM in a diamagnetic matrix thus cancelling the internal field.

    4. Enzyme Catalysis

      Excited-State Charge Separation in the Photochemical Mechanism of the Light-Driven Enzyme Protochlorophyllide Oxidoreductase

      Dr. Derren J. Heyes, Dr. Samantha J. O. Hardman, Tobias M. Hedison, Robin Hoeven, Dr. Greg M. Greetham, Prof. Michael Towrie and Prof. Nigel S. Scrutton

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201409881

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      Shining light on enzyme catalysis: Time-resolved spectroscopy has shown how light energy is harnessed to power catalysis in the light-driven enzyme protochlorophyllide oxidoreductase. Excited-state interactions between the enzyme and substrate result in a polarized and highly reactive double bond to trigger a subsequent nucleophilic attack of NADPH.

    5. [3+2] Cycloaddition Reactions

      Addition of Nitromethane to a Disilene and a Digermene: Comparison to Surface Reactivity and the Facile Formation of 1,3,2-Dioxazolidines

      Nada Y. Tashkandi, Frederick Parsons, Jiacheng Guo and Prof. Kim M. Baines

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201409707

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      Nitromethane addition to tetramesityldisilene and tetramesityldigermene leads to the formation of 1,3,2,4,5-dioxazadisil- and digermolidine ring systems, respectively. The 1,3,2,4,5-dioxazadisilolidine isomerizes to the 1,4,2,3,5-dioxazadisilolidine ring system, whereas the 1,3,2,4,5-dioxazadigermolidine undergoes ring opening to the isomeric oxime.

    6. Asymmetric Catalysis

      Catalytic Asymmetric Intramolecular Homologation of Ketones with α-Diazoesters: Synthesis of Cyclic α-Aryl/Alkyl β-Ketoesters

      Dr. Wei Li, Fei Tan, Xiaoyu Hao, Gang Wang, Yu Tang, Prof. Dr. Xiaohua Liu, Dr. Lili Lin and Prof. Dr. Xiaoming Feng

      Article first published online: 8 DEC 2014 | DOI: 10.1002/anie.201409572

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      A chiral­ N,N′-dioxide–Sc(OTf)3 complex catalyzes the asymmetric intramolecular homologation of simple ketones with α-diazoesters. This method gives access to chiral cyclic α-aryl/alkyl β-ketoesters with an all-carbon quaternary stereocenter. The reaction proceeds under mild reaction conditions through an intramolecular addition/rearrangement process, thereby generating the β-ketoesters in high yield and enantiomeric excess.

  19. Cover Pictures

    1. You have free access to this content
      Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li+/H+ Exchange in Aqueous Solutions

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

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201410930

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      Super-stable separators (solid electrolytes) are required for novel aqueous-based high-energy lithium batteries, to enable their long-term operation. In their Communication (DOI: 10.1002/anie.201408124), C. Ma, M. Chi, et al. demonstrate excellent stability and conductivity of the cubic Li7La3Zr2O12 garnet in neutral and strongly basic solutions, indicating it may be the ideal solid electrolyte for next-generation high-energy lithium batteries.

  20. Communications

    1. Oxygen Reduction Reaction

      Sulfur-Doped Graphene Derived from Cycled Lithium–Sulfur Batteries as a Metal-Free Electrocatalyst for the Oxygen Reduction Reaction

      Zhaoling Ma, Shuo Dou, Anli Shen, Li Tao, Prof. Liming Dai and Prof. Shuangyin Wang

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201410258

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      Reuse and recycle: By continuous charge/discharge cycling of Li–S batteries containing graphene–sulfur composites, graphene was recycled as sulfur-doped graphene. This material was used as a metal-free electrocatalyst for the oxygen reduction reaction.

    2. Phase Transitions

      Photoliquefiable Ionic Crystals: A Phase Crossover Approach for Photon Energy Storage Materials with Functional Multiplicity

      Keita Ishiba, Dr. Masa-aki Morikawa, Chie Chikara, Dr. Teppei Yamada, Katsunori Iwase, Mika Kawakita and Prof. Dr. Nobuo Kimizuka

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201410184

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      Going through a phase: ICs of azobenzene derivatives show photoinduced IC–IL phase transition (photoliquefaction) upon UV irradiation, and the resulting cis-azobenzene ILs are reversibly photocrystallized by illumination with visible light. The photoliquefaction of ICs is accompanied by a significant increase in ionic conductivity at ambient temperature and holds potential as energy storage materials.

    3. Photochemistry

      The Profound Effect of the Ring Size in the Electrocyclic Opening of Cyclobutene-Fused Bicyclic Systems

      Michael J. Ralph, Prof. Dr. David C. Harrowven, Dr. Steven Gaulier, Dr. Sean Ng and Prof. Dr. Kevin I. Booker-Milburn

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201410115

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      cis­ or­ trans? The thermal electrocyclic ring opening of a homologous series of [n.2.0]-fused bicyclic systems proceeds via cyclic cis,trans-dienes, in accordance with the Woodward–Hoffmann rules. Highly strained smaller cyclic dienes (≤9 members) undergo isomerization to the stable trans,trans system, while larger cyclic cis,trans dienes (≥10 members) are isolable.

    4. Endocytosis

      Stiffness-Dependent In Vitro Uptake and Lysosomal Acidification of Colloidal Particles

      Raimo Hartmann, Marcel Weidenbach, Martin Neubauer, Prof. Andreas Fery and Prof. Wolfgang J. Parak

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201409693

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      Stiffness matters: The properties of colloidal particles determine their uptake into cells. Only the mechanical stiffness of microparticles was varied, whereas other parameters were kept constant. The uptake was monitored in situ by analyzing individual particle trajectories including the progress of endocytosis. Soft particles with low stiffness are transported faster to lysosomes than stiffer ones.

  21. Author Profiles

    1. Hon Wai Lam

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201411361

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      I admire creative people. My favorite saying is “Too much analysis leads to paralysis”.

  22. Communications

    1. Peptidomimetics

      Stabilization of the Cysteine-Rich Conotoxin MrIA by Using a 1,2,3-Triazole as a Disulfide Bond Mimetic

      Dr. Alessandro Gori, Dr. Ching-I A. Wang, Dr. Peta J. Harvey, Dr. K. Johan Rosengren, Rebecca F. Bhola, Prof. Maria L. Gelmi, Renato Longhi, Prof. Macdonald J. Christie, Prof. Richard J. Lewis, Prof. Paul F. Alewood and Dr. Andreas Brust

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201409678

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      Click fix: Disulfide bond engineering of a χ-conopeptide (left) delivered selectively formed bioactive 1,2,3-triazole–disulfide hybrids (right) with vastly improved stability and function in a neuropathic pain model. The structural implications and broad impact of this selective folding and disulfide mimetic strategy for the stabilization of disulfide-rich peptides is discussed.

    2. Selective Oxidations

      Chloroacetate-Promoted Selective Oxidation of Heterobenzylic Methylenes under Copper Catalysis

      Dr. Jianming Liu, Xin Zhang, Hong Yi, Dr. Chao Liu, Ren Liu, Dr. Heng Zhang, Prof. Dr. Kelei Zhuo and Prof. Dr. Aiwen Lei

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201409580

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      Molecular oxygen can be used for the selective oxidation of C[BOND]H bonds of N-heterocyclic compounds to the corresponding ketones with a copper catalyst and ethyl chloroacetate as a promoter. In this transformation, various substituted N-heterocyclic compounds were well tolerated. Preliminary mechanistic investigations indicated that organic radical species were involved in the overall process.

    3. Cancer Therapy

      Marriage of Scintillator and Semiconductor for Synchronous Radiotherapy and Deep Photodynamic Therapy with Diminished Oxygen Dependence

      Dr. Chen Zhang, Prof. Kuaile Zhao, Prof. Wenbo Bu, Dr. Dalong Ni, Dr. Yanyan Liu, Prof. Jingwei Feng and Prof. Jianlin Shi

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201408472

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      An exemplary marriage: A scintillator and a semiconductor are combined to form an ionizing-radiation-induced photodynamic therapy agent based on a core–shell CeIII-doped LiYF4@SiO2@ZnO structure. The downconverted ultraviolet fluorescence from the system under X-ray irradiation enables the generation of electron–hole pairs in ZnO nanoparticles, which gives rise to the formation of biotoxic hydroxyl radicals.

    4. Lipids

      Self-Assembly Structure Formation during the Digestion of Human Breast Milk

      Dr. Stefan Salentinig, Stephanie Phan, Dr. Adrian Hawley and Prof. Ben J. Boyd

      Article first published online: 5 DEC 2014 | DOI: 10.1002/anie.201408320

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      Baby fat: An infant′s complete diet, human breast milk, is the key to its development and survival. The self-assembly of the lipid digestion products inside the breast milk fat droplet drives structure formation with a high internal surface area. The structure formation is necessarily linked to its function as a carrier for poorly water-soluble molecules in the digestive tract of the infant.

    5. Chromium Complexes

      A Heterobimetallic Superoxide Complex formed through O2 Activation between Chromium(II) and a Lithium Cation

      Dipl.-Chem. Fabian Schax, B. Sc. Simon Suhr, Dr. Eckhard Bill, Dr. Beatrice Braun, Dr. Christian Herwig and Prof. Dr. Christian Limberg

      Article first published online: 4 DEC 2014 | DOI: 10.1002/anie.201409294

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      A superoxide in an oxide environment: A heterobimetallic superoxide was accessed by reaction of a mononuclear lithium siloxido chromate(II) with O2 at low temperatures to yield a mononuclear chromium(III) superoxide complex. The crystal-structure and spectroscopic data reveal that the superoxido ligand interacts with an adjacent lithium cation, which may have aided the O2 activation.