Angewandte Chemie International Edition

Cover image for Vol. 56 Issue 10

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, ChemPhotoChem, ChemPlusChem, Zeitschrift für Chemie

  1. Communications

    1. Water-Based NMR Spectroscopy

      Heteronuclear 1D and 2D NMR Resonances Detected by Chemical Exchange Saturation Transfer to Water

      Ricardo P. Martinho, Mihajlo Novakovic, Dr. Gregory L. Olsen and Prof. Dr. Lucio Frydman

      Version of Record online: 27 FEB 2017 | DOI: 10.1002/anie.201611733

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      NMR resonances from heteronuclei can be detected through the modulation that they impose on a strong H2O resonance (shown in red) by combining a 2D heteronuclear NMR sequence with a 2D NMR approach relying on chemical exchange saturation transfer principles (HetFLEX). 1D 15N and 2D 1H/15N NMR spectra of small molecules and peptides can be recorded with substantial amplification.

    2. Gas-Phase Reactions | Very Important Paper

      Formation of Gas-Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions

      Li-Xue Jiang, Chongyang Zhao, Dr. Xiao-Na Li, Prof. Hui Chen and Prof. Sheng-Gui He

      Version of Record online: 27 FEB 2017 | DOI: 10.1002/anie.201611483

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      The formate anion, HCO2, was identified in the reaction of CO2 with the metal hydride FeH. The FeH anions were produced by laser ablation, and the reaction with CO2 was analyzed by mass spectrometry and quantum-chemical calculations. The formation of gas-phase HCO2 was predicted to proceed by facile hydride transfer.

    3. Small-Molecule Activation | Hot Paper

      An Intramolecular Silylene Borane Capable of Facile Activation of Small Molecules, Including Metal-Free Dehydrogenation of Water

      Dr. Zhenbo Mo, Dr. Tibor Szilvási, Yu-Peng Zhou, Dr. Shenglai Yao and Prof. Dr. Matthias Driess

      Version of Record online: 27 FEB 2017 | DOI: 10.1002/anie.201700625

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      A single for two: The first single-component N-heterocyclic silylene borane activates a variety of small molecules, such as O2, N2O, CO2, H2, and H2O. Notably, the activation of H2O by 1 makes it a metal-free system for dehydrogenation of H2O.

    4. Methane Activation | Hot Paper

      Catalytic Reaction Rates Controlled by Metal Oxidation State: C−H Bond Cleavage in Methane over Nickel-Based Catalysts

      Dr. Fanglin Che, Dr. Su Ha and Dr. Jean-Sabin McEwen

      Version of Record online: 27 FEB 2017 | DOI: 10.1002/anie.201611796

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      A bottom-up fundamental study demonstrates that the catalytic activity of the first C−H bond cleavage in methane is controlled by the local oxidation state of nickel. Increasing positive field strength (A) or inclusion of low concentrations of interfacial carbon species (B) leads to a partial positive charge in the nickel cluster, which can accelerate C−H cleavage.

    5. Organocatalysis

      Enantioselective Reactions of 2-Sulfonylalkyl Phenols with Allenic Esters: Dynamic Kinetic Resolution and [4+2] Cycloaddition Involving ortho-Quinone Methide Intermediates

      Ping Chen, Kai Wang, Wengang Guo, Xianghui Liu, Prof. Yan Liu and Prof. Can Li

      Version of Record online: 27 FEB 2017 | DOI: 10.1002/anie.201700250

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      Resolutely following the chosen path: 2-Sulfonylalkyl phenols were transformed into chiral benzylic sulfones with Et3N and a cinchonine-derived catalyst I by dynamic kinetic resolution (DKR) via an ortho-quinone methide (o-QM; see scheme). In contrast, 2-(tosylmethyl)sesamols and -naphthols, which form stable o-QMs, underwent formal [4+2] cycloaddition under similar conditions with another cinchona alkaloid catalyst II to give 4-substituted chromans.

    6. Catalytic Enantioselective γ-Selective Additions of 2-Allylazaarenes to Activated Ketones

      Xiangbin Bai, Guangkuo Zeng, Tianju Shao and Prof. Dr. Zhiyong Jiang

      Version of Record online: 27 FEB 2017 | DOI: 10.1002/anie.201700190

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      Remote functionalization: The excellent γ-selectivity of 2-allylazaarenes was realized in allylation reactions with activated ketones, including isatins and trifluoromethyl ketones. In the presence of either an amino-acid-based tertiary amine or quaternary ammonium salt, two series of tertiary hydroxy-containing moieties were successfully introduced at the remote δ-position of azaarenes.

    7. Nanosheets

      Photofunctionality in Porphyrin-Hybridized Bis(dipyrrinato)zinc(II) Complex Micro- and Nanosheets

      Dr. Ryota Sakamoto, Toshiki Yagi, Ken Hoshiko, Dr. Shinpei Kusaka, Ryota Matsuoka, Dr. Hiroaki Maeda, Dr. Zheng Liu, Dr. Qian Liu, Prof. Dr. Wai-Yeung Wong and Dr. Hiroshi Nishihara

      Version of Record online: 27 FEB 2017 | DOI: 10.1002/anie.201611785

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      Sheet lighting: A liquid/liquid interfacial synthesis gives bis(dipyrrinato)zinc(II) complex micro- or nanosheets containing porphyrin. The nanosheet deposited on a SnO2 electrode functions as a photoanode. The photoresponse covers the whole visible wavelength range (400–650 nm), with a maximum quantum efficiency greater than that of the nanosheet without porphyrin.

    8. Peptide Cyclization | Hot Paper

      Precisely Regulated and Efficient Locking of Linear Peptides into Stable Multicyclic Topologies through a One-Pot Reaction

      Weidong Liu, Yiwu Zheng, Dr. Xudong Kong, Prof. Christian Heinis, Prof. Yibing Zhao and Prof. Chuanliu Wu

      Version of Record online: 27 FEB 2017 | DOI: 10.1002/anie.201610942

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      Bioactive tricyclic peptide ligands: A small phenyl molecule with four isosteric thiolate-reactive groups of varied reactivity was discovered. This molecule was used in combination with cysteine/penicillamine thiolate groups of different nucleophilic reactivity for precisely regulated and efficient locking of a linear peptide into multicyclic topologies through a one-pot reaction.

  2. Cover Pictures

    1. You have free access to this content
      Facile Synthesis of Polycyclic Pentalenes with Enhanced Hückel Antiaromaticity

      Hiroya Oshima, Prof. Dr. Aiko Fukazawa and Prof. Dr. Shigehiro Yamaguchi

      Version of Record online: 24 FEB 2017 | DOI: 10.1002/anie.201701354

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      Pentalene with eight π-electrons shows pronounced antiaromaticity, which gets lost, however, when the scaffold is stabilized by fused benzene rings. In their Communication (DOI: 10.1002/anie.201611344), A. Fukazawa, S. Yamaguchi, and H. Oshima report a strategy for restoring the lost antiaromaticity in dibenzo[a,e]pentalene: Fusion with four highly aromatic rings at the peripheral positions gives rise to enhanced antiaromaticity.

  3. Communications

    1. Iron Cluster Catalysis

      Alkene Hydrogenations by Soluble Iron Nanocluster Catalysts

      Dr. Tim N. Gieshoff, Dr. Uttam Chakraborty, Matteo Villa and Prof. Dr. Axel Jacobi von Wangelin

      Version of Record online: 24 FEB 2017 | DOI: 10.1002/anie.201612548

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      An iron-catalyzed hydrogenation has been developed based on the simple ternary catalyst system Fe[N(SiMe3)2]2/iBu2AlH. Clean hydrogenations of challenging alkenes proceeded under very mild conditions (1–4 bar H2, 20 °C). The simple mixing of the ferrous salt, reductant, and ligand is particularly user-friendly. Isolation of soluble Fe nanoclusters provides insight into reductive catalyst formation and nanoparticle aggregation.

    2. Nanophotonics

      Lattice-Matched Epitaxial Growth of Organic Heterostructures for Integrated Optoelectronic Application

      Dr. Yi Zhang, Prof. Qing Liao, Xinguo Wang, Prof. Jiannian Yao and Prof. Hongbing Fu

      Version of Record online: 24 FEB 2017 | DOI: 10.1002/anie.201700447

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      An organic laser: Lattice-matched epitaxial growth is employed in the preparetion of branched nanowire heterostructures. A microribbon backbone of BBOT (2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene) functions as blue-emitting microlaser source to pump the nanowire branches of BODIPY.

    3. Homogeneous Catalysis

      Palladium-Catalyzed Pyrazole-Directed sp3 C−H Bond Arylation for the Synthesis of β-Phenethylamines

      Dr. Nurbey Gulia and Prof. Olafs Daugulis

      Version of Record online: 24 FEB 2017 | DOI: 10.1002/anie.201611407

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      Palladium-catalyzed, pyrazole-directed sp3 C−H bond arylation by aryl iodides is reported. The reaction employs a Pd(OAc)2 catalyst and silver(I) oxide as a halide-removal agent and base precursor, and it proceeds in either acetic acid or acetic acid/hexafluoroisopropanol solvent. Ozonolysis of the pyrazole moiety affords pharmaceutically important β-phenethylamines.

    4. Cyanides | Very Important Paper

      Iridium-Catalyzed Reductive Strecker Reaction for Late-Stage Amide and Lactam Cyanation

      Dr. Ángel L. Fuentes de Arriba, Elena Lenci, Dr. Mahendra Sonawane, Odilon Formery and Prof. Dr. Darren J. Dixon

      Version of Record online: 24 FEB 2017 | DOI: 10.1002/anie.201612367

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      Magic nitrile! A highly chemoselective iridium-catalyzed reductive Strecker reaction of tertiary amides and lactams has been developed. The protocol is simple to perform, broad in scope, highly efficient, and has been successfully applied to the late-stage functionalization of tertiary amides in drugs, naturally occurring alkaloids and peptides. TMDS=tetramethyldisiloxane, TMS=trimethylsilyl, Vaska's complex=IrCl(CO)[P(C6H5)3]2.

  4. Corrigenda

    1. You have free access to this content
      Corrigendum: Spectroscopic Capture and Reactivity of a Low-Spin Cobalt(IV)-Oxo Complex Stabilized by Binding Redox-Inactive Metal Ions

      Seungwoo Hong, Florian F. Pfaff, Eunji Kwon, Yong Wang, Mi-Sook Seo, Eckhard Bill, Dr. Kallol Ray and Prof. Dr. Wonwoo Nam

      Version of Record online: 24 FEB 2017 | DOI: 10.1002/anie.201701623

      This article corrects:
  5. Communications

    1. Energetic Materials

      Azido and Tetrazolo 1,2,4,5-Tetrazine N-Oxides

      Dr. David E. Chavez, Dr. Damon A. Parrish, Dr. Lauren Mitchell and Dr. Greg H. Imler

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201612496

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      The oxidation products of 3,6-diazido-1,2,4,5-tetrazine (1) and 6-amino-[1,5-b]tetrazolo-1,2,4,5-tetrazine (2) have been characterized. 3,6-Diazido-1,2,4,5-tetrazine-1,4-dioxide (see picture) was produced by oxidation of 1 with peroxytrifluoroacetic acid, and more effectively using hypofluorous acid, and 2 can be oxidized to its mono- and di-N-oxide. These products display promising performance as energetic materials.

  6. Minireviews

    1. Bioisosteres

      Sulfonimidamides in Medicinal and Agricultural Chemistry

      Dr. Praveen K. Chinthakindi, Dr. Tricia Naicker, Dr. Niranjan Thota, Prof. Thavendran Govender, Prof. Hendrik G. Kruger and Prof. Dr. Per I. Arvidsson

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201610456

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      Gaining momentum: Sulfonimidamides are receiving increasing attention as bioisosteres of sulfonamides and as an important functional group in the design of pharmacologically active compounds. In this Minireview, medicinal and agricultural applications of this pharmacophore are summarized and discussed.

  7. Communications

    1. Metal-Free C−C Coupling

      Brønsted Acid-Catalyzed Oxygenative Bimolecular Friedel–Crafts-type Coupling of Ynamides

      Dilip V. Patil, Seung Woo Kim, Quynh H. Nguyen, Hanbyul Kim, Dr. Shan Wang, Tuan Hoang and Prof. Dr. Seunghoon Shin

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201612471

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      A synthetic surrogate of α-oxo carbene is accessed by Brønsted acid-catalysis of ynamides. Keteniminium ions generated by the protonation of ynamides are chemoselectively attacked by pyridine-N-oxides and form potent electrophiles for Friedel–Crafts-type SN2′ addition of nucleophiles. This metal-free approach is milder (room temperature) than related transition-metal-catalyzed processes.

    2. Metallacycles

      Hydroxy-Directed Ruthenium-Catalyzed Alkene/Alkyne Coupling: Increased Scope, Stereochemical Implications, and Mechanistic Rationale

      Dr. Stephan M. Rummelt, Dr. Gui-Juan Cheng, Dr. Puneet Gupta, Prof. Walter Thiel and Prof. Alois Fürstner

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201700342

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      Peripheral but quintessential: The ability of hydroxy groups to engage in interligand hydrogen bonding with the polarized [Ru-Cl] unit of a catalyst powers highly regioselective alkene/alkyne coupling reactions. Stereochemical information is relayed from the propargylic site to the nascent C−C-bond through chiral-at-metal ruthenium intermediates.

    3. Natural Product Synthesis

      Asymmetric Total Syntheses of Kopsia Indole Alkaloids

      Lingying Leng, Xiaohan Zhou, Qi Liao, Falu Wang, Dr. Hao Song, Dr. Dan Zhang, Dr. Xiao-Yu Liu and Prof. Yong Qin

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201700831

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      Targeting the core: Asymmetric total syntheses of a group of structurally complex Kopsia alkaloids have been achieved by employing a unified synthetic strategy. Key to the success was an intramolecular cyclopropanation, a SmI2-promoted acyloin condensation, as well as a radical-based rearrangement process.

    4. Heterogeneous Catalysis

      Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes

      Elena Pérez-Gallent, Dr. Marta C. Figueiredo, Dr. Federico Calle-Vallejo and Prof. Marc T. M. Koper

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201700580

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      Solid support: FTIR spectroscopy provides evidence for the formation of a hydrogenated CO dimer intermediate during CO reduction on Cu(100) electrodes. This confirms the widely accepted yet experimentally unproven hypothesis of a C−C coupling at the early stages of the CO reduction mechanism. The reductive dimerization step is structure sensitive and favored by sites with square symmetry.

    5. Olefin Functionalization

      Iron-Catalyzed Decarboxylative Alkyl Etherification of Vinylarenes with Aliphatic Acids as the Alkyl Source

      Wujun Jian, Liang Ge, Yihang Jiao, Bo Qian and Prof. Dr. Hongli Bao

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201612365

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      Introducing peroxides: Alkyl diacyl peroxides and peresters generated from aliphatic acids enable the first iron-catalyzed alkyl etherification of olefins with general alkyl groups. Primary, secondary and tertiary aliphatic acids as well as primary and secondary alcohols are suitable for this reaction.

    6. Asymmetric Synthesis | Hot Paper

      Dual Nickel- and Photoredox-Catalyzed Enantioselective Desymmetrization of Cyclic meso-Anhydrides

      Erin E. Stache, Prof. Tomislav Rovis and Prof. Abigail G. Doyle

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201700097

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      Catalytic teamwork: Cyclic anhydrides are efficiently desymmetrized through dual nickel- and photoredox-catalyzed alkylation using benzylic trifluoroborates salts as pronucleophiles. A mechanistic nuance illustrates that an intermediate in the catalytic cycle undergoes epimerization leading to trans keto-acid products from cis anhydrides under modified reaction conditions.

  8. News

    1. Pittcon 2017 Award Winners

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201701395

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  9. Communications

    1. CO2 Reduction | Hot Paper

      Reduced SnO2 Porous Nanowires with a High Density of Grain Boundaries as Catalysts for Efficient Electrochemical CO2-into-HCOOH Conversion

      Bijandra Kumar, Veerendra Atla, J. Patrick Brian, Sudesh Kumari, Tu Quang Nguyen, Mahendra Sunkara and Dr. Joshua M. Spurgeon

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201612194

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      Against the grain: An electrochemically reduced SnO2 porous nanowire catalyst (Sn-pNWs) with a high density of grain boundaries (GBs) has an energy conversion efficiency for CO2-into-HCOOH that is higher than analogous catalysts of reduced SnO2-based materials. The high density of GBs within the porous structure is decisive.

    2. Single-Molecule Electrochemistry

      Gold Nanorod-Enhanced Fluorescence Enables Single-Molecule Electrochemistry of Methylene Blue

      M.Sc. Weichun Zhang, Dr. Martín Caldarola, M.Sc. Biswajit Pradhan and Prof. Dr. Michel Orrit

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201612389

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      Electric light orchestrated: The low fluorescence quantum yield of the redox-sensitive dye Methylene Blue (MB) can be overcome by using individual gold nanorods. The resulting enhanced fluorescence allows electrochemical measurements with fluorescent readout to be carried out at the single-molecule level. The mid-point potential of each single molecule can be determined through its redox-induced fluorescence blinking dynamics.

    3. Superbases | Hot Paper

      A Phosphorus Bisylide: Exploring a New Class of Superbases with Two Interacting Carbon Atoms as Basicity Centers

      Dr. Julius F. Kögel, Dr. Davor Margetić, Dr. Xiulan Xie, Dr. Lars H. Finger and Prof. Dr. Jörg Sundermeyer

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201612446

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      Ping-pong with protons: The first superbase with two interacting P-ylide entities lets a proton bounce between two carbon atoms and exhibits a remarkable proton affinity with an experimental pKBH+ value of 33.3±0.2 on the MeCN scale. The high basicity arises from the rapid exchange of the “acidic” proton between the two basic carbon atoms after protonation.

    4. F⋅⋅⋅F Interactions

      A Direct Link from the Gas to the Condensed Phase: A Rotational Spectroscopic Study of 2,2,2-Trifluoroethanol Trimers

      Dr. Javix Thomas, Dr. Nathan A. Seifert, Prof. Dr. Wolfgang Jäger and Prof. Dr. Yunjie Xu

      Version of Record online: 23 FEB 2017 | DOI: 10.1002/anie.201612161

      Thumbnail image of graphical abstract

      Staying in contact: How trans-2,2,2-trifluoroethanol (TFE) becomes a significant conformation in the liquid phase while it is unstable in the isolated gas phase is a much-debated topic. The experimental detection of a TFE trimer containing one trans-TFE subunit shows that the attractive C−F⋅⋅⋅F−C contact interactions play a key role in preferential stabilization of trans versus gauche-TFE in the trimer.

    5. Synthetic Methods | Very Important Paper

      Two-Phase Reactions in Microdroplets without the Use of Phase-Transfer Catalysts

      Dr. Xin Yan, Dr. Heyong Cheng and Prof. Richard N. Zare

      Version of Record online: 22 FEB 2017 | DOI: 10.1002/anie.201612308

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      It's all about the interface: Biphasic reactions are carried out in microdroplets without using a phase-transfer catalyst. Reactions occur within milliseconds in moderate to good yields.

    6. Host–Guest Interactions

      A Polyaromatic Molecular Clip That Enables the Binding of Planar, Tubular, and Dendritic Compounds

      Keisuke Jono, Dr. Akira Suzuki, Prof. Dr. Munetaka Akita, Dr. Ken Albrecht, Prof. Dr. Kimihisa Yamamoto and Dr. Michito Yoshizawa

      Version of Record online: 22 FEB 2017 | DOI: 10.1002/anie.201612489

      Thumbnail image of graphical abstract

      Guests of all shapes and sizes welcome: A molecular clip with a C-shaped conformation was synthesized by the covalent linkage of two bent bisanthracene amphiphiles with a biphenyl spacer bearing hydrophilic pendants (see structure). The acyclic, open cavity of the polyaromatic clip captures not only planar pigments and cylindrical single-walled carbon nanotubes but also highly branched macromolecules (dendrimers) in water.

    7. Medicinal Chemistry

      An Irreversible Inhibitor of HSP72 that Unexpectedly Targets Lysine-56

      Jonathan Pettinger, Dr. Yann-Vaï Le Bihan, Marcella Widya, Dr. Rob L. M. van Montfort, Prof. Keith Jones and Dr. Matthew D. Cheeseman

      Version of Record online: 22 FEB 2017 | DOI: 10.1002/anie.201611907

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      Simply irreversible: The stress-inducible molecular chaperone, HSP72, is an important target in oncology but few validated inhibitors have emerged. To overcome the high affinity and abundance of its endogenous substrates, an irreversible nucleotide-competitive inhibitor, which unexpectedly targeted lysine-56, was discovered by rational design.

    8. Solid-State NMR Spectroscopy

      Solid-State 17O NMR Reveals Hydrogen-Bonding Energetics: Not All Low-Barrier Hydrogen Bonds Are Strong

      Dr. Jiasheng Lu, Dr. Ivan Hung, Dr. Andreas Brinkmann, Dr. Zhehong Gan, Dr. Xianqi Kong and Prof. Dr. Gang Wu

      Version of Record online: 22 FEB 2017 | DOI: 10.1002/anie.201700488

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      Breaking a hydrogen bond: The enthalpy of hydrogen bond formation for the O⋅⋅⋅H⋅⋅⋅N low-barrier hydrogen bond in nicotinic acid crystals was determined experimentally. A solid-state 17O NMR approach was used to directly measure the energy required to break the low-barrier hydrogen bond.

    9. Natural Product Synthesis

      Biomimetic Total Synthesis of (±)-Verrubenzospirolactone

      Hiu C. Lam, Dr. Henry P. Pepper, Prof. Christopher J. Sumby and Dr. Jonathan H. George

      Version of Record online: 22 FEB 2017 | DOI: 10.1002/anie.201700114

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      High five: A five-step total synthesis of (±)-verrubenzospirolactone (1) has been achieved using a biomimetic, intramolecular Diels–Alder reaction of a 2H-chromene to form two rings and four stereocenters in the final step. This Diels–Alder reaction occurs spontaneously at 30 °C “on-water”, thus suggesting that it is likely to be non-enzymatic in nature.

  10. News

  11. Communications

    1. Hypervalent Compounds

      4,5-Dimethyl-2-Iodoxybenzenesulfonic Acid Catalyzed Site-Selective Oxidation of 2-Substituted Phenols to 1,2-Quinols

      Prof. Dr. Muhammet Uyanik, Tatsuya Mutsuga and Prof. Dr. Kazuaki Ishihara

      Version of Record online: 21 FEB 2017 | DOI: 10.1002/anie.201612463

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      An oxidation cocktail: A site-selective hydroxylative dearomatization of phenols to deliver either 1,2-quinols or their cyclodimers, catalyzed by 4,5-Me2IBS with Oxone, is described. Importantly, both the reaction rate and site-selectivity were improved by the introduction of a trialkylsilylmethyl substituent at the 2-position of the phenols. The corresponding 1,2-benzoquinols could be transformed into various useful structural motifs by [4+2] cycloaddition cascade reactions.

    2. Chemical Vapor Transport

      Two-Dimensional Semiconductors Grown by Chemical Vapor Transport

      Dake Hu, Dr. Guanchen Xu, Lei Xing, Dr. Xingxu Yan, Dr. Jingyi Wang, Jingying Zheng, Zhixing Lu, Prof. Peng Wang, Prof. Xiaoqing Pan and Prof. Liying Jiao

      Version of Record online: 21 FEB 2017 | DOI: 10.1002/anie.201700439

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      Layer by layer: The controllable synthesis of highly crystalline two-dimensional (2D) semiconducting atomic layers has been achieved by using an old crystal growth technique, chemical vapor transport. This approach opens a new avenue for the chemical synthesis of high-quality 2D semiconductors.

    3. NMR Spectroscopy

      Positional Enrichment by Proton Analysis (PEPA): A One-Dimensional 1H-NMR Approach for 13C Stable Isotope Tracer Studies in Metabolomics

      Dr. Maria Vinaixa, Dr. Miguel A. Rodríguez, Dr. Suvi Aivio, Jordi Capellades, Dr. Josep Gómez, Dr. Nicolau Canyellas, Dr. Travis H. Stracker and Dr. Oscar Yanes

      Version of Record online: 21 FEB 2017 | DOI: 10.1002/anie.201611347

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      PEPA is a novel technique for extending the high-throughput of 1H-1D-NMR metabolic profiling to 13C stable isotope tracing. The approach broadens the range of isotopically enriched metabolites detected in cellular extracts, thus accelerating the implementation of NMR in cell metabolism studies.

    4. Hybrid Microcontainers

      Synthesis of Dual-Stimuli-Responsive Microcontainers with Two Payloads in Different Storage Spaces for Preprogrammable Release

      Dr. Ying Cong, Dr. Qiuju Li, Prof. Min Chen and Prof. Limin Wu

      Version of Record online: 21 FEB 2017 | DOI: 10.1002/anie.201612291

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      Out of the box: Dual-responsive hybrid microcontainers with two payloads in separate storage spaces—Nile red in the mesopores of silica nanoparticles and 5(6)-carboxyfluorescein diacetate (CFDA) in the hollow core of the microcapsules—were prepared by the straightforward UV-initiated polymerization of Pickering emulsions. The release of Nile red and CFDA could be selectively activated by changing the temperature or pH value (see picture).

    5. Photoredox Catalysis

      Multicomponent Oxyalkylation of Styrenes Enabled by Hydrogen-Bond-Assisted Photoinduced Electron Transfer

      Adrian Tlahuext-Aca, R. Aleyda Garza-Sanchez and Prof. Frank Glorius

      Version of Record online: 21 FEB 2017 | DOI: 10.1002/anie.201700049

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      OH, I see: An efficient strategy to activate N-(acyloxy)phthalimides towards direct photoinduced electron transfer with photoexcited catalysts was developed. This strategy enables efficient visible-light-mediated formation of alkyl radicals that can be used to achieve the challenging oxyalkylation of styrenes under mild redox-neutral conditions.

    6. Photoanodes

      Surviving High-Temperature Calcination: ZrO2-Induced Hematite Nanotubes for Photoelectrochemical Water Oxidation

      Chengcheng Li, Ang Li, Zhibin Luo, Jijie Zhang, Xiaoxia Chang, Zhiqi Huang, Dr. Tuo Wang and Prof. Dr. Jinlong Gong

      Version of Record online: 21 FEB 2017 | DOI: 10.1002/anie.201611330

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      Survival training: Hematite nanotube arrays (Fe2O3-NTs) surviving high-temperature calcination were prepared by solid-state reaction between an FeOOH nanorod core and ZrO2 shell. Their greatly improved photoelectrochemical water oxidation performance originates from their nanostructured morphology and shortened charge collection distance (see picture; W=depletion layer width).

    7. Halogen Bonds

      Self-Assembly of Iodine in Superfluid Helium Droplets: Halogen Bonds and Nanocrystals

      Yunteng He, Jie Zhang, Lei Lei and Wei Kong

      Version of Record online: 21 FEB 2017 | DOI: 10.1002/anie.201611922

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      Atom distances in iodine dimer were revealed from electron diffraction in superfluidic helium droplets. The distance between atoms 1 and 3 is 3.65 Å, much smaller than the van der Waals distance of 4.3 Å.

  12. Cover Pictures

    1. You have free access to this content
      Catalytic Reaction Rates Controlled by Metal Oxidation State: C−H Bond Cleavage in Methane over Nickel-Based Catalysts

      Dr. Fanglin Che, Dr. Su Ha and Dr. Jean-Sabin McEwen

      Version of Record online: 20 FEB 2017 | DOI: 10.1002/anie.201701296

      Thumbnail image of graphical abstract

      Riding high on a wave of positivity: Methane C−H activation over nickel clusters is promoted by low concentrations of surface carbon, interfacial carbide species, or an increase in the local oxidation state of nickel in response to a positive electric field. In their Communication (DOI: 10.1002/anie.201611796), J.-S. McEwen, S. Ha, and F. Che deliver fundamental insights into the role of surface carbon and electric field within an electrochemical device for hydrocarbon conversion.

  13. Communications

    1. Rhodium Catalysis

      Fulvene Synthesis by Rhodium(I)-Catalyzed [2+2+1] Cycloaddition: Synthesis and Catalytic Activity of Tunable Cyclopentadienyl Rhodium(III) Complexes with Pendant Amides

      Soichi Yoshizaki, Dr. Yu Shibata and Prof. Dr. Ken Tanaka

      Version of Record online: 20 FEB 2017 | DOI: 10.1002/anie.201612590

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      A spectacular rhod(ium) show: A RhI+/segphos complex catalyzed the [2+2+1] cycloaddition of 1,6-diynes with cyclopropylideneacetamides to provide substituted fulvenes. The reductive complexation of these products with RhCl3 in EtOH furnished the corresponding dinuclear cyclopentadienyl RhIII complexes (see scheme), which were highly active catalysts for oxidative annulation and cyclization through C(sp2)−H and C(sp3)−H functionalization.

  14. Editorial

    1. You have free access to this content
      New Polymers: Beautiful Structures, But How Can We Bring Them to the Market?

      Prof. Dr. Brigitte Voit

      Version of Record online: 20 FEB 2017 | DOI: 10.1002/anie.201700811

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      “… Nobody in our academic polymer community doubts that polymers are the materials of the 21st century, and will continue to enable and drive the development of future technologies, and ensure our high standard of living and wellbeing in the context of both an aging population and the energy transformation. However, we should be aware that there is a difference between polymers and plastics …” Read more about this perspective in the Guest Editorial by Brigitte Voit.

  15. Communications

    1. Palladium Catalysts | Hot Paper

      Detection of Palladium(I) in Aerobic Oxidation Catalysis

      Jonathan N. Jaworski, Scott D. McCann, Dr. Ilia A. Guzei and Prof. Shannon S. Stahl

      Version of Record online: 20 FEB 2017 | DOI: 10.1002/anie.201700345

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      Catalyst entanglement: Catalyst dimerization is observed in both the aerobic palladium-catalyzed allylic C−H acetoxylation and aza-Wacker cyclization. A novel PdI species is rigorously characterized in catalysis which has implications for palladium catalyst design and presents insights into catalyst deactivation.

    2. Electrocatalysis | Very Important Paper

      Understanding of Strain Effect in Electrochemical Reduction of CO2: Using Pd Nanostructures as an Ideal Platform

      Dr. Hongwen Huang, Huanhuan Jia, Zhao Liu, Pengfei Gao, Jiangtao Zhao, Prof. Zhenlin Luo, Prof. Jinlong Yang and Prof. Jie Zeng

      Version of Record online: 20 FEB 2017 | DOI: 10.1002/anie.201612617

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      No strain, no gain: Pd octahedra and icosahedra with similar sizes are used as a well-defined platform to study the effect of surface strain in electrochemical reduction of CO2. The results show that tensile strain improves catalytic activity by shifting up the d-band center and thus strengthening the adsorption of key intermediate COOH*.

  16. Author Profile

    1. Authors Profile

      Version of Record online: 20 FEB 2017 | DOI: 10.1002/anie.201700715

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  17. Communications

    1. Macrocycles

      One-Pot Assembly of Amino Acid Bridged Hybrid Macromulticyclic Cages through Multiple Multicomponent Macrocyclizations

      Prof. Dr. Ludger A. Wessjohann, Dr. Oliver Kreye and Prof. Dr. Daniel G. Rivera

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201610801

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      Let's get together: A new multimacrocyclization strategy enables the one-pot multicomponent synthesis of hybrid molecular cages through reaction-based self-assembly. Dilution and metal-template-driven macrocyclization conditions proved efficient in the production of high cage complexity with low synthetic cost in a four-component reaction (4CR).

    2. Electron Donors

      A Stable Hexakis(guanidino)benzene: Realization of the Strongest Neutral Organic Four-Electron Donor

      Benjamin Eberle, Dr. Elisabeth Kaifer and Prof. Dr. Hans-Jörg Himmel

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201611189

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      Multistage electron donor: The first hexakis(guanidino)benzene derivative donates four electrons at a record low potential.

    3. Homogeneous Catalysis

      Palladium-Catalyzed Direct Stereoselective Synthesis of Deoxyglycosides from Glycals

      Dr. Abhijit Sau, Ryan Williams, Dr. Carlos Palo-Nieto, Dr. Antonio Franconetti, Dr. Sandra Medina and Dr. M. Carmen Galan

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201612071

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      Sweet dreams (are made of this): Palladium(II) in combination with a monodentate phosphine ligand enables the unprecedented direct and α-stereoselective catalytic synthesis of deoxyglycosides from glycals. Mechanistic studies suggest that in the presence of N-phenyl-2-(di-tert-butylphosphino)pyrrole, the reaction proceeds via an alkoxy palladium intermediate that increases the proton acidity and oxygen nucleophilicity of the alcohol.

    4. Thermal Conductivity

      Low-Temperature Anharmonicity in Cesium Chloride (CsCl)

      Dr. Mattia Sist, Karl Frederik Færch Fischer, Dr. Hidetaka Kasai and Prof. Bo Brummerstedt Iversen

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201700638

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      Heating system: At room temperature CsCl has a very low thermal conductivity which increases at lower temperatures. High-resolution single-crystal X-ray diffraction unexpectedly reveals an increase of anharmonicity below 100 K.

  18. Cover Pictures

    1. You have free access to this content
      Hydronium-Ion Batteries with Perylenetetracarboxylic Dianhydride Crystals as an Electrode

      Xingfeng Wang, Clement Bommier, Dr. Zelang Jian, Zhifei Li, Raghu S. Chandrabose, Ismael A. Rodríguez-Pérez, Prof. P. Alex Greaney and Prof. Xiulei Ji

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201701390

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      An acidic aqueous solution acts as an electrolyte for a hydronium-ion battery where the charge carrier is H3O+. In their Communication (DOI: 10.1002/anie.201700148), X. L. Ji et al. provide the evidence that hydronium ions can be reversibly inserted into and extracted from 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). The expansion and contraction of the PTCDA lattice correspond to H3O+ intercalation and deintercalation, respectively, as revealed by ex situ XRD studies and density functional calculations.

  19. Communications

    1. Organocatalysis

      Catalytic Asymmetric Intramolecular [4+2] Cycloaddition of In Situ Generated ortho-Quinone Methides

      Dr. Youwei Xie and Prof. Dr. Benjamin List

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201612149

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      Chromane synthesis: An organocatalytic asymmetric intramolecular [4+2] cycloaddition of in situ generated ortho-quinone methides is described. In the presence of a chiral imidophosphoric acid catalyst, various salicylaldehydes react with dienyl alcohols to afford highly functionalized furanochromanes or pyranochromanes in excellent diastereo- and enantoselectivity.

  20. Cover Pictures

    1. You have free access to this content
      Photoelectrochemical Reduction of Carbon Dioxide to Methanol through a Highly Efficient Enzyme Cascade

      Su Keun Kuk, Dr. Raushan K Singh, Dr. Dong Heon Nam, Ranjitha Singh, Prof. Dr. Jung-Kul Lee and Prof. Dr. Chan Beum Park

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201701353

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      An artificial photosynthetic platform has been created by combining a photo-electrochemical cell and a multienzyme cascade to mimic natural photosynthesis in green plants. J. K. Lee, C. B. Park, and co-workers describe in their Communication (DOI: 10.1002/anie.201611379) how the use of water as an electron donor, a hematite photoanode and a bismuth ferrite photocathode for the regeneration of NADH with visible light, as well as a three-dehydrogenase cascade system allows the highly selective and fast conversion of carbon dioxide into methanol.

    2. You have free access to this content
      Energy Transfer Dynamics of Formate Decomposition on Cu(110)

      Jiamei Quan, Prof. Takahiro Kondo, Prof. Guichang Wang and Prof. Junji Nakamura

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201701351

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      The butterfly effect: Decomposition of formate is a thermal non-equilibrium process from which a large amount of energy is released and transformed into the internal energies of CO2. In their Communication (DOI: 10.1002/anie.201611342), J. Nakamura et al. describe nascent CO2 molecules desorbing from a copper surface with vibrating “wings” analogous to translational and vibrational energies. A mountain depicted in the background represents the energetics of formate decomposition.

  21. Communications

    1. Homogeneous Catalysis | Hot Paper

      Carbonyls as Latent Alkyl Carbanions for Conjugate Additions

      Xi-Jie Dai, Dr. Haining Wang and Prof. Dr. Chao-Jun Li

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201700059

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      Hidden talents: Carbonyls can act as latent carbon nucleophiles for conjugate additions through a ruthenium-catalyzed process. The reaction relies on homogeneous ruthenium(II) catalysis combined with phosphines as spectator ligands and hydrazine as the reducing agent. This method enables the incorporation of highly functionalized alkyl fragments into a vast array of electron-deficient olefins under mild reaction conditions.

    2. Cross-Coupling

      Visible-Light-Promoted Asymmetric Cross-Dehydrogenative Coupling of Tertiary Amines to Ketones by Synergistic Multiple Catalysis

      Qi Yang, Dr. Long Zhang, Chen Ye, Prof. Dr. Sanzhong Luo, Prof. Dr. Li-Zhu Wu and Prof. Dr. Chen-Ho Tung

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201700572

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      Working together: Synergistic multiple catalytic cycles enable an asymmetric cross-dehydrogenative coupling between tertiary amines and simple ketones with high diastereo- and enantioselectivity under visible-light irradiation. This process is enabled by a simple chiral primary amine catalyst through the coupling of a catalytic enamine intermediate and an iminium cation intermediate in situ generated from tetrahydroisoquinoline derivatives by Ru/Co catalysis.

    3. Silicones

      (Aminomethyl)pyridine Complexes for the Cobalt-Catalyzed Anti-Markovnikov Hydrosilylation of Alkoxy- or Siloxy(vinyl)silanes with Alkoxy- or Siloxyhydrosilanes

      Dr. Kangsang L. Lee

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201612460

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      More than 25 siloxanes with siloxy or alkoxy functional groups at both termini are obtained in high yields using a cobalt catalyst derived from (aminomethyl)pyridine ligands and CoBr2 (see Scheme). This protocol can also be applied for the hydrosilylation of polymeric vinylsilanes by hydrosilanes to prepare silicones.

  22. Cover Pictures

    1. You have free access to this content
      Enantioselective Aza-Ene-type Reactions of Enamides with Gold Carbenes Generated from α-Diazoesters

      Feng Zhao, Nan Li, Tao Zhang, Zhi-Yong Han, Shi-Wei Luo and Prof. Dr. Liu-Zhu Gong

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201701298

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      Carbophilic gold carbenes generated by the decomposition of α-diazoesters are highly reactive towards enamides, undergoing an unprecedented aza-ene-type reaction. In their Communication (DOI: 10.1002/anie.201612208), S.-W. Luo, L.-Z. Gong, and co-workers show that the presence of 0.1 mol % of a chiral Brønsted acid is sufficient to obtain synthetically significant γ-keto esters in high yields and with excellent enantioselectivities.

  23. Communications

    1. Cascade Reactions

      Palladium-Catalyzed Oxidative Cascade Carbonylative Spirolactonization of Enallenols

      Dr. Youai Qiu, Bin Yang, Dr. Tuo Jiang, Dr. Can Zhu and Prof. Dr. Jan-E. Bäckvall

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201612384

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      All together now: A highly selective cascade reaction for C−C/C−O bond formation through palladium-catalyzed oxidative carbonylation/carbocyclization/alkoxycarbonylation of enallenols was developed, affording spirolactones bearing an all-carbon quaternary center. Preliminary attempts to obtain enantioselectivity in the carbonylative carbocyclization revealed that the VAPOL-type chiral phosphoric acid serves as a good anionic co-catalyst in this transformation.

    2. C−H Activation

      Synthesis of Active Hexafluoroisopropyl Benzoates through Hydrogen-Bond-Enabled Palladium(II)-Catalyzed C−H Alkoxycarbonylation Reaction

      Yang Wang and Prof. Vladimir Gevorgyan

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201611757

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      Let's get active: The title reaction of aryl silanes to deliver active hexafluoroisopropyl (HFIP) benzoate esters features high selectivity and good functional-group tolerance. This method yields products bearing two independently modifiable sites. NMR studies reveal the presence of hydrogen bonding between HFIP and a pyrimidine nitrogen atom of the directing group (DG), and it is thought to be crucial for the success of this alkoxycarbonylation reaction.

    3. Supramolecular Chemistry

      Supramolecularly Engineered Amphiphilic Macromolecules: Molecular Interaction Overrules Packing Parameters

      Prithankar Pramanik, Dr. Debes Ray, Dr. Vinod K. Aswal and Prof. Dr. Suhrit Ghosh

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201611715

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      Amphiphilic block-copolymers: A directional molecular interaction overrules classical packing parameters and enacts new rules for the self-assembly of supramolecularly engineered amphiphilic polymer assemblies. The self-assembly is governed by a distinct H-bonding motif of a single H-bonding moiety present in the entire polymer chain.

    4. C−C Activation

      Selective Arene Cleavage by Direct Insertion of Iridium into the Aromatic Ring

      Martin Jakoobi, Dr. Nathan Halcovitch, Dr. George F. S. Whitehead and Dr. Alexey G. Sergeev

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201611409

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      Running mild: A mild and selective insertion of a metal center into the arene ring is reported. The simple Cp*Ir fragment cleaves strong aromatic C−C bonds in alkylarenes without affecting weaker C−H and C−C bonds. This work reveals a conceptually new type of reactivity that could be important for a range of industrial processes involving the generation of chemicals and fuel from coal and plant biomass.

    5. Interfacial Reaction Dynamics | Hot Paper

      Energy Transfer Dynamics of Formate Decomposition on Cu(110)

      Jiamei Quan, Prof. Takahiro Kondo, Prof. Guichang Wang and Prof. Junji Nakamura

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201611342

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      CO2 desorption during formate decomposition in the steady-state reaction of HCOOH with O2 on Cu(110) is a thermal non-equilibrium process. During formate decomposition a large amount of released energy is transformed into the internal energies of CO2 molecules, which supports an Eley–Rideal-type mechanism for formate synthesis on copper catalysts.

  24. Minireviews

    1. Fluorescent Probes

      Modern Synthetic Avenues for the Preparation of Functional Fluorophores

      Dr. Fabio de Moliner, Dr. Nicola Kielland, Prof. Dr. Rodolfo Lavilla and Dr. Marc Vendrell

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201609394

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      Functional fluorophores enable the fast and accurate profiling of specific biomolecules but these sophisticated structures are often difficult to access through conventional synthetic strategies. Recent advances in the design, preparation, and fine-tuning of fluorophores by means of multicomponent reactions, C−H activation processes, cycloadditions, and biomolecule-based chemical transformations are discussed.

  25. Communications

    1. Natural Product Synthesis

      First Stereoselective Total Synthesis of a Dimeric Naphthoquinonopyrano-γ-lactone: (+)-γ-Actinorhodin

      Dipl.-Chem. Markus Neumeyer and Prof. Dr. Reinhard Brückner

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201611183

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      Pairs of peri MeO groups as mediators allowed seemingly distant Br or I substituents to exert regio- and diastereocontrol during naphthalene functionalization by electrophilic aromatic substitution. A bromonaphthalene-fused pyrano-γ-lactone resulted, which was dimerized in a Suzuki coupling. Removal of the methoxy groups and oxidation gave isomerically pure (+)-γ-actinorhodin in eleven steps.

  26. Essays

    1. History of Chemistry

      Michael Polanyi: Patriarch of Chemical Dynamics and Tacit Knowing

      Prof. Dr. Dudley R. Herschbach

      Version of Record online: 17 FEB 2017 | DOI: 10.1002/anie.201610968

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      Connecting Science and the Humanities was the title of the symposium on Michael Polanyi that took place at the Technische Universität Berlin (Technical University of Berlin) in October 2016. This essay, which appraises the scientific and philosophical contributions of Michael Polanyi, is based on the presentation given by Dr. Herschbach on this occasion. In the picture: Polanyi in 1931.

  27. Communications

    1. Chemoselectivity

      Determining the Origin of Rate-Independent Chemoselectivity in CuAAC Reactions: An Alkyne-Specific Shift in Rate-Determining Step

      Ciaran P. Seath, Dr. Glenn A. Burley and Dr. Allan J. B. Watson

      Version of Record online: 16 FEB 2017 | DOI: 10.1002/anie.201612288

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      The old switcheroo: A kinetic and spectroscopic analysis of alkyne-dependent chemoselectivity in the copper-catalyzed azide–alkyne click (CuAAC) reaction is reported. Studies of six alkyne subtypes reveal that the rate-determining step (RDS) of an aromatic ynamine class is shifted from acetylide formation to the azide ligation/migratory insertion event allowing chemoselectivity independent of overall rate.

    2. Nanotechnology

      Patchy Nanofibers from the Thin Film Self-Assembly of a Conjugated Diblock Copolymer

      Dr. Emily L. Kynaston, Yuan Fang, Joseph G. Manion, Nimrat K. Obhi, Dr. Jane Y. Howe, Prof. Dmitrii F. Perepichka and Prof. Dwight S. Seferos

      Version of Record online: 16 FEB 2017 | DOI: 10.1002/anie.201700134

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      Self-assembly required: Patchy nanofibers can be accessed from the self-assembly of an all-conjugated, polyselenophene-block-polythiophene copolymer. This unexpected morphology consists of sub-10 nm polythiophene- and polyselenophene-rich domains and is unprecedented for both conjugated polymers and diblock copolymers in general.

    3. PCET Reactions

      Outer-Sphere 2 e/2 H+ Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes

      Dr. Mauricio Cattaneo, Scott A. Ryken and Prof. James M. Mayer

      Version of Record online: 16 FEB 2017 | DOI: 10.1002/anie.201612642

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      2 e/2 H+ transfer reactions: Multielectron redox chemistry is central to many catalytic and energy storage processes. A variety of 2 e/2 H+ reactions are reported, with substrates that possess or form two O−H, N−H, S−H, or C−H bonds. The reactions interconvert RuII-bis(amine) and RuIV-bis(amido) complexes.

    4. Bioconjugation | Very Important Paper

      Palladium-Mediated Arylation of Lysine in Unprotected Peptides

      Dr. Hong Geun Lee, Dr. Guillaume Lautrette, Prof. Bradley L. Pentelute and Prof. Stephen L. Buchwald

      Version of Record online: 16 FEB 2017 | DOI: 10.1002/anie.201611202

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      Defenses down: In the presence of a preformed biarylphosphine-supported palladium(II)–aryl complex and a weak base, lysine amino groups in unprotected peptides underwent C−N bond formation at room temperature (see scheme). The process was applicable to the conjugation of a variety of organic compounds, including complex drug molecules, to peptides and was also successfully applied to the formation of cyclic peptides through macrocyclization.

  28. Reviews

    1. Vesicles

      Vesicles in Nature and the Laboratory: Elucidation of Their Biological Properties and Synthesis of Increasingly Complex Synthetic Vesicles

      Dr. Francisco Fernandez-Trillo, Prof. Liam M. Grover, Dr. Alex Stephenson-Brown, Dr. Paul Harrison and Prof. Paula M. Mendes

      Version of Record online: 16 FEB 2017 | DOI: 10.1002/anie.201607825

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      Inspiration–imitation–innovation: Parallel to the elucidation of the biological properties and physiological function of vesicles, increasingly elegant artificial vesicles are being reported. This Review provides an overview of the complex and rapidly developing fields of natural and synthetic vesicles and shows how the two fields can profit from one another.

  29. Communications

    1. Arenes

      Template-Assisted meta-C−H Alkylation and Alkenylation of Arenes

      Sukdev Bag, Dr. Ramasamy Jayarajan, Rahul Mondal and Prof. Dr. Debabrata Maiti

      Version of Record online: 16 FEB 2017 | DOI: 10.1002/anie.201611360

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      On target: Pyrimidine-based, template-assisted meta-C−H alkylation and alkenylation with allyl alcohols and protected allyl alcohols has been developed. Sulfonyl, carbonyl, and phosphonyl esters were used as linkers between the directing group (DG) and target meta-C−H bond of arene.

    2. Protein-Templated Reactions

      Protein-Templated Formation of an Inhibitor of the Blood Coagulation Factor Xa through a Background-Free Amidation Reaction

      Mike Jaegle, Prof. Dr. Torsten Steinmetzer and Prof. Dr. Jörg Rademann

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201611547

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      A protein molds its own killer: The protein factor Xa induces the ligation of two weakly bound fragments into a potent, superadditive inhibitor through amide bond formation (see scheme, bottom). Suitable peptide esters react on the protein surface in a non-catalytic, autoinhibited mechanism without background reaction in the free solution.

    3. Polyoxometalate Self-Assembly | Hot Paper

      Photoresponsive Nanosheets of Polyoxometalates Formed by Controlled Self-Assembly Pathways

      Keita Ishiba, Dr. Takao Noguchi, Dr. Hiroaki Iguchi, Dr. Masa-aki Morikawa, Prof. Dr. Kenji Kaneko and Prof. Dr. Nobuo Kimizuka

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201612473

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      Controlling energy landscapes: Polyoxometalates and ether linkage-enriched ammonium ions spontaneously self-assemble into rectangular, ultrathin nanosheets under controlled conditions in water. These nanosheets are reduced by photoillumination. Site-specific photoetching and photodeposition of silver nanoparticles is demonstrated.

    4. Surface Plasmon Resonance

      Mechanical Trap Surface-Enhanced Raman Spectroscopy for Three-Dimensional Surface Molecular Imaging of Single Live Cells

      Qianru Jin, Prof. Ming Li, Beril Polat, Santosh K. Paidi, Aimee Dai, Amy Zhang, Dr. Jayson V. Pagaduan, Prof. Ishan Barman and Prof. David H. Gracias

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201700695

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      Individual cells are captured by Au nanostar-coated micromechanical traps, which fold up and surround the cell surface and function as a surface-enhanced Raman spectroscopy sensor. Through this non-invasive label-free approach, proteins and lipids can be identified on the cell surface, and the spectra can be used to reconstruct a 3D microscopic image of the cellular surface chemical composition.

  30. Cover Pictures

    1. You have free access to this content
      (Ge4Bi14)4−: A Case of “Element Segregation” on the Molecular Level

      Dr. Robert J. Wilson and Prof. Dr. Stefanie Dehnen

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201701352

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      (Ge4Bi14)4− represents the largest Bi-containing main-group polyanion that is not stabilized by ligands or endohedral atoms. Its structure comprises motifs from smaller polybismuthide anions, like Bi73− or Bi113−, and clearly prefers the spatial separation of Bi atoms from a Ge4 waist in the center of the anion—unlike binary relatives with homologous element combinations that favor a maximum number of heteroatomic bonds, as confirmed by DFT calculations and described by S. Dehnen and R. J. Wilson in their Communication (DOI: 10.1002/anie.201611422).

  31. Communications

    1. Interface Phenomena | Hot Paper

      Cation-Selective Channel Regulated by Anions According to Their Hofmeister Ranking

      Dr. Philip A. Gurnev, Torri C. Roark, Dr. Horia I. Petrache, Dr. Alexander J. Sodt and Dr. Sergey M. Bezrukov

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201611335

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      Hofmeister effects: The conductance of a purely cation-selective peptide pore is regulated by anions in correlation with their position in the Hofmeister series (see picture). Moreover, the pore conformational dynamics are highly sensitive to the anion species. Both effects are related to preferential depletion of kosmotropic anions (accumulation of chaotropic anions) at the membrane–water interface.

  32. Cover Pictures

    1. You have free access to this content
      Organoselenium-Catalyzed Regioselective C−H Pyridination of 1,3-Dienes and Alkenes

      Lihao Liao, Ruizhi Guo and Prof. Dr. Xiaodan Zhao

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201701294

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      A gift from the moon goddesses Selene and Chang'e: Pyridinium salts are formed in an organoselenium-catalyzed regioselective C−H pyridination of alkenes as described by X. Zhao et al. in their Communication (DOI: 10.1002/anie.201610657). The new pyridinium salts were prepared from 1,3-dienes and fluoropyridinium salts using diselenide catalysts personified as lunar goddesses Selene (Greek) and Chang'e (Chinese).

    2. You have free access to this content
      Remote Regulation of Membrane Channel Activity by Site-Specific Localization of Lanthanide-Doped Upconversion Nanocrystals

      Xiangzhao Ai, Linna Lyu, Yang Zhang, Dr. Yanxia Tang, Jing Mu, Fang Liu, Yixi Zhou, Prof. Zhenghong Zuo, Prof. Gang Liu and Prof. Bengang Xing

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201701355

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      Spatiotemporal regulation of membrane channel activity in living systems has been achieved by irradiation with near-IR light (λ=808 nm), as reported by B. Xing and co-workers in their Communication (DOI: 10.1002/anie.201612142). Metabolic glycan biosynthesis is used to attach lanthanide-doped upconversion nanocrystals (UCNs) to the cell surface through copper-free click cyclization. Cation influx can be controlled by irradiation and membrane-associated activities manipulated in living cells and zebrafish.

    3. You have free access to this content
      By-Product-Free Siloxane-Bond Formation and Programmed One-Pot Oligosiloxane Synthesis

      Dr. Kazuhiro Matsumoto, Dr. Kappam Veettil Sajna, Dr. Yasushi Satoh, Dr. Kazuhiko Sato and Dr. Shigeru Shimada

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201701293

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      Oligosiloxanes can be obtained in a single flask in a programmed fashion. In their Communication (DOI: 10.1002/anie.201611623), S. Shimada and co-workers report a novel oligosiloxane synthesis consisting of three successive reactions in one pot: iridium-catalyzed hydrosilylation, boron-catalyzed rearrangement, and boron-catalyzed cross coupling. The sequence of SiR2 units in the oligosiloxane product can be controlled by simply changing the order of hydrosilane addition.

  33. Highlights

    1. Biocatalysis

      The First Biocatalytic Carbon–Silicon Bond Formation

      Prof. Dr. Stephan Lütz

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201612543

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      Linking two worlds: As a further expansion of the biocatalytic repertoire, carbene insertion into Si−H bonds catalyzed by the heme protein cytochrome c was recently reported. This new biocatalyst holds great promise because it enables the highly selective incorporation of silicon into molecules without prior protection of existing functional groups.

  34. Communications

    1. Extended π-Conjugated Systems

      A Stable Saddle-Shaped Polycyclic Hydrocarbon with an Open-Shell Singlet Ground State

      Ji Ma, Dr. Junzhi Liu, Prof. Dr. Martin Baumgarten, Yubin Fu, Prof. Dr. Yuan-Zhi Tan, Karl Sebastian Schellhammer, Dr. Frank Ortmann, Prof. Dr. Gianaurelio Cuniberti, Dr. Hartmut Komber, Dr. Reinhard Berger, Prof. Dr. Klaus Müllen and Prof. Dr. Xinliang Feng

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201611689

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      Stay in the saddle: A curved polycyclic hydrocarbon synthesized by extending the twisted bischrysene core by two indene units displayed a stable singlet biradical structure in the ground state. X-ray crystallographic analysis clearly revealed its saddle-shaped conformation.

    2. Hybrid Polyoxometalates

      Cation Translocation around Single Polyoxometalate–Organic Hybrid Cluster Regulated by Electrostatic and Cation–π Interactions

      Dr. Dong Li, Zhuonan Liu, Dr. Jie Song, Hui Li, Dr. Baofang Zhang, Dr. Panchao Yin, Dr. Zhaoxiong Norm Zheng, Prof. Dr. James E. Roberts, Prof. Dr. Mesfin Tsige, Prof. Dr. Craig L. Hill and Prof. Dr. Tianbo Liu

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201612008

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      Near and far: Spectroscopic and theoretical studies on the dynamic translocation process of countercations around a polyoxometalate–organic hybrid anionic molecular cluster show that electrostatic interactions and cation–π interactions regulate the position of small countercations around single clusters.

    3. Surface Chemistry

      You have full text access to this OnlineOpen article
      Rapid and Complete Surface Modification with Strain-Promoted Oxidation-Controlled Cyclooctyne-1,2-Quinone Cycloaddition (SPOCQ)

      Rickdeb Sen, Dr. Jorge Escorihuela, Prof. Dr. Floris van Delft and Prof. Dr. Han Zuilhof

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201612037

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      Throwing DARTs at a surface: The strain-promoted oxidation-controlled cyclooctyne-1,2-quinone cycloaddition (SPOCQ) between bicyclo[6.1.0]nonyne (BCN) and a surface-bound quinone revealed an unprecedented 100 % conjugation efficiency.

    4. Fluorescent Labeling | Hot Paper

      In Vivo Gold Complex Catalysis within Live Mice

      Kazuki Tsubokura, Dr. Kenward K. H. Vong, Dr. Ambara R. Pradipta, Dr. Akihiro Ogura, Sayaka Urano, Dr. Tsuyoshi Tahara, Dr. Satoshi Nozaki, Dr. Hirotaka Onoe, Dr. Yoichi Nakao, Regina Sibgatullina, Dr. Almira Kurbangalieva, Dr. Yasuyoshi Watanabe and Dr. Katsunori Tanaka

      Version of Record online: 15 FEB 2017 | DOI: 10.1002/anie.201610273

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      The first metal-catalyzed reaction that proceeds within live mice is based on a targeting approach with glycans. Glycoalbumin–AuIII complexes can be accumulated in specific organs where they catalyze amide bond formation between a propargyl ester probe and amine groups on nearby proteins. The selective targeting was confirmed by whole body fluorescence imaging and analysis of dissected tissues.

    5. Cross-Coupling | Very Important Paper

      Oxygen Activated, Palladium Nanoparticle Catalyzed, Ultrafast Cross-Coupling of Organolithium Reagents

      Dorus Heijnen, Filippo Tosi, Dr. Carlos Vila, Dr. Marc C. A. Stuart, Prof. Dr. Philip H. Elsinga, Dr. Wiktor Szymanski and Prof. Dr. Ben L. Feringa

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201700417

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      No oxygen, no coupling: Molecular oxygen was shown to be crucial for the fast palladium-catalyzed cross-coupling of organolithium reagents developed herein. Reactions times down to 5 s provide a novel procedure for the preparation of radiolabeled compounds.

    6. Homogeneous Catalysis

      A General and Highly Selective Cobalt-Catalyzed Hydrogenation of N-Heteroarenes under Mild Reaction Conditions

      Dr. Rosa Adam, Dr. Jose R. Cabrero-Antonino, Dr. Anke Spannenberg, Dr. Kathrin Junge, Dr. Ralf Jackstell and Prof. Matthias Beller

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612290

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      Reduction! Quinolines and related N-heteroarenes are hydrogenated using [Co]/L. The reactions proceed under mild conditions in a highly selective manner.

    7. Ge4Se3Te Structure

      Unexpected Ge–Ge Contacts in the Two-Dimensional Ge4Se3Te Phase and Analysis of Their Chemical Cause with the Density of Energy (DOE) Function

      M. Sc. Michael Küpers, M. Sc. Philipp M. Konze, Dipl.-Chem. Stefan Maintz, Dr. Simon Steinberg, Dr. Antonio M. Mio, Dr. Oana Cojocaru-Mirédin, Dr. Min Zhu, Dr. Merlin Müller, Dr. Martina Luysberg, Prof. Dr. Joachim Mayer, Prof. Dr. Matthias Wuttig and Prof. Dr. Richard Dronskowski

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612121

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      Ge–Ge contacts and the DOE: Ge4Se3Te, a layered structure with van der Waals interactions and unexpected Ge–Ge contacts, was crystallized, structurally characterized, and analyzed by electron microscopy. The nature of its electronic structure was characterized by chemical bonding analysis and the newly introduced density of energy (DOE) function.

    8. Protein Chemistry

      Inversion of the Side-Chain Stereochemistry of Indvidual Thr or Ile Residues in a Protein Molecule: Impact on the Folding, Stability, and Structure of the ShK Toxin

      Dr. Bobo Dang, Dr. Rong Shen, Dr. Tomoya Kubota, Dr. Kalyaneswar Mandal, Prof. Dr. Francisco Bezanilla, Prof. Dr. Benoit Roux and Prof. Dr. Stephen B. H. Kent

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612398

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      Ch-ch-ch-changes: Guided by molecular dynamics calculations, chemical protein synthesis was used to explore the impact of allo-Thr and allo-Ile substitutions for individual Thr and Ile residues on the folding, crystal structure, and stability of the ShK protein. The experimental folding and thermal stability data matched well with the computational results.

    9. Water Oxidation

      Hollow Iron–Vanadium Composite Spheres: A Highly Efficient Iron-Based Water Oxidation Electrocatalyst without the Need for Nickel or Cobalt

      Dr. Ke Fan, Dr. Yongfei Ji, Haiyuan Zou, Dr. Jinfeng Zhang, Bicheng Zhu, Dr. Hong Chen, Quentin Daniel, Prof. Yi Luo, Prof. Jiaguo Yu and Prof. Licheng Sun

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201611863

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      Missing, but not missed: Vanadium-doped FeOOH is a low-cost, highly efficient iron-based electrocatalyst for water oxidation without Ni or Co participation. It exhibits a low overpotential 390 mV (10 mA cm−2 catalytic current density), low Tafel slope of 36.7 mV dec−1, and a considerable durability.

    10. Heterobimetallic Complexes

      Enhancement of C−H Oxidizing Ability in Co–O2 Complexes through an Isolated Heterobimetallic Oxo Intermediate

      Daniel E. DeRosha, Dr. Brandon Q. Mercado, Prof. Dr. Gudrun Lukat-Rodgers, Prof. Dr. Kenton R. Rodgers and Prof. Dr. Patrick L. Holland

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612010

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      Odd couple: Treatment of a side-on dioxygen complex of cobalt with a low-valent iron or cobalt diketiminate complex affords a homobimetallic Co/Co or a heterobimetallic Fe/Co oxo complex, respectively. C−H activation in the Co/Fe complex is three orders of magnitude faster than in the homobimetallic analogue.

  35. Cover Pictures

    1. You have free access to this content
      Synthetic Channel Specifically Inserts into the Lipid Bilayer of Gram-Positive Bacteria but not that of Mammalian Erythrocytes

      Min Zhang, Ping-Ping Zhu, Pengyang Xin, Wen Si, Prof. Zhan-Ting Li and Prof. Jun-Li Hou

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201701292

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      Synthetic transmembrane channels, a kind of rationally designed molecules that can transport ions by formation of nanopores that span the lipid bilayer, provide an alternative strategy for the development of membrane-active antimicrobials. However, few such channels show membrane selectivity. In their Communication (DOI: 10.1002/anie.201612093), J.-L Hou and co-workers report a channel that is able to specifically insert into the lipid bilayers of Gram-positive bacteria but not those of mammalian erythrocytes.

  36. Communications

    1. Asymmetric Synthesis

      Synthesis of Enantiopure C3-Symmetric Triangular Molecules

      Dr. Tomoya Miura, Takayuki Nakamuro, Dr. Scott G. Stewart, Dr. Yuuya Nagata and Prof. Dr. Masahiro Murakami

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612585

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      My hat, it has three corners: Enantiopure C3-symmetric triangular macrocycles were synthesized by means of triple asymmetric cyclopropanation. This method is successfully extended to the synthesis of an enantiopure hydrocarbon, which owes its chirality to asymmetric distribution of H/D atoms on the benzene rings.

    2. Gold Catalysis

      On the Gold-Catalyzed Generation of Vinyl Cations from 1,5-Diynes

      M. Sc. Thomas Wurm, M. Sc. Janina Bucher, Sarah B. Duckworth, Dr. Matthias Rudolph, Dr. Frank Rominger and Prof. Dr. A. Stephen K. Hashmi

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201700057

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      Positive intermediates: The combination of non-terminal 1,5-diynes with cationic gold complexes enables the generation of highly reactive vinyl cations that can be used for the synthesis of unsymmetrically substituted dibenzopentalenes. Quantum-chemical calculations indicate a fast valence tautomer equilibrium between a gold alkyne complex and the vinyl cation.

    3. Molecularly Imprinted Polymers

      Enzyme-Initiated Free-Radical Polymerization of Molecularly Imprinted Polymer Nanogels on a Solid Phase with an Immobilized Radical Source

      Dr. Mira Daoud Attieh, Dr. Yi Zhao, Prof. Assem Elkak, Dr. Aude Falcimaigne-Cordin and Prof. Karsten Haupt

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612667

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      Mighty Immobilized Peroxidase: The radical polymerization of methacrylate or vinyl monomers and cross-linkers was initiated by immobilized horseradish peroxidase (HRP) to prepare molecularly imprinted polymer (MIP) nanogels in aqueous media (see scheme). MIP nanoparticles with sizes between 50 and 300 nm were obtained with good binding properties and high selectivity for the target molecule, the herbicide 2,4-dichlorophenoxyacetic acid.

    4. Bioorthogonal Chemistry

      Steering Siglec–Sialic Acid Interactions on Living Cells using Bioorthogonal Chemistry

      Christian Büll, Torben Heise, Niek van Hilten, Johan F. A. Pijnenborg, Victor Bloemendal, Lotte Gerrits, Esther D. Kers-Rebel, Dr. Tina Ritschel, Dr. Martijn H. den Brok, Prof. Dr. Gosse J. Adema and Dr. Thomas J. Boltje

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612193

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      Clicking the immune system off: We report a method to rapidly reprogram the binding of sialic acid sugars on living cells to their cognate Siglec receptors through glycoengineering and click chemistry. Binding could be improved by more than 100-fold and in a selective manner. The modified cells showed potent immunosuppressive activity resulting from strong signaling through Siglecs on immune cells.

    5. Asymmetric Catalysis

      Enantioselective Aza-Ene-type Reactions of Enamides with Gold Carbenes Generated from α-Diazoesters

      Feng Zhao, Nan Li, Tao Zhang, Zhi-Yong Han, Shi-Wei Luo and Prof. Dr. Liu-Zhu Gong

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612208

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      How low can you go? Carbophilic gold carbenes derived from α-diazoesters react with enamides in an unprecedented aza-ene-type reaction. The presence of 0.1 mol % of a chiral Brønsted acid is sufficient to achieve excellent yields and enantioselectivities.

    6. Artificial Photosynthesis

      A Ruthenium Complex–Porphyrin–Fullerene-Linked Molecular Pentad as an Integrative Photosynthetic Model

      Masanori Yamamoto, Jens Föhlinger, Dr. Jonas Petersson, Prof. Dr. Leif Hammarström and Prof. Dr. Hiroshi Imahori

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201612456

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      Pent-up energy: A ruthenium-based water oxidation catalyst linked to porphyrin–fullerene units in a molecular pentad has been synthesized. Transient absorption indicated the photoinduced multistep electron transfer afforded a long-lived hole–electron pair, and photocatalytic water oxidation by the pentad was achieved in the presence of sacrificial oxidant.

    7. Allylic Compounds

      Enantioselective Dearomatization of Naphthol Derivatives with Allylic Alcohols by Cooperative Iridium and Brønsted Acid Catalysis

      Dan Shen, Qiliang Chen, Peipei Yan, Prof. Dr. Xiaofei Zeng and Prof. Dr. Guofu Zhong

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201609693

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      Co-op: The cooperative dual-catalytic system of a chiral iridium complex and phosphoric acid achieves highly enantioselective allylic dearomatization reactions of naphthols with racemic secondary allylic alcohols. The desired β-naphthalenones, bearing an all-carbon quaternary center, were obtained in good yields. Both β-naphthalenone enantiomers can be obtained by simply employing opposite enantiomeric ligands.

    8. Foldamers

      Reversible Stereoselective Folding/Unfolding Fueled by the Interplay of Photoisomerism and Hydrogen Bonding

      Dr. Christopher R. Opie, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Version of Record online: 14 FEB 2017 | DOI: 10.1002/anie.201610279

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      Know when to fold 'em: A linear molecular architecture equipped with complementary three-fold hydrogen bonding units embedded with a photoswitchable trans-tetrafluoroazobenzene moiety was synthesized. The trans to cis photoisomerism of the azobenzene unit induced changes in the molecular architecture as a result of intramolecular hydrogen bonding as evidenced by NMR spectroscopy and size exclusion chromatography.

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