Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 49

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

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

Online ISSN: 1521-3773

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

  1. Book Reviews

    1. The Chemistry of Molecular Imaging. Edited by Nicholas Long and Wing-Tak Wong.

      Isabel Santos

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201510176

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      John Wiley and Sons, Hoboken, 2015. 408 pp., hardcover, € 149.00.—ISBN 978-1118093276

  2. Communications

    1. Asymmetric Catalysis

      Catalytic Asymmetric Mannich Reactions with Fluorinated Aromatic Ketones: Efficient Access to Chiral β-Fluoroamines

      Prof. Dr. Barry M. Trost, Dr. Tanguy Saget, Andreas Lerchen and Chao-I (Joey) Hung

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201509719

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      Work of a Pro: A Zn/Prophenol-catalyzed direct Mannich reaction using α-fluoroketones allows efficient construction of β-fluoroamine motifs with high enantio- and diastereoselectivities. A stereocomplementary aldol reaction is also described. Boc=tert-butoxycarbonyl.

    2. Metal–Organic Frameworks

      Unraveling Inter- and Intrachain Electronics in Polythiophene Assemblies Mediated by Coordination Nanospaces

      Michael W. A. MacLean, Takashi Kitao, Dr. Takeo Suga, Prof. Dr. Motohiro Mizuno, Prof. Dr. Shu Seki, Dr. Takashi Uemura and Prof. Susumu Kitagawa

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201510084

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      Solitary confinement: The controlled assembly of polythiophene within the channels of a metal–organic framework was carried out. This system was used to demonstrate the assembly packing structure as a way of controlling the optical and electronic properties of the conjugated polymer.

    3. Quorum Sensing | Hot Paper

      Fimbrolide Natural Products Disrupt Bioluminescence of Vibrio By Targeting Autoinducer Biosynthesis and Luciferase Activity

      Weining Zhao, Nicola Lorenz, Prof. Dr. Kirsten Jung and Prof. Dr. Stephan A. Sieber

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201508052

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      Studies in­ Vibrio: Fimbrolides represent natural products that interfere with quorum sensing in various organisms. Despite their importance in biological studies their cellular mechanisms have remained unknown. Chemical proteomics have been utilized to identify proteins involved in autoinducer biosynthesis (LuxS) and luciferase activity (LuxE) as molecular targets.

    4. Photoswitches | Very Important Paper

      Light-Controlled Interconversion between a Self-Assembled Triangle and a Rhombicuboctahedral Sphere

      Muxin Han, Dr. Yuansu Luo, Dr. Bernd Damaschke, Dr. Laura Gómez, Dr. Xavi Ribas, Anex Jose, Patrick Peretzki, Prof. Dr. Michael Seibt and Prof. Dr. Guido H. Clever

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201508307

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      Lights, action! Irradiation with light of different wavelengths triggers the reversible conversion of small, self-assembled Pd3L6 rings based on photochromic dithienylethene ligands into rhombicuboctahedral Pd24L48 spheres measuring 7 nm across.

    5. Gold Catalysis

      Gold-Catalyzed C[BOND]H Annulation of Anthranils with Alkynes: A Facile, Flexible, and Atom-Economical Synthesis of Unprotected 7-Acyl Indoles

      Hongming Jin, Long Huang, Jin Xie, Matthias Rudolph, Frank Rominger and A. Stephen K. Hashmi

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201508309

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      Good as gold: The gold-catalyzed C[BOND]H annulation of anthranil derivatives with alkynes offers a facile, flexible, and atom-economical one-step route to unprotected 7-acylindoles. The reaction proceeds via an α-imino gold carbene intermediate, which promotes ortho-aryl C[BOND]H functionalization to afford the product. The transformation proceeds with a broad range of substrates under mild conditions.

    6. Antimicrobial Resistance

      Adjuvants Based on Hybrid Antibiotics Overcome Resistance in Pseudomonas aeruginosa and Enhance Fluoroquinolone Efficacy

      Dr. Bala Kishan Gorityala, Dr. Goutam Guchhait, Dinesh M. Fernando, Soumya Deo, Prof. Sean A. McKenna, Prof. George G. Zhanel, Prof. Ayush Kumar and Prof. Frank Schweizer

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201508330

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      Rescue me: Adjuvants that rescue the activity of fluoroquinolone antibiotics against multidrug-resistant and extremely drug resistant Pseudomonas aeruginosa can be generated by linking tobramycin to ciprofloxacin. The adjuvant combines the antibacterial modes of ciprofloxacin with the membrane-destabilizing effects of aminoglycosides, thereby resulting in enhanced cell penetration of fluoroquinolones and other antibiotics into P. aeruginosa.

    7. Charge Separation

      You have full text access to this OnlineOpen article
      Remarkable Dependence of the Final Charge Separation Efficiency on the Donor–Acceptor Interaction in Photoinduced Electron Transfer

      Dr. Tomohiro Higashino, Tomoki Yamada, Masanori Yamamoto, Prof. Dr. Akihiro Furube, Prof. Dr. Nikolai V. Tkachenko, Taku Miura, Prof. Dr. Yasuhiro Kobori, Dr. Ryota Jono, Prof. Dr. Koichi Yamashita and Prof. Dr. Hiroshi Imahori

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201509067

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      Optimization of donor–acceptor electronic coupling remarkably inhibits the undesirable rapid decay of the singlet charge-separated state to the ground state, yielding the final long-lived, triplet charge-separated state with circa 100 % efficiency. This finding is relevant to the rational design of artificial photosynthesis and organic photovoltaic cells.

    8. Lithium Ion Batteries

      Li2C2, a High-Capacity Cathode Material for Lithium Ion Batteries

      Na Tian, Dr. Yurui Gao, Yurong Li, Prof.Dr. Zhaoxiang Wang, Prof.Dr. Xiaoyan Song and Prof.Dr. Liquan Chen

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201509083

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      Lithium carbide (Li2C2) is shown to function as a potential cathode material for lithium ion batteries. At least half of the lithium can be extracted and reinserted in Li2C2 during cycling. These results open the door to future applications of alkali and alkaline earth metal electrodes.

  3. Reviews

    1. Silicon Nanocrystals

      Silicon Nanocrystals and Silicon-Polymer Hybrids: Synthesis, Surface Engineering, and Applications

      Dr. Mita Dasog, Julian Kehrle, Prof. Dr. Bernhard Rieger and Prof. Dr. Jonathan G. C. Veinot

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201506065

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      The grand old newcomer: Silicon may be the “grand old semiconductor”, however, it is a relative newcomer to the field of quantum dots. Silicon nanocrystals (Si-NCs) are emerging as a promising, non-toxic, and greener alternative to Group II–VI and III–V quantum dots. This Review highlights how surface chemistry can be used to engineer properties of Si-NCs and adapt them towards modern applications, such as sensors, photovoltaics, and light-emitting diodes.

  4. Communications

    1. Oxygenations

      Peroxygenase-Catalyzed Oxyfunctionalization Reactions Promoted by the Complete Oxidation of Methanol

      Dr. Yan Ni, Dr. Elena Fernández-Fueyo, Dr. Alvaro Gomez Baraibar, Dr. René Ullrich, Prof. Dr. Martin Hofrichter, Prof. Dr. Hideshi Yanase, Prof. Dr. Miguel Alcalde, Prof. Dr. Willem J. H. van Berkel and Dr. Frank Hollmann

      Article first published online: 26 NOV 2015 | DOI: 10.1002/anie.201507881

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      Fueled by methanol: Peroxygenases catalyze stereoselective oxyfunctionalizations by utilizing H2O2. To efficiently generate this oxidant in situ, a new enzymatic cascade process for the reductive activation of molecular oxygen with methanol as a stoichiometric reductant has been developed. This system was applied to the stereoselective hydroxylation of ethylbenzene to (R)-1-phenylethanol.

    2. Enzyme Catalysis

      Blocking Deprotonation with Retention of Aromaticity in a Plant ent-Copalyl Diphosphate Synthase Leads to Product Rearrangement

      Kevin C. Potter, Dr. Jiachen Zi, Dr. Young J. Hong, Samuel Schulte, Brandi Malchow, Prof. Dr. Dean J. Tantillo and Prof. Dr. Reuben J. Peters

      Article first published online: 25 NOV 2015 | DOI: 10.1002/anie.201509060

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      Make the swap: Substitution of histidine, comprising part of the catalytic base group in the ent-copalyl diphosphate synthases, leads to rearrangements. Through a series of 1,2-hydride and methyl shifts of the initially formed bicycle, predominant formation of (−)-kolavenyl diphosphate is observed. Further mutational analysis and quantum chemical calculations provide mechanistic insight into the basis for this profound effect on product outcome.

    3. Heterogeneous Catalysis

      Water-Enhanced Synthesis of Higher Alcohols from CO2 Hydrogenation over a Pt/Co3O4 Catalyst under Milder Conditions

      Dr. Zhenhong He, Dr. Qingli Qian, Dr. Jun Ma, Dr. Qinglei Meng, Dr. Huacong Zhou, Dr. Jinliang Song, Prof. Dr. Zhimin Liu and Prof. Dr. Buxing Han

      Article first published online: 25 NOV 2015 | DOI: 10.1002/anie.201507585

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      Water can enhance the synthesis of C2–C4 alcohols (C2+OH) from CO2 hydrogenation over Pt/Co3O4 significantly. The alcohols can be produced at a lower temperature with satisfactory activity and selectivity. DMI=1,3-dimethyl-2-imidazolidinone.

    4. Synthetic Methods

      Enantioselective Synthesis of 3 a-Amino-Pyrroloindolines by Copper-Catalyzed Direct Asymmetric Dearomative Amination of Tryptamines

      Dr. Chuan Liu, Ji-Cheng Yi, Dr. Zhong-Bo Zheng, Prof. Dr. Yong Tang, Prof. Li-Xin Dai and Prof. Dr. Shu-Li You

      Article first published online: 25 NOV 2015 | DOI: 10.1002/anie.201508570

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      A direct asymmetric dearomative amination of tryptamines with O-(2,4-dinitrophenyl)hydroxylamine (DPH) was achieved using CuBr-bisoxazoline complex as a catalyst, affording 3a-amino-pyrroloindolines in good enantioselectivity under mild reaction conditions. The synthetic value of this method was demonstrated in the total synthesis of (−)-psychotriasine in a highly concise manner.

    5. Organocatalysis

      A Catalyst Designed for the Enantioselective Construction of Methyl- and Alkyl-Substituted Tertiary Stereocenters

      Dr. Aurélie Claraz, Dr. Gokarneswar Sahoo, Dénes Berta, Dr. Ádám Madarász, Dr. Imre Pápai and Prof. Dr. Petri M. Pihko

      Article first published online: 25 NOV 2015 | DOI: 10.1002/anie.201509302

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      Methyls by design: Systematic three-point optimization affords an amine catalyst which provides ready access to chiral α-methyl-substituted and other α-alkyl-substituted thioesters in high enantiomeric purity (see example). Natural product building blocks, such as the C4–C13 segment of bistramide A, can be quickly accessed with the catalyst.

  5. News

    1. Société Chimique de France Prizes 2015

      Article first published online: 25 NOV 2015 | DOI: 10.1002/anie.201509907

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  6. Communications

    1. Silylene Complexes

      Stabilization of a Silaaldehyde by its η2 Coordination to Tungsten

      Dr. Tetsuya Fukuda, Dr. Hisako Hashimoto, Prof. Dr. Shigeyoshi Sakaki and Prof. Dr. Hiromi Tobita

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201507956

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      Closing the circle: Anionic silylene complexes, prepared by proton abstraction from pyridine-stabilized hydrido(hydrosilylene) compounds, were oxidized using pyridine-N-oxide to form η2-silaaldehyde complexes. Formation of a W-Si-O three-membered ring was confirmed by X-ray crystallography.

    2. Synthetic Methods

      You have full text access to this OnlineOpen article
      Palladium(II)-Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO: A Redox-Neutral, Phosphine-Free Transformation

      Alex S. Deeming, Dr. Claire J. Russell and Prof. Michael C. Willis

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201508370

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      Staying neutral: Pd(OAc)2 promotes the addition of aryl and heteroaryl boronic acids to the sulfur dioxide surrogate 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO) thus delivering the corresponding sulfinates. When combined with an electrophilic trap, this redox-neutral system provides a straightforward route for the one-pot preparation of a broad range of sulfones and sulfonamides.

    3. Optical Voltage Sensors

      Plasmonic/Nonlinear Optical Material Core/Shell Nanorods as Nanoscale Plasmon Modulators and Optical Voltage Sensors

      Dr. Anxiang Yin, Dr. Qiyuan He, Zhaoyang Lin, Dr. Liang Luo, Yuan Liu, Sen Yang, Hao Wu, Dr. Mengning Ding, Prof. Yu Huang and Prof. Xiangfeng Duan

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201508586

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      Nanoscale optical voltage sensors: The nanoscale integration of plasmonic and nonlinear optical materials can enable the creation of a new generation of sub-wavelength “electric-plasmonic-optical” modulators and nanoscale optical voltage sensors.

    4. Semiconductor Surfaces

      Air Passivation of Chalcogen Vacancies in Two-Dimensional Semiconductors

      Dr. Yuanyue Liu, Dr. Pauls Stradins and Dr. Su-Huai Wei

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201508828

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      The interaction between air and chalcogen vacancies (VX), the most typical defects in 2D semiconductors (SCs), is calculated. The chemisorbed O2 changes the VX from commonly believed harmful carrier-traps to electronically benign sites. This unusual behavior originates from the isovalence between O2 and X when bonded with metal. A facile approach is proposed from this to improve the performance of 2D SCs by using air/O2 to passivate the defects.

    5. Metal–Graphene Catalysis

      One-Step Pyrolysis Preparation of 1.1.1 Oriented Gold Nanoplatelets Supported on Graphene and Six Orders of Magnitude Enhancement of the Resulting Catalytic Activity

      Dr. Ana Primo, Ivan Esteve-Adell, Dr. Simona N. Coman, Natalia Candu, Prof. Vasile I. Parvulescu and Prof. Hermenegildo Garcia

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201508908

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      Easy gold–graphene nanohybrid catalysts: Graphene and 1.1.1 facet-oriented Au nanoparticles form simultaneously upon pyrolysis of chitosan-embedding AuCl4, and exhibit high catalytic activity.

    6. Self-Assembly | Hot Paper

      Two-Dimensional Nanoporous Networks Formed by Liquid-to-Solid Transfer of Hydrogen-Bonded Macrocycles Built from DNA Bases

      Nerea Bilbao, Iris Destoop, Prof. Steven De Feyter and Dr. David González-Rodríguez

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201509233

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      DNA base pairing is used to produce hydrogen-bonded macrocycles whose supramolecular structure can be transferred from solution to a solid substrate. A hierarchical assembly process ultimately leads to two-dimensional nanostructured porous networks that are able to host size-complementary guests.

    7. Lewis Adducts

      Dative Bonding between Group 13 Elements Using a Boron-Centered Lewis Base

      Prof. Dr. Holger Braunschweig, Dr. Rian D. Dewhurst, Leanne Pentecost, Dr. Krzysztof Radacki, Dr. Alfredo Vargas and Dr. Qing Ye

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201509289

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      An electron-rich monovalent boron compound is used as a Lewis base to prepare adducts with Group 13 Lewis acids, leading to the first noncluster Lewis adducts between a boron-centered Lewis base and a main-group Lewis acid.

    8. Biosynthesis | Very Important Paper

      Production of New Cladosporin Analogues by Reconstitution of the Polyketide Synthases Responsible for the Biosynthesis of this Antimalarial Agent

      Rachel V. K. Cochrane, Randy Sanichar, Gareth R. Lambkin, Béla Reiz, Dr. Wei Xu, Prof. Yi Tang and Prof. John C. Vederas

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201509345

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      The highly reducing and non-reducing polyketide synthase pair that is responsible for the production of cladosporin in Cladosporium cladosporioides has been identified and heterologously expressed, and its functional activity has been demonstrated. A putative lysyl-tRNA synthetase is also contained within the cladosporin gene cluster and proposed to be necessary for self-resistance in the organism.

    9. Dynamic Covalent Chemistry | Hot Paper

      Building Giant Carbocycles by Reversible C[BOND]C Bond Formation

      Dr. Daniel Beaudoin, Olivier Levasseur-Grenon, Dr. Thierry Maris and Prof. Dr. James D. Wuest

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201509608

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      Giant macrocyclic hydrocarbons can be obtained by a facile approach that is based on the reversible formation of carbon–carbon bonds. Extended spirobifluorene-substituted derivatives of Wittig’s hydrocarbon were synthesized and found to undergo oligomerization, leading to the largest hydrocarbon that has been crystallized and characterized by X-ray diffraction to date.

    10. CO2 Reduction | Hot Paper

      Ultrathin Co3O4 Layers Realizing Optimized CO2 Electroreduction to Formate

      Shan Gao, Xingchen Jiao, Zhongti Sun, Prof. Wenhua Zhang, Prof. Yongfu Sun, Dr. Chengming Wang, Qitao Hu, Xiaolong Zu, Fan Yang, Shuyang Yang, Liang Liang, Ju Wu and Prof. Yi Xie

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201509800

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      The thinner, the better: 1.72 nm thick Co3O4 layers were synthesized through a fast-heating strategy. Benefiting from the ultralarge fraction of surface atoms and increased density of states, the 1.72 nm thick Co3O4 layers are active in the electrocatalytic reduction of CO2 to formate and have a current density over 20 times higher than bulk samples.

  7. Minireviews

    1. Synthetic Methods

      You have full text access to this OnlineOpen article
      Transfer Hydrosilylation

      Prof. Dr. Martin Oestreich

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201508879

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      Fair trade: Transfer hydrosilylation is a technique that, unlike the conceptually related transfer hydrogenation, had not been considered for nearly a century. The recently developed radical and ionic transition-metal-free variants rely on aromatization of a cyclohexa-1,4-diene during release of a silicon radical and cation, respectively. Subsequent reaction with typical unsaturated substrates (e.g. alkenes) terminates the transfer process (see scheme).

  8. Communications

    1. Oxidation

      You have full text access to this OnlineOpen article
      Structurally Defined Molecular Hypervalent Iodine Catalysts for Intermolecular Enantioselective Reactions

      Dr. Stefan Haubenreisser, Dr. Thorsten H. Wöste, Dr. Claudio Martínez, Prof. Dr. Kazuaki Ishihara and Prof. Dr. Kilian Muñiz

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201507180

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      The “I”s have it: The enantioselective vicinal dioxygenation of styrene derivatives under mild conditions is catalyzed by chiral hypervalent iodine(III) compounds which are formed in situ from aryl iodines. Through hydrogen bonds, the ortho-substituents give rise to a chiral helical environment around the iodine(III) center and thus enable high asymmetric induction.

    2. O2 Activation

      Synergistic Substrate and Oxygen Activation in Salicylate Dioxygenase Revealed by QM/MM Simulations

      Dr. Subhendu Roy and Prof. Dr. Johannes Kästner

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201506363

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      The non-heme FeII center in salicylate 1,2-dioxygenase (SDO) synergistically activates salicylate and O2 to facilitate the reductive cleavage of O2, as revealed by QM/MM simulations. The reactive oxygen species is a covalent salicylate–FeII–O2 complex, and O2 activation happens without a proton source.

    3. CO2 Activation | Hot Paper

      Capture of CO2 by a Cationic Nickel(I) Complex in the Gas Phase and Characterization of the Bound, Activated CO2 Molecule by Cryogenic Ion Vibrational Predissociation Spectroscopy

      Dr. Fabian S. Menges, Stephanie M. Craig, Niklas Tötsch, Dr. Aaron Bloomfield, Subrata Ghosh, Prof. Dr. Hans-Jörg Krüger and Prof. Dr. Mark A. Johnson

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201507965

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      Highly distorted: A CO2 molecule is activated in the gas phase by a cationic mononuclear nickel(I) complex containing a tetraazamacrocyclic ligand. The resulting complex was structurally characterized by mass-selected vibrational predissociation spectroscopy, which indicated that this complex features a highly distorted CO2 molecule bound to the metal center in an η2-C,O coordination mode.

    4. Mechanochromic Fluorescence

      A Mechanochromic Single Crystal: Turning Two Color Changes into Tricolored Switch

      Zhiyong Ma, Zhijian Wang, Xiao Meng, Zhimin Ma, Dr. Zejun Xu, Prof. Yuguo Ma and Prof. Xinru Jia

      Article first published online: 24 NOV 2015 | DOI: 10.1002/anie.201507197

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      Tricolor switch: A single crystal of M-4-B was obtained by attaching the boron of BH3 to the amine linker between a tetraphenylethylene unit and rhodamine B. M-4-B showed a novel sequential tricolor switching from deep-blue to bluish-green and to a reddish color upon grinding. The boron atom played a key role in obtaining the single crystal (see picture: O red, N blue, B yellow).

  9. Author Profiles

    1. Geert-Jan Boons

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201510191

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      My favorite author (fiction) is Louis Paul Boon. The downside of my job is spending too much time away from home.

  10. Communications

    1. Drug Delivery Nanotubes

      Visible-Light-Triggered Drug Release from TiO2 Nanotube Arrays: A Controllable Antibacterial Platform

      Jingwen Xu, Xuemei Zhou, Dr. Zhida Gao, Prof. Dr. Yan-Yan Song and Prof. Dr. Patrik Schmuki

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508710

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      A visible-light-triggered drug delivery system is constructed based on a double-layered stack of TiO2 nanotubes. The key for visible light drug release is a hydrophobic cap on the nanotubes containing Au nanoparticles, where SPR with the TiO2 conduction band provides the active species for chain scission. The system was tested in antibacterial experiments against E. coli.

    2. Protein–Protein Interactions

      A Chemical Inhibitor of the Skp2/p300 Interaction that Promotes p53-Mediated Apoptosis

      Dr. Misook Oh, Dr. Ji Hoon Lee, Heejo Moon, Yu-Jung Hyun and Prof. Dr. Hyun-Suk Lim

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508716

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      Skp2 inhibitor: The discovery of a chemical inhibitor of the Skp2/p300 interaction is reported. The inhibitor is able to specifically inhibit non-proteolytic activity without affecting Skp2 proteolytic activity. Thus, the inhibitor can be developed as a chemical probe of Skp2 non-proteolytic function during tumorigenesis.

    3. Electronic Spectroscopy

      The Electronic Spectrum of the Fulvenallenyl Radical

      Arghya Chakraborty, Dr. Jan Fulara and Prof. Dr. John P. Maier

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508961

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      Finding proof: The fullvenallenyl radical, a key intermediate in the formation of polycyclic aromatic hydrocarbons, was produced in 6 K neon matrices after mass-selective deposition of C7H5 and C7H5+ generated from organic precursors in a hot cathode ion source. On the basis of electronic absorption spectra and calculated excitation energies, the key absorption system (blue arrows) is assigned to the 1 2B1[LEFTWARDS ARROW]X 2B1 transition of the radical.

    4. Surface Chemistry

      Methanol Conversion into Dimethyl Ether on the Anatase TiO2(001) Surface

      Feng Xiong, Yan-Yan Yu, Zongfang Wu, Guanghui Sun, Liangbing Ding, Yuekang Jin, Prof. Dr. Xue-Qing Gong and Prof. Dr. Weixin Huang

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201509021

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      Let's face't: The methanol-to-dimethyl ether (DME) reaction was unambiguously identified to occur by the dehydration coupling of methoxy species at the fourfold-coordinated Ti4+ sites (Ti4c) on a mineral anatase TiO2(001)-(1×4) surface. The results show, for the first time, the predicted higher reactivity of this facet relative to other reported TiO2 facets.

    5. Photocatalysis

      Visible-Light Photoredox-Catalyzed C[BOND]H Difluoroalkylation of Hydrazones through an Aminyl Radical/Polar Mechanism

      Pan Xu, Guoqiang Wang, Yuchen Zhu, Weipeng Li, Prof. Dr. Yixiang Cheng, Prof. Dr. Shuhua Li and Prof. Dr. Chengjian Zhu

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508698

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      Grab an electron from aminyl radical: The unprecedented title reaction involving aldehyde-derived hydrazones was developed. A variety of versatile difluorinated hydrazones were synthesized under mild reaction conditions and in good to excellent yields. Mechanistic analysis and theoretical calculations suggest an aminyl radical/polar crossover mechanism.

    6. Aptamers | Hot Paper

      Oligonucleotide-based Mimetics of Hepatocyte Growth Factor

      Dr. Ryosuke Ueki, Ayaka Ueki, Naoto Kanda and Prof. Shinsuke Sando

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508572

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      Bridging the gap: A 100-mer ssDNA was developed as a potent hepatocyte growth factor (HGF) mimetic. This ssDNA was designed to induce receptor dimerization at the cell surface and subsequent signal transduction in the same way as the natural growth factor. This new class of synthetic ligands reproduced growth factor induced cellular behaviors, including cell migration and proliferation.

    7. Nanoplasmonics | Hot Paper

      You have full text access to this OnlineOpen article
      Plasmonic Surfaces for Cell Growth and Retrieval Triggered by Near-Infrared Light

      Dr. Juan J. Giner-Casares, Dr. Malou Henriksen-Lacey, Dr. Isabel García and Prof. Dr. Luis M. Liz-Marzán

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201509025

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      Cell harvesting: Tailored plasmonic substrates can be used to capture various types of cells, which can be further released by irradiation with near-infrared (NIR) light without being damaged. Facile functionalization with RGD peptide allows tuning the morphology of integrin-rich cells.

    8. Biomass Conversion | Hot Paper

      Production of Diethyl Terephthalate from Biomass-Derived Muconic Acid

      Rui Lu, Prof. Dr. Fang Lu, Jiazhi Chen, Dr. Weiqiang Yu, Qianqian Huang, Junjie Zhang and Prof. Dr. Jie Xu

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201509149

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      Diethyl terephthalate is obtained from biomass-derived trans,trans-muconic acid through a cascade process combining esterification, Diels–Alder cycloaddition, and dehydrogenation. The esterification reaction significantly improves the solubility of the diester product in ethanol and promotes the Diels–Alder reaction.

    9. Alkene Hydroamination

      Regioselective, Asymmetric Formal Hydroamination of Unactivated Internal Alkenes

      Yumeng Xi, Trevor W. Butcher, Dr. Jing Zhang and Prof. John F. Hartwig

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201509235

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      A regio- and enantioselective formal hydroamination of unsymmetrical, unactivated internal alkenes occurs with a silane and hydroxylamine derivative. The regioselectivity is controlled by the electronic effects of ether, ester, and sulfonamide groups in the homoallylic position. This method provides direct access to 1,3-aminoalcohols with high enantioselectivity.

    10. Lipophilicity | Very Important Paper

      Investigating the Influence of (Deoxy)fluorination on the Lipophilicity of Non-UV-Active Fluorinated Alkanols and Carbohydrates by a New log P Determination Method

      Prof. Dr. Bruno Linclau, Zhong Wang, Dr. Guillaume Compain, Vincent Paumelle, Dr. Clement Q. Fontenelle, Dr. Neil Wells and Dr. Alex Weymouth-Wilson

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201509460

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      A variation of the “shake-flask method” was development for the straightforward determination of the lipophilicity (log P) of fluorinated compounds and is based on the relative integration of the 19F NMR peaks of a sample and an internal reference for each phase (oct=octanol). The influence of different fluorination motifs on the lipophilicity of various aliphatic alkanols and carbohydrates was determined.

    11. Antibiotics

      Total Synthesis and Structural Reassignment of Aspergillomarasmine A

      Daohong Liao, Shaoqiang Yang, Jianyu Wang, Jian Zhang, Benke Hong, Fan Wu and Prof. Dr. Xiaoguang Lei

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201509960

      Thumbnail image of graphical abstract

      Resistance is futile: The natural product aspergillomarasmine A (AMA) is a potent inhibitor of metallo-β-lactamase-1, which mediates resistance to β-lactam antibiotics. The presented total synthesis of AMA allowed a reassignment of its stereochemical configuration. The synthetic route is amenable to the efficient preparation of analogues for the development of potent and selective metallo-β-lactamase inhibitors.

  11. Highlights

    1. Bent Molecules

      Single-Handed Towards Nanosized Organic Molecules

      Prof. Dr. Michael Mastalerz

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201509420

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      Hand in hand: Enantiopure reactants have been used to generate rigid molecular tweezers by Buchwald–Hartwig aminations. These result in the phenazine units curving in only one direction with formation of one product exclusively.

  12. Communications

    1. Mass Spectrometry

      Probing the Lipid Annular Belt by Gas-Phase Dissociation of Membrane Proteins in Nanodiscs

      Dr. Michael T. Marty, Kin Kuan Hoi, Dr. Joseph Gault and Prof. Carol V. Robinson

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508289

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      Membrane proteins: Gas-phase dissociation of membrane proteins in nanodisc lipoprotein complexes by collisional activation yielded membrane proteins with many lipids bound in distinct shells. High-resolution orbitrap mass spectrometry provided unprecedented resolution of the dissociation products.

    2. Organic Semiconductors | Hot Paper

      Layered Electron Acceptors by Dimerization of Acenes End- Capped with 1,2,5-Thiadiazoles

      Debin Xia, Prof. Dr. Xin Guo, Prof. Dr. Long Chen, Prof. Dr. Martin Baumgarten, Dr. Ashok Keerthi and Prof. Dr. Klaus Müllen

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508361

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      Dimerization of heteroacenes: Layered electron acceptors equipped with terminal 1,2,5-thiadiazole groups were constructed using a one-pot protocol of acene dimerization. Crystal structures of the compounds and their photophysical and electrochemical properties were studied.

    3. Biaryl Synthesis | Hot Paper

      Practical Organocatalytic Synthesis of Functionalized Non-C2-Symmetrical Atropisomeric Biaryls

      Dr. Hongyin Gao, Prof. Dr. Qing-Long Xu, Craig Keene, Dr. Muhammed Yousufuddin, Prof. Dr. Daniel H. Ess and Prof. Dr. László Kürti

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508419

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      An organic acid catalyzed direct arylation of aromatic C(sp2)[BOND]H bonds in phenols and naphthols was developed. This transformation is operationally simple, does not require an external oxidant, is readily scaled up, and the structurally diverse biaryls are formed with complete regioselectivity. Density functional calculations suggest a mechanism involving a mixed-acetal formation/[3,3]-sigmatropic rearrangement sequence.

    4. Cross-Coupling

      α-Arylation/Heteroarylation of Chiral α-Aminomethyltrifluoro-borates by Synergistic Iridium Photoredox/Nickel Cross-Coupling Catalysis

      Dr. Mirna El Khatib, Dr. Ricardo Augusto Massarico Serafim and Prof. Gary A. Molander

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201506147

      Thumbnail image of graphical abstract

      Making light of it: A novel dual catalytic route to enantiopure benzylic amines is outlined, and it takes advantage of photoredox catalysis in conjunction with nickel-catalyzed cross-coupling. The starting materials are robust organotrifluoroborates that can engage, with an expanded range of densely functionalized aryl- and heteroaryl halides, in the title reaction.

    5. Drug Design

      Modular PROTAC Design for the Degradation of Oncogenic BCR-ABL

      Ashton C. Lai, Dr. Momar Toure, Dr. Doris Hellerschmied, Jemilat Salami, Dr. Saul Jaime-Figueroa, Dr. Eunhwa Ko, Dr. John Hines and Prof. Craig M. Crews

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201507634

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      Induced protein degradation is an emerging field that has the potential to overcome many challenges faced by traditional inhibitor-based drug design. A modular approach to PROTAC design is presented that enables targeted degradation of the therapeutically relevant BCR-ABL oncogenic protein.

    6. Organic Biradicaloids

      Cethrene: A Helically Chiral Biradicaloid Isomer of Heptazethrene

      Dr. Prince Ravat, Dr. Tomáš Šolomek, Dr. Michel Rickhaus, Priv.-Doz.Dr. Daniel Häussinger, Dr. Markus Neuburger, Prof. Martin Baumgarten and Dr. Michal Juríček

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201507961

      Thumbnail image of graphical abstract

      “C” versus “Z”: In chiral biradicaloid cethrene (“C”) the singlet–triplet energy gap is smaller than that in planar heptazethrene (“Z”) because of the helical twist. Cethrene gives well-resolved EPR and NMR spectra and its structure was confirmed by 2D NMR spectroscopy. The helical compound undergoes a transformation to a planar hydrocarbon and “lives” for several hours at room temperature.

  13. Highlights

    1. Detoxification of Nerve Agents

      Breaking Down Chemical Weapons by Metal–Organic Frameworks

      Dr. Suvendu Sekhar Mondal and Prof. Dr. Hans-Jürgen Holdt

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201508407

      Thumbnail image of graphical abstract

      Seek and destroy: Filtration schemes and self-detoxifying protective fabrics based on ZrIV-containing the metal—organic frameworks (MOFs) MOF-808 and UiO-66 doped with LiOtBu have been developed that capture and hydrolytically detoxify simulants of nerve agents and mustard gas. Both MOFs function as highly catalytic elements in these applications.

  14. Communications

    1. Membrane Proteins

      A Self-Assembled Respiratory Chain that Catalyzes NADH Oxidation by Ubiquinone-10 Cycling between Complex I and the Alternative Oxidase

      Andrew J. Y. Jones, James N. Blaza, Hannah R. Bridges, Benjamin May, Anthony L. Moore and Judy Hirst

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201507332

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      Chained together: Mitochondrial complex I is crucial for respiration, but its reactions with ubiquinone-10 (Q10) are poorly understood because Q10 is extremely hydrophobic. An artificial electron transport chain comprising complex I, Q10, and a quinol oxidase was self-assembled in synthetic vesicles and used to study Q10 reduction in a fully defined environment. This self-assembled system is suitable for studying any enzyme that uses a quinone/quinol substrate.

    2. Homogeneous Catalysis

      Iron-Catalyzed Direct Diazidation for a Broad Range of Olefins

      Yong-An Yuan, Deng-Fu Lu, Yun-Rong Chen and Prof. Hao Xu

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201507550

      Thumbnail image of graphical abstract

      With iron hand: The title reaction proceeds at room temperature and tolerates a broad range of both unfunctionalized and highly functionalized olefins. It also provides a convenient synthetic approach to a variety of nitrogen-containing building blocks. Preliminary mechanistic studies suggest both Lewis acid activation and iron-enabled redox-catalysis are crucial for selective the azido-group transfer.

    3. Analytical Chemistry | Very Important Paper

      Dose-Dependent Response of Personal Glucose Meters to Nicotinamide Coenzymes: Applications to Point-of-Care Diagnostics of Many Non-Glucose Targets in a Single Step

      Dr. Jingjing Zhang, Prof. Dr. Yu Xiang, Miao Wang, Dr. Ananda Basu and Prof. Dr. Yi Lu

      Article first published online: 23 NOV 2015 | DOI: 10.1002/anie.201507563

      Thumbnail image of graphical abstract

      Glucose & Personal: A wide range of non-glucose targets can be detected by using the dose-dependent response of personal glucose meters to nicotinamide coenzymes, such as the reduced form of nicotinamide adenine dinucleotide (NADH). Cascade enzymatic reactions result in the target-induced consumption or production of NADH, which in turn is detected by the glucose meter. This point-of-care device can be used for highly sensitive blood analysis in a single step.

  15. Author Profiles

    1. Yixin Lu

      Article first published online: 20 NOV 2015 | DOI: 10.1002/anie.201508283

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      My favorite food is lobster. My favorite place on earth is The Maldives.

  16. Communications

    1. Synthetic Methods

      An Exclusively trans-Selective Chlorocarbamoylation of Alkynes Enabled by a Palladium/Phosphaadamantane Catalyst

      Christine M. Le, Xiao Hou, Theresa Sperger, Prof. Dr. Franziska Schoenebeck and Prof. Dr. Mark Lautens

      Article first published online: 20 NOV 2015 | DOI: 10.1002/anie.201507883

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      A new­ trans-formation: The use of bulky, electron-deficient phosphaadamantane ligands in combination with sterically hindered alkynes enabled a palladium(0)-catalyzed alkyne chlorocarbamoylation reaction with high reactivity and exclusive trans selectivity.

    2. Fluorescent Crystals

      Stimuli-Responsive Reversible Fluorescence Switching in a Crystalline Donor–Acceptor Mixture Film: Mixed Stack Charge-Transfer Emission versus Segregated Stack Monomer Emission

      Sang Kyu Park, Illhun Cho, Dr. Johannes Gierschner, Jin Hong Kim, Dr. Jong H. Kim, Dr. Ji Eon Kwon, Oh Kyu Kwon, Dong Ryeol Whang, Jung-Hwa Park, Prof. Byeong-Kwan An and Prof. Soo Young Park

      Article first published online: 20 NOV 2015 | DOI: 10.1002/anie.201508210

      Thumbnail image of graphical abstract

      To mix or not to mix: A donor–acceptor (D-A) charge-transfer (CT) crystalline film was designed to realize stimuli-responsive reversible fluorescence switching media. Owing to the loosely packed CT state, reorganization between the red-emissive mixed CT phase and blue-emissive demixed self-sorted phase can be demonstrated by external triggers such as solvent, thermal, and piezomechanical stimuli.

    3. Gene Delivery

      High DNA-Binding Affinity and Gene-Transfection Efficacy of Bioreducible Cationic Nanomicelles with a Fluorinated Core

      Long-Hai Wang, Prof. Dr. De-Cheng Wu, Prof. Dr. Hang-Xun Xu and Prof. Dr. Ye-Zi You

      Article first published online: 20 NOV 2015 | DOI: 10.1002/anie.201508695

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      Reliable transport and delivery: Bioreducible cationic nanomicelles exhibited remarkably high DNA-binding affinity to completely condense DNA at an N/P ratio of 1. The efficiency with which the resulting nanomicelle/DNA polyplexes delivered genes into cells was much higher than that of a cationic polymer (see picture). In some cases, even at a low N/P ratio of 2, the gene-transfection efficiency was similar to that observed with viral vectors.

    4. Transmetalation

      Functionalizations of Mixtures of Regioisomeric Aryllithium Compounds by Selective Trapping with Dichlorozirconocene

      M. Sc. Alicia Castelló-Micó, Dr. Simon A. Herbert, Dr. Thierry León, Prof. Dr. Thomas Bein and Prof. Dr. Paul Knochel

      Article first published online: 20 NOV 2015 | DOI: 10.1002/anie.201508719

      Thumbnail image of graphical abstract

      Zirconium is the choice: Mixtures of regioisomeric aryllithium compounds can now be selectively transmetalated with Cp2ZrCl2 based on steric effects. Since the most sterically encumbered lithium species is not transmetalated, it can react with various electrophiles.

    5. Self-Assembly

      Role of the Symmetry of Multipoint Hydrogen Bonding on Chelate Cooperativity in Supramolecular Macrocyclization Processes

      Carlos Montoro-García, Jorge Camacho-García, Dr. Ana M. López-Pérez, Dr. María J. Mayoral, Nerea Bilbao and Dr. David González-Rodríguez

      Article first published online: 20 NOV 2015 | DOI: 10.1002/anie.201508854

      Thumbnail image of graphical abstract

      Symmetry matters: Analysis of the intrinsic chelate effect that multipoint H-bonding patterns exert on the overall energy of dinucleoside cyclic systems showed that the magnitude of the effective molarity (EM) is regulated by the symmetry of the H-bonding pattern. In our case, the EM value was about three orders of magnitude lower for the symmetric DAD–ADA pattern than for the unsymmetric ADD–DAA and DDA–AAD patterns (see picture).

    6. Photochemistry

      A Light-Activated Olefin Metathesis Catalyst Equipped with a Chromatic Orthogonal Self-Destruct Function

      Dr. Revannath L. Sutar, Efrat Levin, Danielle Butilkov, Prof. Israel Goldberg, Dr. Ofer Reany and Prof. N. Gabriel Lemcoff

      Article first published online: 20 NOV 2015 | DOI: 10.1002/anie.201508966

      Thumbnail image of graphical abstract

      Light giveth and light taketh: A new catalyst promotes olefin metathesis when irradiated with UV-A and is decomposed by UV-C. Complex light-guided chemical processes based on olefin metathesis, including polymerization, can be carried out by this protocol.

    7. Brook Rearrangement | Hot Paper

      Type II Anion Relay Chemistry: Exploiting Bifunctional Weinreb Amide Linchpins for the One-Pot Synthesis of Differentiated 1,3-Diketones, Pyrans, and Spiroketals

      Dr. Mark Farrell, Bruno Melillo and Dr. Amos B. Smith III

      Article first published online: 20 NOV 2015 | DOI: 10.1002/anie.201509342

      Thumbnail image of graphical abstract

      A highly effective bifunctional linchpin for type II anion relay chemistry has been developed. The mechanistically novel negative-charge migration that comprises a Brook rearrangement is initiated by a stabilized tetrahedral intermediate that is generated by nucleophilic addition to a Weinreb amide rather than by a simple, epoxide-derived oxyanion.

  17. Reviews

    1. Lithium Batteries

      Ionic-Liquid-Based Polymer Electrolytes for Battery Applications

      Irene Osada, Henrik de Vries, Prof. Dr. Bruno Scrosati and Prof. Dr. Stefano Passerini

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201504971

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      Safety net: Polymer electrolytes are a safe alternative to conventional liquid electrolytes in lithium batteries. Their main drawback is low ionic conductivity at room temperature. The most promising solution for this issue is incorporation of ionic liquids, which enhance the performance without decline in safety. This Review elucidates the interactions in these ternary polymer electrolytes and their performance in lithium-metal polymer batteries.

  18. Communications

    1. Fluorescent Probes | Hot Paper

      A Rotational BODIPY Nucleotide: An Environment-Sensitive Fluorescence-Lifetime Probe for DNA Interactions and Applications in Live-Cell Microscopy

      Dr. Dmytro Dziuba, Dr. Piotr Jurkiewicz, Dr. Marek Cebecauer, Prof. Dr. Martin Hof and Prof. Dr. Michal Hocek

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201507922

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      Rotational probe: A probe comprising a nucleoside linked to a meso-substituted BODIPY fluorescent molecular rotor (see figure) can be used to sense changes in the DNA microenvironment both in vitro and in living cells. Changes in the fluorescence lifetime of the probe allow detection of interaction with DNA-binding proteins or lipids.

    2. Monolayers | Very Important Paper

      Synthesis of a Two-Dimensional Covalent Organic Monolayer through Dynamic Imine Chemistry at the Air/Water Interface

      Wenyang Dai, Feng Shao, Jacek Szczerbiński, Ryan McCaffrey, Prof. Dr. Renato Zenobi, Dr. Yinghua Jin, Prof. Dr. A. Dieter Schlüter and Prof. Dr. Wei Zhang

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201508473

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      On the edge: A large, two-dimensional, covalently bound organic monolayer was synthesized through dynamic imine chemistry at the air/water interface. The imine-linked chemical structure of the aromatic monolayer was characterized by tip-enhanced Raman spectroscopy (TERS) and further supported by density functional theory (DFT) simulations.

    3. Pentacenes

      Stabilizing Pentacene By Cyclopentannulation

      Sambasiva R. Bheemireddy, Dr. Pamela C. Ubaldo, Peter W. Rose, Dr. Aaron D. Finke, Prof. Junpeng Zhuang, Prof. Lichang Wang and Prof. Kyle N. Plunkett

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201508650

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      Five in a row: A palladium-catalyzed cyclopentannulation followed by a DDQ-mediated dehydrogenation converts a partially hydrogenated pentacene precursor into stabilized pentacenes. These pentacene derivatives are excellent electron acceptors and have small energy gaps. DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

    4. Heterocycle Synthesis

      Synthesis of Carbazole Alkaloids by Ring-Closing Metathesis and Ring Rearrangement–Aromatization

      Kalyan Dhara, Tirtha Mandal, Joydeb Das and Prof. Dr. Jyotirmayee Dash

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201508746

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      Just a hop, skip, and a jump away: The addition of allyl Grignard/indium reagents to isatins, ring-closing metathesis (RCM), and ring rearrangement–aromatization (RRA) provided carbazole derivatives in high overall yield (see scheme). The RCM step afforded spirocyclic 3-oxindoles, which underwent acid-catalyzed RRA to give carbazoles. A step-economical tandem RCM/RRA process was also developed and applied to the synthesis of carbazole alkaloids.

    5. Structural Biology

      N-linked Glycans of Chloroviruses Sharing a Core Architecture without Precedent

      Prof. Cristina De Castro, Dr. Immacolata Speciale, Prof. Garry Duncan, Dr. David D. Dunigan, Dr. Irina Agarkova, Prof. Rosa Lanzetta, Dr. Luisa Sturiale, Dr. Angelo Palmigiano, Prof. Domenico Garozzo, Prof. Antonio Molinaro, Prof. Michela Tonetti and Prof. James L. Van Etten

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201509150

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      Glycan signature: Chloroviruses glycosylate their capsid protein in a host-independent process. These N-linked glycans have unprecedented structures, and each is virus-specific, but all share the same core motif. Conservation in the core region occurs at two different levels: the most conserved region comprises five residues and inclusion of the sixth extends this strictly conserved core. This core oligosaccharide represents a new type of N-glycosylation.

  19. Highlights

    1. DNA Repair

      DNA Repair

      Prof. Dr. Thomas Carell

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201509770

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      DNA is constantly damaged by various endogenous and exogenous events. Repair systems constantly scan the genome for DNA lesions and replace damaged and mismatched bases, which finally enables the complex DNA double strand to store genetic information. This year’s Nobel Prize in Chemistry was awarded to pioneers in this field, T. Lindahl, P. Modrich, and A. Sancar.

  20. Communications

    1. Molecular Machines | Hot Paper

      Hierarchical Self-Assembly of Supramolecular Muscle-Like Fibers

      Antoine Goujon, Dr. Guangyan Du, Dr. Emilie Moulin, Dr. Gad Fuks, Prof. Dr. Mounir Maaloum, Prof. Dr. Eric Buhler and Prof. Dr. Nicolas Giuseppone

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201509813

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      Supramolecular polymers: The integrated actuation of switchable mechanical bonds in bundles of supramolecular polymers leads to dynamic mesostructures (see picture). A new kind of hydrogen-bonded supramolecular polymers is described which incorporate molecular machines in the form of acid–base switchable [c2]daisy chain rotaxanes.

    2. Difluorocarbene | Hot Paper

      Reaction of Diazo Compounds with Difluorocarbene: An Efficient Approach towards 1,1-Difluoroolefins

      Zhikun Zhang, Weizhi Yu, Chenggui Wu, Chengpeng Wang, Yan Zhang and Prof. Dr. Jianbo Wang

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201509711

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      Formal carbene dimerization: The difluoromethylenation of diazo compounds was achieved under mild conditions with TMSCF2Br as the difluoromethylene source and tetrabutylammonium bromide (TBAB) as the initiator. The chemoselective formal carbene dimerization is achieved owing to the electronic properties and the relative stability of the difluorocarbene intermediate.

    3. Electrocatalysis

      Single-Crystalline Ultrathin Nickel Nanosheets Array from In Situ Topotactic Reduction for Active and Stable Electrocatalysis

      Dr. Yun Kuang, Guang Feng, Pengsong Li, Yongmin Bi, Dr. Yaping Li and Prof. Xiaoming Sun

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201509616

      Thumbnail image of graphical abstract

      Low-cost electrocatalysts: Ultrathin nickel nanosheets were synthesized by gently reducing a Ni(OH)2 nanosheet array on a metal substrate (see picture). The electrocatalytic performance of the Ni nanosheets was tested on the oxidation of hydrazine and the hydrogen-evolution reaction.

    4. Radical Reactions

      A Free-Radical-Promoted Stereospecific Decarboxylative Silylation of α,β-Unsaturated Acids with Silanes

      Lizhi Zhang, Zhaojia Hang and Prof. Dr. Zhong-Quan Liu

      Article first published online: 19 NOV 2015 | DOI: 10.1002/anie.201509537

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      A radical transformation: A stereospecific decarboxylative silylation of acrylic and propiolic acids with silanes was developed. This method provides an efficient and convenient approach to various synthetically useful alkenyl and alkynyl organosilicon compounds through the reaction of α,β-unsaturated acids with silanes. Spin-trapping and EPR experiments support a radical addition/elimination process.

    5. Methane Activation

      Efficient Room-Temperature, Au+-Mediated Coupling of a Carbene Ligand with Methane To Generate C2Hx (x=4, 6)

      Dr. Shaodong Zhou, Dr. Jilai Li, Dr. Xiao-Nan Wu, Dr. Maria Schlangen and Prof. Helmut Schwarz

      Article first published online: 18 NOV 2015 | DOI: 10.1002/anie.201509320

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      The thermal reactions of the closed-shell, “naked” gold–carbene complex [Au(CH2)]+ with methane have been explored by using FTICR mass spectrometry complemented by quantum chemical calculations. The insertion of the carbene ligand into the C[BOND]H bond of methane have been addressed mechanistically and the origin of the counterintuitive high reactivity of [Au(CH2)]+ towards this most inert hydrocarbon is discussed.

    6. Reaction Mechanisms

      Fundamental Difference in Reductive Lithiations with Preformed Radical Anions versus Catalytic Aromatic Electron-Transfer Agents: N,N-Dimethylaniline as an Advantageous Catalyst

      Dr. Nicole Kennedy, Prof. Peng Liu and Prof. Theodore Cohen

      Article first published online: 18 NOV 2015 | DOI: 10.1002/anie.201508971

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      Surface deep: The reductive lithiation of phenyl thioethers proceeds by either preformed aromatic radical anions or by lithium metal and an aromatic electron-transfer catalyst. These two methods are fundamentally different: reductions with radical anions occur in solution, whereas the catalytic reaction occurs on the surface of lithium, which is constantly reactivated by the catalyst. A catalytic amount of N,N-dimethylaniline (DMA) and Li ribbon can achieve reductive lithiation.

    7. Asymmetric Catalysis

      Kinetic Resolution of β-Sulfonyl Ketones through Enantioselective β-Elimination using a Cation-Binding Polyether Catalyst

      Liang Li, Yidong Liu, Yang Peng, Lei Yu, Xiaoyan Wu and Prof. Hailong Yan

      Article first published online: 18 NOV 2015 | DOI: 10.1002/anie.201508127

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      Paired off: The title reaction leads to effective resolution of a wide range of β-sulfonyl ketones (1) with high stereoselectivity. Key to the success of this process is the favorable secondary interactions of the catalyst with the Lewis basic groups on the substrate. The enone product can be easily converted into the racemic starting material and allows effective recycling, and thus isolation of β-sulfonyl ketones in high yield and excellent enantioselectivity.

    8. Nanoparticle Catalysis

      A Rhodium Nanoparticle–Lewis Acidic Ionic Liquid Catalyst for the Chemoselective Reduction of Heteroarenes

      Alena Karakulina, Aswin Gopakumar, Dr. İsmail Akçok, Bastien L. Roulier, Dr. Thomas LaGrange, Dr. Sergey A. Katsyuba, Dr. Shoubhik Das and Prof. Dr. Paul J. Dyson

      Article first published online: 18 NOV 2015 | DOI: 10.1002/anie.201507945

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      A rhodium nanoparticle catalyst immobilized in a Lewis acidic ionic liquid is described. The combined system catalyzes the hydrogenation of quinolines, pyridines, benzofurans, and furan to access the corresponding heterocycles.

    9. Cage Compounds

      High-Nuclearity Silver Thiolate Clusters Constructed with Phosphonates

      Dr. Yun-Peng Xie, Dr. Jun-Ling Jin, Prof. Xing Lu and Prof. Thomas C. W. Mak

      Article first published online: 18 NOV 2015 | DOI: 10.1002/anie.201507512

      Thumbnail image of graphical abstract

      Elaborate Ag–S nanoclusters: Two unprecedented 1D assemblies and an anionic cluster based on silver(I) thiolate cages as their surface components and phosphonate-functionalized silver(I) clusters as cores are reported. The picture shows the outer cationic [Ag36(tBuS)24]12+ cluster that encapsulates the inner anionic [MoO4@Ag12(nBuPO3)8S6]18− cluster.

    10. Fluorescent Probes

      Highly Efficient Far Red/Near-Infrared Solid Fluorophores: Aggregation-Induced Emission, Intramolecular Charge Transfer, Twisted Molecular Conformation, and Bioimaging Applications

      Dr. Hongguang Lu, Yadan Zheng, Dr. Xiaowei Zhao, Dr. Lijuan Wang, Suqian Ma, Xiongqi Han, Dr. Bin Xu, Prof. Wenjing Tian and Prof. Hui Gao

      Article first published online: 18 NOV 2015 | DOI: 10.1002/anie.201507031

      Thumbnail image of graphical abstract

      Twisted emissions: Fluorophores with aggregation-induced emission (AIE) in the solid state are reported. The emissions range from the orange to far red/near-infrared (FR/NIR) regions, and the molecules have twisted molecular conformations. The bioimaging performance of the designed fluorophores shows that they have potential as FR/NIR fluorescent probes for biological applications.

    11. Alkyne Cross-Coupling

      Stereocontrolled Synthesis of Vinyl Boronates and Vinyl Silanes via Atom-Economical Ruthenium-Catalyzed Alkene–Alkyne Coupling

      Prof. Dr. Barry M. Trost, Dr. Dennis C. Koester and Alastair N. Herron

      Article first published online: 17 NOV 2015 | DOI: 10.1002/anie.201509238

      Thumbnail image of graphical abstract

      Selectivity at will: A Ru-catalyzed alkene–alkyne coupling reaction of allyl boronates with various alkynes is reported. The double bond geometry in the generated vinyl boranes can be remotely controlled by the juxtaposing boron and silicon groups on the alkyne substrate. The synthetic utility of the coupling products has been demonstrated in a variety of synthetic transformations.

    12. Electrochemistry | Hot Paper

      The Electrochemical Characterization of Single Core–Shell Nanoparticles

      Lucy R. Holt, Dr. Blake J. Plowman, Dr. Neil P. Young, Dr. Kristina Tschulik and Prof. Richard G. Compton

      Article first published online: 17 NOV 2015 | DOI: 10.1002/anie.201509008

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      Getting to the core of the matter: The electrochemical characterization of core–shell nanoparticles is demonstrated, providing a quantitative approach to measure the core and shell dimensions on an individual nanoparticle basis. Excellent agreement was obtained between this method and electron microscopy analysis, establishing this as a powerful characterization tool for core–shell nanoparticles.

    13. C[BOND]H Activation

      Catalytic Electrophilic C[BOND]H Silylation of Pyridines Enabled by Temporary Dearomatization

      Simon Wübbolt and Prof. Dr. Martin Oestreich

      Article first published online: 17 NOV 2015 | DOI: 10.1002/anie.201508181

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      Breaking the Law: Reversible 1,4-hydrosilylation of substituted pyridines was used to break and reestablish its aromaticity. The intermediate 1,4-dihydropyridine reacts as an enamine with a catalytically generated silicon electrophile, followed by deprotonation. The whole sequence is promoted by a single catalyst. This strategy addresses the C[BOND]H bond at C5 of the electron-deficient arene rather than the C[BOND]H bond in proximity to the nitrogen donor.

    14. Natural Products

      Enantioselective Total Synthesis of (−)-Martinellic Acid

      Mukesh Pappoppula and Prof. Aaron Aponick

      Article first published online: 17 NOV 2015 | DOI: 10.1002/anie.201507849

      Thumbnail image of graphical abstract

      Short and sweet: An enantioselective synthesis of the natural product martinellic acid is reported. The synthesis employs a Cu-catalyzed alkyne addition to a substituted quinoline and requires the use of the axially chiral imidazole-based biaryl ligand StackPhos, and is the most concise enantioselective total synthesis of martinellic acid reported to date. Cbz=benzyloxycarbonyl.

    15. Biomolecular Delivery

      A High-Throughput Platform for Formulating and Screening Multifunctional Nanoparticles Capable of Simultaneous Delivery of Genes and Transcription Factors

      Prof. Yang Liu, Juanjuan Du, Dr. Jin-sil Choi, Dr. Kuan-Ju Chen, Dr. Shuang Hou, Ming Yan, Prof. Wei-Yu Lin, Kevin Sean Chen, Tracy Ro, Prof. Gerald S. Lipshutz, Prof. Lily Wu, Prof. Linqi Shi, Prof. Yunfeng Lu, Prof. Hsian-Rong Tseng and Prof. Hao Wang

      Article first published online: 17 NOV 2015 | DOI: 10.1002/anie.201507546

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      Special delivery: Integration of microfluidic systems with a supramolecular synthetic strategy results in a high-throughput approach to formulating and screening multifunctional supramolecular nanoparticles (see figure). The nanoparticles are self-assembled from a collection of functional modules (proteins, genes, ligands, and a scaffold) and can simultaneously deliver both a gene and transcription factor either in vitro or in vivo.

    16. Conducting Textile

      Semiconducting Fabrics by In Situ Topochemical Synthesis of Polydiacetylene: A New Dimension to the Use of Organogels

      Baiju P. Krishnan, Dr. Somnath Mukherjee, Dr. Pacheri M. Aneesh, Dr. Manoj A. G. Namboothiry and Prof. Dr. Kana M. Sureshan

      Article first published online: 17 NOV 2015 | DOI: 10.1002/anie.201507475

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      A diyne-functionalized sugar gelator was synthesized that, upon self-assembly, preorganizes the diyne motifs for photochemical polymerization to polydiacetylene. This was exploited to make semiconducting fabrics by in situ polymerization to PDA. While the diyne motif forms the conducting PDA, the carbohydrate motif anchors the monomer, and thus the polymer, to the fabric through hydrogen bonds.

    17. Surface Chemistry | Very Important Paper

      Covalently Attached Liquids: Instant Omniphobic Surfaces with Unprecedented Repellency

      Dr. Liming Wang and Prof. Dr. Thomas J. McCarthy

      Article first published online: 16 NOV 2015 | DOI: 10.1002/anie.201509385

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      Omniphobic surfaces that are stable under pressure and durable at elevated temperatures were obtained by acid-catalyzed graft polycondensation of dimethyldimethoxysilane. The slippery omniphobic covalently attached liquid (SOCAL) surfaces show extremely low contact angle hysteresis (≤1°) and low sliding angles for liquids with surface tensions from 78.2 to 18.4 mN m−1.

    18. Bioorthogonal Chemistry | Very Important Paper

      A Bioorthogonal Reaction of N-Oxide and Boron Reagents

      Dr. Justin Kim and Prof. Carolyn R. Bertozzi

      Article first published online: 16 NOV 2015 | DOI: 10.1002/anie.201508861

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      The bond-cleaving reaction between N-oxide and diboron reagents features second-order rate constants as high as 2.3×103M−1 s−1. Diboron reagents display minimal cell toxicity at millimolar concentrations, penetrate cell membranes, and reduce N-oxides inside mammalian cells. This new bioorthogonal reaction is thus well-suited for chemically activating molecules within cells.

    19. Receptor Signaling

      Identification of a Conformational Equilibrium That Determines the Efficacy and Functional Selectivity of the μ-Opioid Receptor

      Dr. Junya Okude, Dr. Takumi Ueda, Dr. Yutaka Kofuku, Motohiko Sato, Naoyuki Nobuyama, Keita Kondo, Yutaro Shiraishi, Takuya Mizumura, Kento Onishi, Mei Natsume, Dr. Masahiro Maeda, Dr. Hideki Tsujishita, Dr. Takefumi Kuranaga, Prof. Dr. Masayuki Inoue and Prof. Dr. Ichio Shimada

      Article first published online: 16 NOV 2015 | DOI: 10.1002/anie.201508794

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      An open and closed case: NMR analysis of different ligand-bound states of the μ-opioid receptor revealed that the intracellular cavity of the receptor exists in an equilibrium between closed and multiple open conformations, and that the population of each open conformation determines the G-protein- and β-arrestin-mediated signaling levels (see picture). These findings provide structural insight into the biased signaling of G-protein-coupled receptors.

    20. Oxygen Reduction Reaction

      Conductivity-Dependent Completion of Oxygen Reduction on Oxide Catalysts

      Dong-Gyu Lee, Ohhun Gwon, Han-Saem Park, Su Hwan Kim, Juchan Yang, Prof. Sang Kyu Kwak, Prof. Guntae Kim and Prof. Hyun-Kon Song

      Article first published online: 16 NOV 2015 | DOI: 10.1002/anie.201508129

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      Conductivity makes the difference: Conductive environments surrounding active sites, achieved by more conductive perovskite catalysts (BSCFO, NBSCO) or higher carbon contents, result in a higher number of electrons transferred during complete four-electron (4e) reduction of oxygen, changing the rate-determining step from a two-step 2e process to a single-step 1e process.

    21. Metal–Support Interactions

      Stabilization of Palladium Nanoparticles on Nanodiamond–Graphene Core–Shell Supports for CO Oxidation

      Liyun Zhang, Dr. Hongyang Liu, Dr. Xing Huang, Xueping Sun, Prof. Zheng Jiang, Prof. Robert Schlögl and Prof. Dangsheng Su

      Article first published online: 16 NOV 2015 | DOI: 10.1002/anie.201507821

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      A core–shell material with a nanodiamond core and a defective graphene shell (ND@G) was fabricated and used as a support for palladium nanoparticles (Pd/NG@G). Owing to strong metal–support interactions, Pd/ND@G is a more efficient catalyst of CO oxidation than palladium nanoparticles supported on onion-like carbon (OLC).

    22. Polyketides

      Stereochemical Studies of the Karlotoxin Class Using NMR Spectroscopy and DP4 Chemical-Shift Analysis: Insights into their Mechanism of Action

      Dr. Amanda L. Waters, Dr. Joonseok Oh, Prof. Allen R. Place and Prof. Mark T. Hamann

      Article first published online: 16 NOV 2015 | DOI: 10.1002/anie.201507418

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      In bloom: Harmful algal bloom toxins derived from the dinoflagellate Karlodinium sp. produce an interesting suite of complex polyketides which have been shown to have hemolytic, cytotoxic and ichthyotoxic activity. Better understanding the mechanism of action for this class of compounds could lead to the development of new agents for targeting cancer-cell membranes.

    23. Macrocycles

      The Synthesis of Structurally Diverse Macrocycles By Successive Ring Expansion

      Christiana Kitsiou, Jordan J. Hindes, Phillip I'Anson, Paula Jackson, Thomas C. Wilson, Eleanor K. Daly, Hannah R. Felstead, Peter Hearnshaw and Dr. William P. Unsworth

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201509153

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      Expanding the family: Macrocycles can be generated using a telescoped acylation/ring-expansion sequence, leading to the insertion of linear fragments into cyclic β-ketoesters without performing a discrete macrocyclization step. The β-ketoester motif is regenerated in the ring-expanded product, therefore the same sequence of steps can be repeated, allowing macrocycles with precise substitution patterns to be “grown” from smaller rings.

    24. Boration

      Synthesis of 1,1-Diborylalkenes through a Brønsted Base Catalyzed Reaction between Terminal Alkynes and Bis(pinacolato)diboron

      Akira Morinaga, Kazunori Nagao, Prof. Dr. Hirohisa Ohmiya and Prof. Dr. Masaya Sawamura

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201509218

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      Put a B on it: A method for the synthesis of 1,1-diborylalkenes through a Brønsted base catalyzed reaction between terminal alkynes and bis(pinacolato)diboron has been developed. The procedure allows direct synthesis of functionalized 1,1-diborylalkenes from various terminal alkynes including propiolates, propiolamides, and 2-ethynylazoles.

    25. Surface Patterning

      Corrosion-Mediated Self-Assembly (CMSA): Direct Writing Towards Sculpturing of 3D Tunable Functional Nanostructures

      Dr. Jing Wang and Prof. Dr. Ghim Wei Ho

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201509356

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      Brass was sculptured into 3D functional nanocomposites by a direct-writing technique induced by corrosion-mediated self-assembly. The resulting nanocomposite served as an effective photocatalyst for enhanced hydrogen generation and organic dye degradation.

    26. Homogeneous Catalysis

      Zinc-Catalyzed Dehydrogenative Cross-Coupling of Terminal Alkynes with Aldehydes: Access to Ynones

      Shan Tang, Li Zeng, Yichang Liu and Prof. Aiwen Lei

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201509042

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      Cross paths: The title reaction for C(sp2)[BOND]H/C(sp)[BOND]H cross-coupling of terminal alkynes with aldehydes was developed. It provides a simple way to access ynones from readily available materials under mild reaction conditions. Notably, a good reaction selectivity and efficiency could be achieved with a 1:1 ratio of terminal alkyne and aldehyde.

    27. Homogeneous Catalysis | Very Important Paper

      Insertion Homo- and Copolymerization of Diallyl Ether

      Dr. Zhongbao Jian and Prof. Dr. Stefan Mecking

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201508930

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      Di-allyl versus mono-allyl monomer: Diallyl ether as a monomer allows for an unprecedented incorporation (20 mol %) and enhanced activity of an allyl monomer in insertion copolymerizations. Even homopolymerization of diallyl ether is possible, thereby yielding poly(diallyl ether) with degrees of polymerization of DPn≈44, which has previously been difficult for allyl monomers by any polymerization mechanism.

    28. Peptide Structure

      Resonance Energy Transfer Relates the Gas-Phase Structure and Pharmacological Activity of Opioid Peptides

      Vladimir Kopysov and Dr. Oleg V. Boyarkin

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201508915

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      The FRET of pain: Resonance energy transfer, detected by a combination of cold ion spectroscopy and mass spectrometry, is used to estimate the Tyr–Phe spacing for enkephalins in the gas phase. These distances appear to differ substantially in enkephalins (pain-relief drugs) with different pharmacological efficiencies.

    29. Glycoconjugates | Very Important Paper

      Glycocalyx Engineering with a Recycling Glycopolymer that Increases Cell Survival In Vivo

      Elliot C. Woods, Nathan A. Yee, Jeff Shen and Prof. Carolyn R. Bertozzi

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201508783

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      Keepin’ it sweet! A panel of glycopolymers bearing a variety of lipids were used to identify constructs that persist on cell membranes. Cholesterylamine-anchored glycopolymers are internalized but recycle to allow for the continuous display of cell-surface glycopolymers for ten days. Furthermore, these mimetics enhance the survival of nonmalignant cells in a zebrafish model of metastasis.

    30. Metalloregulatory Proteins

      Specificity of the Metalloregulator CueR for Monovalent Metal Ions: Possible Functional Role of a Coordinated Thiol?

      Dániel Szunyogh, Hajnalka Szokolai, Prof. Peter W. Thulstrup, Prof. Flemming H. Larsen, Prof. Béla Gyurcsik, Dr. Niels Johan Christensen, Dr. Monika Stachura, Prof. Lars Hemmingsen and Prof. Attila Jancsó

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201508555

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      What a difference an H makes: Investigations of AgI, ZnII, and HgII binding to model systems suggest that the selectivity of CueR proteins for monovalent metal ions and their allosteric mechanism may be controlled by the protonation of a coordinating cysteine residue. Quantum chemically optimized structures of the CueR metal site with Cys 112 protonated show that the Ser 77 backbone carbonyl oxygen atom is “pulled” towards the metal site (see picture).

    31. Phosphorylation

      Diastereoselective Synthesis of Glycosyl Phosphates by Using a Phosphorylase–Phosphatase Combination Catalyst

      Dr. Patricia Wildberger, Martin Pfeiffer, Prof. Dr. Lothar Brecker and Prof. Dr. Bernd Nidetzky

      Article first published online: 13 NOV 2015 | DOI: 10.1002/anie.201507710

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      Clever combination: Phosphatase-catalyzed diastereoselective synthesis of various glycosyl phosphates from unprotected aldose substrates was achieved, with α-D-glucose 1-phosphate, derived from the phosphorylase-catalyzed conversion of sucrose and inorganic phosphate, as the phosphoryl donor. Simultaneous and sequential two-step transformations by the phosphorylase–phosphatase combination catalyst gave α-D-/β-L-aldose 1-phosphates in up to 70 % yield.