Chemistry - A European Journal

Cover image for Vol. 21 Issue 50

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

Editor: Neville Compton, Deputy Editors: Anne Deveson, Elisabeth Roedern

Impact Factor: 5.731

ISI Journal Citation Reports © Ranking: 2014: 22/157 (Chemistry Multidisciplinary)

Online ISSN: 1521-3765

Associated Title(s): Angewandte Chemie International Edition, Chemistry – An Asian Journal, ChemistryOpen, ChemistrySelect, ChemBioChem, ChemCatChem, ChemElectroChem, ChemMedChem, ChemPhysChem, ChemPlusChem, ChemSusChem, European Journal of Inorganic Chemistry, European Journal of Organic Chemistry

  1. Corrigenda

    1. You have free access to this content
  2. Communications

    1. Multicomponent Reactions

      Bifunctional Furfuryl Cations Strategy: Three-Component Synthesis of Enamidyl Triazoles

      Hengtuo Yang, Dr. Jing Gou, Jiawei Guo, Dongyu Duan, Prof. Dr. Yu-Ming Zhao, Prof. Dr. Binxun Yu and Prof. Dr. Ziwei Gao

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201504330

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      Heterocycle reassembling: 5-Halofurylcarbinol can serve as a bifunctional platform to react with an azide and amine by a Lewis acid promoted three-component reaction. It involves a novel formal [3+2] cycloaddition/ring-opening/amidation cascade, enabling the expediently and efficient construction of a diverse set of highly functional enamidyl triazoles (see scheme).

  3. Full Papers

    1. Synthetic Methods

      Synthesis of Three-Dimensional Butterfly Slit-Cyclobisazaanthracenes and Hydrazinobisanthenes through One-Step Cyclodimerization and Their Properties

      Dr. Koji Yamamoto and Prof. Dr. Shuhei Higashibayashi

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201504144

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      Fly like a butterfly! Three-dimensional butterfly-shaped slit cyclobisazaanthracenes were synthesized by Ni-mediated one-step cyclodimerization of dibromoazaanthracenes. Hydrazinobisanthenes obtained by closing the slit were found to possess a butterfly or a plane structure depending on the heterocycle (see scheme).

  4. Communications

    1. Chirality

      You have full text access to this OnlineOpen article
      Circularly Polarized Luminescence from Helically Chiral N,N,O,O-Boron-Chelated Dipyrromethenes

      Rua B. Alnoman, Dr. Sandra Rihn, Daniel C. O'Connor, Fiona A. Black, Dr. Bernard Costello, Dr. Paul G. Waddell, Prof. William Clegg, Prof. Robert D. Peacock, Prof. Wouter Herrebout, Dr. Julian G. Knight and Dr. Michael J. Hall

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201504484

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      Absolute stereochemistry: Helically chiral N,N,O,O-boron chelated dipyrromethenes showed solution-phase circularly polarized luminescence (CPL) in the red region of the visible spectrum. The parent dipyrromethene is desymmetrised through O chelation of boron by the 3,5-ortho-phenolic substituents, inducing a helical chirality in the fluorophore (see figure).

  5. Full Papers

    1. Total Synthesis

      Symmetry-Driven Strategy for the Assembly of the Core Tetracycle of (+)-Ryanodine: Synthetic Utility of a Cobalt-Catalyzed Olefin Oxidation and α-Alkoxy Bridgehead Radical Reaction

      Dr. Masanori Nagatomo, Dr. Koji Hagiwara, Kengo Masuda, Masaki Koshimizu, Takahiro Kawamata, Yuki Matsui, Dr. Daisuke Urabe and Prof. Dr. Masayuki Inoue

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503640

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      Total synthesis of ryanodine, part 1: (+)-Ryanodine (1) is a potent modulator of intracellular calcium release channels, designated as ryanodine receptors. A simple and efficient strategy for the enantioselective construction of the core tetracycle by specific recognition of the C2-symmetric substructure embedded within 1 was devised (see scheme; MOM=methoxymethyl). Moreover, a two-step ketone formation and a α-alkoxy bridgehead radical reaction were developed as the new powerful methodologies.

    2. Asymmetric Total Synthesis of (+)-Ryanodol and (+)-Ryanodine

      Kengo Masuda, Masaki Koshimizu, Dr. Masanori Nagatomo and Prof. Dr. Masayuki Inoue

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503641

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      Total synthesis of ryanodine, part 2: (+)-Ryanodine (1) is the ester derivative of 1H-pyrrole-2-carboxylic acid and the complex terpenoid (+)-ryanodol (2), which possesses eleven contiguous stereogenic centers on the pentacyclic ring system. The total synthesis of both 2 and 1 was realized from the enantiopure tetracycle. The new, two-step protocol was developed to attach the pyrrole moiety onto the hindered alcohol, enabling the completion of the first chemical construction of 1 (see scheme).

    3. Self-Assembly

      Cyclic Tetramers of Zinc Chlorophylls as a Coupled Light-Harvesting Antenna–Charge-Separation System

      Dr. Yoshinao Shinozaki, Prof. Kei Ohkubo, Prof. Shunichi Fukuzumi, Dr. Kosuke Sugawa and Prof. Joe Otsuki

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503789

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      Dual functionality: A coupled light-harvesting and charge-separation system is constructed by coordination-directed assembly of specifically functionalized chlorophyll molecules, in which nearly 100 % charge separation is achieved once a photon is absorbed (see figure; EnT=energy transfer, ET=electron transfer).

    4. Contrast Agents

      Chemical Exchange Saturation Transfer (CEST) Agents: Quantum Chemistry and MRI

      Jikun Li, Xinxin Feng, Wei Zhu, Nikita Oskolkov, Tianhui Zhou, Boo Kyung Kim, Noman Baig, Prof. Michael T. McMahon and Prof. Eric Oldfield

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503942

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      Compare and contrast: The use of DFT calculations permits good predictions of chemical shifts in CEST MRI agents. The most promising leads are nontoxic and have excellent activity in mice kidney MR imaging (see figure).

    5. Li-Ion Batteries

      Synergistic Ternary Composite (Carbon/Fe3O4@Graphene) with Hollow Microspherical and Robust Structure for Li-Ion Storage

      Xingxing Li, Xueying Zheng, Prof. Jie Shao, Tian Gao, Qiang Shi and Prof. Dr. Qunting Qu

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201504035

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      Robust hollow structure: Graphene-wrapped hollow C/Fe3O4 microspheres are rationally designed and prepared through a novel facile strategy. The synergistic effect of carbon, Fe3O4, and graphene leads to excellent Li-storage performance (see figure).

  6. Communications

    1. Enzymes

      A Combined Crystallographic and Theoretical Study Explains the Capability of Carboxylic Acids to Adopt Multiple Binding Modes in the Active Site of Carbonic Anhydrases

      Dr. Emma Langella, Dr. Katia D'Ambrosio, Dr. Melissa D'Ascenzio, Dr. Simone Carradori, Dr. Simona M. Monti, Prof. Claudiu T. Supuran and Dr. Giuseppina De Simone

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503748

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      Mapping enzymes: Carboxylates are the least investigated class of inhibitors of carbonic anhydrases (CAs). Here we explain the versatility of binding of these molecules to CAs by examining a new adduct of CA II with N-carboxymethyl-saccharin (see figure).

  7. Full Papers

    1. Metal–Organic Frameworks

      Structural Effects in Visible-Light-Responsive Metal–Organic Frameworks Incorporating ortho-Fluoroazobenzenes

      Dr. Sonia Castellanos, Dr. Alexis Goulet-Hanssens, Fangli Zhao, Alla Dikhtiarenko, Alexey Pustovarenko, Prof. Stefan Hecht, Prof. Jorge Gascon, Prof. Freek Kapteijn and Dr. David Bléger

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503503

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      Photo-MOFs respond to green and blue: Incorporating all-visible azobenzene photoswitches into microporous metal–organic frameworks (MOFs) confer good photochromic properties and the ability to photomodulate CO2 uptake on irradiation with visible light. The influence of the structures of the MOFs on the photoswitching ability of confined fluoroazobenzene moieties was investigated (see figure).

    2. Acceptor–Donor Conjugates | Hot Paper

      Engaging Copper(III) Corrole as an Electron Acceptor: Photoinduced Charge Separation in Zinc Porphyrin–Copper Corrole Donor–Acceptor Conjugates

      Dr. Thien H. Ngo, David Zieba, Whitney A. Webre, Gary N. Lim, Prof. Dr. Paul A. Karr, Scheghajegh Kord, Dr. Shangbin Jin, Dr. Katsuhiko Ariga, Marzia Galli, Prof. Dr. Steve Goldup, Dr. Jonathan P. Hill and Prof. Dr. Francis D'Souza

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503490

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      Donor–acceptor conjugates based on zinc porphyrin as the electron donor and copper(III) corrole as the electron acceptor have been successfully prepared with outstanding yields. Electrochemical and computational studies revealed the electron-deficient nature of copper(III) corrole, leading to phenomena of photoinduced electron transfer from the singlet excited zinc porphyrin to copper corrole, as demonstrated by femtosecond transient spectroscopy.

    3. Donor–Acceptor Systems

      From Dark to Light to Fluorescence Resonance Energy Transfer (FRET): Polarity-Sensitive Aggregation-Induced Emission (AIE)-Active Tetraphenylethene-Fused BODIPY Dyes with a Very Large Pseudo-Stokes Shift

      Esra Şen, Dr. Kadem Meral and Dr. Serdar Atılgan

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503457

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      Don’t FRET, DRET! An approach is presented to create energy-transfer systems that generate a remarkable large pseudo-Stokes shift with high emission intensity in both organic and aqueous media by combining dark resonance energy transfer (DRET) and fluorescence resonance energy transfer (FRET) in one donor–acceptor system (see figure).

    4. Host–Guest Systems

      Silicon- and Tin-Containing Open-Chain and Eight-Membered-Ring Compounds as Bicentric Lewis Acids toward Anions

      Dr. Anicet Siakam Wendji, Dr. Christina Dietz, Dr. Silke Kühn, Michael Lutter, Dr. Dieter Schollmeyer, Dr. Wolf Hiller and Prof. Dr. Klaus Jurkschat

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201502722

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      Attractive centres: A series of silicon- and tin-containing open-chain and eight-membered-ring compounds and their chloride and fluoride complexes has been synthesised and completely characterised. A common characteristic feature of these complexes is the complexation of halide anions by a bicentric Lewis acid that contains two tin centres (see figure).

    5. Substituent Effects

      Exquisite 1D Assemblies Arising from Rationally Designed Asymmetric Donor–Acceptor Architectures Exhibiting Aggregation-Induced Emission as a Function of Auxiliary Acceptor Strength

      Roop Shikha Singh, Sujay Mukhopadhyay, Arnab Biswas and Prof. Daya Shankar Pandey

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503570

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      Emission conditions: Three compounds have been designed and synthesized to investigate aggregation-induced emission (AIE) in an asymmetric donor–acceptor (D–A) construct of A′–D–π–A (A′=auxiliary acceptor) topology. The occurrence of AIE and subsequent optical disparities of these A′–D–π–A architectures are a direct consequence of the comparative strength of A′ (see figure).

    6. Divalent Nitrogen(I) Compounds

      Design, Synthesis, and Structural Analysis of Divalent NI Compounds and Identification of a New Electron-Donating Ligand

      Prof. Dr. Prasad V. Bharatam, Minhajul Arfeen, Neha Patel, Priyanka Jain, Sonam Bhatia, Prof. Dr. Asit K. Chakraborti, Dr. Sadhika Khullar, Vijay Gupta and Prof. Dr. Sanjay K. Mandal

      Article first published online: 30 NOV 2015 | DOI: 10.1002/chem.201503618

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      Divalent by design: Novel systems in which an N+ center is flanked by electron-donating benzimidazole/benzothiazole and cyclohexa-2,5-diene-4-(diaminomethynyl)-1-ylidene ligands were designed and synthesized (see figure). Crystal structure and electronic structure analysis confirmed the presence of dative bond between electron-donating ligands and the N+ center.

    7. Energetic Materials

      Core–Shell Al-Polytetrafluoroethylene (PTFE) Configurations to Enhance Reaction Kinetics and Energy Performance for Nanoenergetic Materials

      Dr. Jun Wang, Dr. Zhiqiang Qiao, Dr. Yuntao Yang, Dr. Jinpeng Shen, Dr. Zhang Long, Dr. Zhaoqian Li, Prof. Dr. Xudong Cui and Dr. Guangcheng Yang

      Article first published online: 27 NOV 2015 | DOI: 10.1002/chem.201503850

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      Shells under control: An in situ chemical vapor deposition combined with the electrical explosion of wires (EEW) method has been applied to fabricate core–shell Al-PTFE nanoenergetic materials. The polytetrafluoroethylene (PTFE) shell prevents nano-Al layers from oxidation and assists in enhancing the reaction kinetics, greatly improving the stability and reactivity of fuels. This synthetic strategy might provide a general approach to prepare other energetic materials (Mg, Si).

    8. Photocatalysis

      Development of Hybrid BiOClxBr1−x-Embedded Alumina Films and Their Application as Highly Efficient Visible-Light-Driven Photocatalytic Reactors

      Hani Gnayem, Dr. Anirban Dandapat and Prof. Yoel Sasson

      Article first published online: 27 NOV 2015 | DOI: 10.1002/chem.201503900

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      Illuminate with alumina: BiOClxBr1−x-loaded (75 wt %) alumina composite films were deposited on a glass container for the fabrication of visible-light-driven photoreactors. These highly stable films showed very good photocatalytic activities (see figure).

    9. Lithium-Ion Batteries | Hot Paper

      Growth of Hollow Transition Metal (Fe, Co, Ni) Oxide Nanoparticles on Graphene Sheets through Kirkendall Effect as Anodes for High-Performance Lithium-Ion Batteries

      Xianbo Yu, Bin Qu, Yang Zhao, Chunyan Li, Prof. Yujin Chen, Prof. Chunwen Sun, Prof. Peng Gao and Dr. Chunling Zhu

      Article first published online: 27 NOV 2015 | DOI: 10.1002/chem.201503897

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      Hollow-lujah! A general strategy based on the nanoscale Kirkendall effect is used to grow hollow transition metal (Fe, Co, or Ni) oxide nanoparticles on graphene sheets. When applied as lithium-ion battery anodes, these hollow transition metal oxide-based composites exhibit excellent electrochemical performance, with high reversible capacities and long-term stabilities at a high current density, superior to most transition metal oxides reported to date.

    10. Vibrational Circular Dichroism

      Interplay of Exciton Coupling and Large-Amplitude Motions in the Vibrational Circular Dichroism Spectrum of Dehydroquinidine

      Dr. Valentin P. Nicu, Dr. Sérgio R. Domingos, M. Sc. Benjamin H. Strudwick, Prof. Dr. Albert M. Brouwer and Prof. Dr. Wybren J. Buma

      Article first published online: 27 NOV 2015 | DOI: 10.1002/chem.201503250

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      Flexibility unleashed: Experimental and theoretical studies of vibrational circular dichroism spectra of a prototypical organocatalyst reveal their remarkable sensitivity towards structural flexibility. Large-amplitude motions are shown to play a key role in determining band shape and intensity. The underlying reason is found to be that even small contributions of polar bond motion to vibrational coordinates can lead to huge signal enhancements through exciton coupling mechanisms (see figure).

    11. Catalysts

      You have full text access to this OnlineOpen article
      Large Ferrierite Crystals as Models for Catalyst Deactivation during Skeletal Isomerisation of Oleic Acid: Evidence for Pore Mouth Catalysis

      Sophie C. C. Wiedemann, Zoran Ristanović, Dr. Gareth T. Whiting, Dr. V. R. Reddy Marthala, Prof. Dr. Jörg Kärger, Prof. Dr. Jens Weitkamp, Dr. Bas Wels, Dr. Pieter C. A. Bruijnincx and Prof. Dr. Bert M. Weckhuysen

      Article first published online: 27 NOV 2015 | DOI: 10.1002/chem.201503551

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      Catalysis at the edge: Large zeolite crystals of ferrierite have been used to study catalyst deactivation in the alkyl isomerisation of oleic and elaidic acid by a combination of micro-spectroscopy methods (see figure). It was found that the markers of catalytic activity were exclusively found near the pore mouths of the larger 10-MR channels of ferrierite at all crystal edges, providing experimental evidence for the concept of pore mouth catalysis.

    12. Chemical Biology

      Native Chemical Ligation to Minimize Aspartimide Formation during Chemical Synthesis of Small LDLa Protein

      Dr. Julien Tailhades, Ashish Sethi, Dr. Emma J. Petrie, Prof. Dr. Paul R. Gooley, Prof. Dr. Ross A. Bathgate, Prof. Dr. John D. Wade and Dr. Mohammed A. Hossain

      Article first published online: 27 NOV 2015 | DOI: 10.1002/chem.201503599

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      Returning to the fold: LDLa is small protein with complex three disulfide bridges and several aspartic acids that are sensitive to aspartimide formation. This study detailed the solution to circumvent formation of asparatimide and successful acquisition of three disulfide bridges. As a result, synthesis of LDLa was successfully achieved with excellent quality.

  8. Communications

    1. Natural Products

      Synthesis of Hydroxypyrrolone Carboxamides Employing Selectfluor

      Tim Carlo Allmann, Dr. Rares-Petru Moldovan, Prof. Dr. Peter G. Jones and Prof. Dr. Thomas Lindel

      Article first published online: 27 NOV 2015 | DOI: 10.1002/chem.201503695

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      Marine compounds: Facile access to hydroxypyrrolone carboxamides is opened by treatment of pyrrole-2-carboxamides with Selectfluor in MeCN/water (4:1) (see scheme). A variety of sensitive functional groups is tolerated, among them aldehydes and alkynes. Bicyclic hydroxypyrrolones have also been obtained.

    2. X-ray Crystallography

      The Radical Anion of Cyclopentasilane-Fused Hexasilabenzvalene

      Dr. Akihiro Tsurusaki and Prof. Dr. Soichiro Kyushin

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201504449

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      Radical chemistry! The radical anion of cyclopentasilane-fused hexasilabenzvalene (see graphic) was synthesized by the reduction of the corresponding neutral compound. X-ray crystallographic analysis showed a more trans-bend structure of the disilene moiety than the neutral compound. The EPR spectrum showed that an unpaired electron exists mainly at the disilene moiety.

  9. Concepts

    1. Organocatalysis

      You have free access to this content
      The Resurgence of the Highly Ylidic N-Heterocyclic Olefins as a New Class of Organocatalysts

      Reece D. Crocker and Dr. Thanh V. Nguyen

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201503575

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      One carbon better: N-Heterocyclic olefins, the alkylidene derivatives of the prevalent N-heterocyclic carbenes, have recently emerged as efficient promoters for CO2 fixation and polymerization reactions. Their extraordinarily strong Lewis/Brønsted basicity suggests great potential as a new class of organocatalysts for a broad range of reactions in synthetic chemistry.

  10. Communications

    1. Organic Synthesis

      You have full text access to this OnlineOpen article
      Copper-Catalyzed Double Additions and Radical Cyclization Cascades in the Re-Engineering of the Antibacterial Pleuromutilin

      Rebecca E. Ruscoe, Dr. Neal J. Fazakerley, Huanming Huang, Prof. Dr. Sabine Flitsch and Prof. Dr. David J. Procter

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201504343

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      Cascade processes: A general synthetic sequence involving simply prepared starting materials provides rapid access to diverse, novel tricyclic architectures inspired by pleuromutilin. SmII-mediated radical cyclization cascades of dialdehydes, prepared using a new, one-pot, copper-catalyzed double organomagnesium addition to β-chlorocyclohexenone, provide rapid access to novel analogues of the core of the important antibacterial (see scheme).

  11. Minireviews

    1. Azafullerenes

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      Azafullerene C59N in Donor–Acceptor Dyads: Synthetic Approaches and Properties

      Dr. Georgios Rotas and Prof. Dr. Nikos Tagmatarchis

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201502190

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      Energy conversion schemes: Donor–acceptor systems based on the azafullerene C59N are reviewed. While focusing on the synthetic strategies, the properties of systems employing this azafullerene as electron or energy acceptor are also presented, unfolding both the synthetic access as well as the unique electronic properties of these systems. Both in dyads in solution as well as in solar cell devices, C59N is revealed as a promising acceptor for energy conversion schemes.

  12. Full Papers

    1. Structural Biology

      Azidoethoxyphenylalanine as a Vibrational Reporter and Click Chemistry Partner in Proteins

      Elise M. Tookmanian, Prof. Dr. Christine M. Phillips-Piro, Prof. Dr. Edward E. Fenlon and Prof. Dr. Scott H. Brewer

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201503908

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      Double duty—report and click: 4-(2-Azidoethoxy)-L-phenylalanine (AePhe) was incorporated into superfolder green fluorescent protein (sfGFP) at two sites. The IR spectra of these sfGFP constructs indicated that the azide vibrational reporter at the 149 site was not fully solvated, which was unexpected. An X-ray crystal structure (see figure) of sfGFP-149-AePhe provides an explanation for the IR data as the flexible linker adopts a conformation which partially buries the azide on the protein surface.

    2. Oxygen Reduction Catalysts

      Dinuclear Cobalt Complexes with a Decadentate Ligand Scaffold: Hydrogen Evolution and Oxygen Reduction Catalysis

      Dr. Carlo Di Giovanni, Dr. Carolina Gimbert-Suriñach, Dr. Michael Nippe, Dr. Jordi Benet-Buchholz, Prof. Jeffrey R. Long, Dr. Xavier Sala and Prof. Antoni Llobet

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201503567

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      Ten arms are better than one: A decadentate dinucleating ligand with a pyridazine bridging group and pyridylic arms was synthesized. The ligand provides a flexible but stable coordination environment that plays a crucial role in the catalytic performance of the complexes in the photochemical hydrogen evolution reaction (HER) and chemical oxygen reduction (ORR) (see figure).

    3. Surface Chemistry

      A Versatile Precursor System for Supercritical Fluid Electrodeposition of Main-Group Materials

      Prof. Philip N. Bartlett, Jennifer Burt, Dr. David A. Cook, Dr. Charles Y. Cummings, Prof. Michael W. George, Prof. Andrew L. Hector, Mahboba M. Hasan, Dr. Jie Ke, Prof. William Levason, Dr. David Pugh, Prof. Gillian Reid, Dr. Peter W. Richardson, Prof. David C. Smith, Joe Spencer, Norhidayah Suleiman and Dr. Wenjian Zhang

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201503301

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      Compatible conditions: The electrodeposition of a range of p-block elements under compatible conditions from supercritical difluoromethane opens up the possibility of electrodepositing sub-20 nm nanostructures of a wide range of p-block binary and ternary alloys and compounds (see figure).

    4. Magnetic Anisotropy | Hot Paper

      An Experimental and Theoretical Investigation on Pentacoordinated Cobalt(III) Complexes with an Intermediate S=1 Spin State: How Halide Ligands Affect their Magnetic Anisotropy

      Deborah Brazzolotto, Dr. Marcello Gennari, Shengying Yu, Dr. Jacques Pécaut, Mathieu Rouzières, Dr. Rodolphe Clérac, Dr. Maylis Orio and Dr. Carole Duboc

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201502997

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      Complex magnetism: The factors that control the magnitude and symmetry of the magnetic anisotropy are investigated for a unique series of halide CoIII complexes (see figure), which possess a rare intermediate S=1 spin ground state and remarkably large axial zero-field splitting.

    5. Dyes

      Near-IR BODIPY Dyes à la Carte—Programmed Orthogonal Functionalization of Rationally Designed Building Blocks

      Dr. Cesar F. A. Gómez-Durán, Ixone Esnal, Dr. Ismael Valois-Escamilla, Arlette Urías-Benavides, Dr. Jorge Bañuelos, Prof. Iñigo López Arbeloa, Dr. Inmaculada García-Moreno and Prof. Eduardo Peña-Cabrera

      Article first published online: 26 NOV 2015 | DOI: 10.1002/chem.201503090

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      Versatile functionalization of the BODIPY core: The borondipyrromethene (BODIPY) system has been derivatized in a versatile manner through a strategy based on orthogonal reactivity (see figure). This has allowed access to some red/NIR-emitting dyes with superior properties to current commercial laser dyes.

    6. Polyoxometalates | Hot Paper

      Metal-Directed Self-Assembly of a Polyoxometalate-Based Molecular Triangle: Using Powerful Analytical Tools to Probe the Chemical Structure of Complex Supramolecular Assemblies

      Dr. Guillaume Izzet, Dr. Andrew Macdonell, Dr. Corentin Rinfray, Madeleine Piot, Séverine Renaudineau, Dr. Etienne Derat, Dr. Benjamin Abécassis, Prof. Dr. Carlos Afonso and Prof. Dr. Anna Proust

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201503363

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      Precise triangulation: A polyoxometalate-based molecular triangle has been synthesized through the metal-driven self-assembly of covalent organic/inorganic hybrid oxo-clusters with remote pyridyl binding sites. The new metallomacrocycle was unambiguously characterized by using 1H NMR and 2D diffusion NMR spectroscopies (DOSY), electrospray ionization travelling wave ion mobility mass spectrometry (ESI-TWIM-MS), small-angle X-ray scattering (SAXS) and molecular modelling (see figure).

  13. Concepts

    1. Phosphorescent Optoelectronics

      Carboranes as a Tool to Tune Phosphorescence

      Xiang Li, Prof. Dr. Hong Yan and Prof. Dr. Qiang Zhao

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201503456

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      Phosphorescent transition-metal complexes (PTMCs) have attracted a great deal of interest because of their excellent luminescent properties. Most recently, carboranes have been demonstrated to be an effective tool to tune phosphorescence of PTMCs due to their unique electronic and steric effects. This Concept article deals with the advances of carborane-functionalized PTMCs for optical applications.

  14. Full Papers

    1. Wittig Reactions | Hot Paper

      Diazo Strategy for the Synthesis of Pyridazines: Pivotal Impact of the Configuration of the Diazo Precursor on the Process

      Prof. Dr. Valerij A. Nikolaev, Dr. David Cantillo, Prof. Dr. C. Oliver Kappe, Dr. Jury J. Medvedev, Prof. Dr. G. K. Surya. Prakash and Dr. Murat B. Supurgibekov

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201503448

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      Configuration is the key: The effect of the configuration of vinyldiazo compounds on the diaza-Wittig cyclization to pyridazines was experimentally and theoretically demonstrated for the first time. Phosphazenes of vinyldiazocarbonyl compounds having cis stereochemistry at the vinyl bond readily produce pyridazines by a diaza-Wittig process, whereas their trans counterparts remain intact under similar reaction conditions. Upon UV irradiation trans-phosphazenes furnish pyridazines through a tandem trans-to-cis isomerization followed by intramolecular cyclization (see scheme).

    2. Enzyme Catalysis

      A Light-Activated Microheater for the Remote Control of Enzymatic Catalysis

      Yuanyuan Cao, Zhen Wang, Shenglong Liao, Jian Wang and Prof. Dr. Yapei Wang

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201503665

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      Hot stuff! A microheater composed of a porous polylactic acid matrix and polydopamine with notable photothermal conversion capability was designed and applied to accelerate enzymatic catalysis under NIR or natural-sunlight irradiation (see figure), which is very promising for the cost-effective remote manipulation of enzymatic applications.

    3. Multifunctional Materials | Hot Paper

      Solid-State Molecular Nanomagnet Inclusion into a Magnetic Metal–Organic Framework: Interplay of the Magnetic Properties

      Marta Mon, Alejandro Pascual-Álvarez, Thais Grancha, Dr. Joan Cano, Dr. Jesús Ferrando-Soria, Prof. Dr. Francesc Lloret, Prof. Dr. Jorge Gascon, Dr. Jorge Pasán, Dr. Donatella Armentano and Dr. Emilio Pardo

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201504176

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      Molecular magnetism meets MOFs! A unique example of solid-state incorporation of a single-ion magnet (SIM) within the pores of a magnetic 3D MOF in a single-crystal to single-crystal process is shown. The resulting host–guest supramolecular aggregate affords the first deep study on the interplay between the internal magnetic field of the MOF and the slow magnetic relaxation of the SIM (see figure).

  15. Communications

    1. Annulation

      Aerobic Dimerization of Enediyne Compounds: Construction of Naphthalene Frameworks

      Dongxu Wang, Fei Ling, Xiang Liu, Zexiang Li and Prof. Dr. Cheng Ma

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201504085

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      De novo-selectivity! A PdII-catalyzed bimolecular aerobic oxidative annulation of enediyne compounds using O2 (1 atm) in the presence of NaI is presented (see scheme; Ts=toluene-4-sulfonyl) that gives access to a class of symmetric naphthalene derivatives and several unsymmetrical naphthalene products containing up to six fully differentiated substituents in a regioisomer-free mode.

    2. Organic synthesis

      Single-Electron Transmetalation: Synthesis of 1,1-Diaryl-2,2,2-trifluoroethanes by Photoredox/Nickel Dual Catalytic Cross-Coupling

      Dr. DaWeon Ryu, David N. Primer, John C. Tellis and Prof. Dr. Gary A. Molander

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201504079

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      Fluorination: A method for the cross-coupling of benzylic α-trifluoromethylated alkylborons with (hetero)aryl bromides has been achieved through application of a photoredox/nickel dual catalytic system. The harsh conditions and high temperatures required by conventional Suzuki-coupling protocols are avoided by exploitation of an odd-electron pathway that permits transmetalation of these recalcitrant reagents at room temperature (see scheme).

    3. Synthetic Methods

      A Novel Pd-Catalysed Annulation Reaction for the Syntheses of Pyrroloindoles and Pyrroloquinolines

      Dr. Dattatraya H. Dethe and Raghavender Boda

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201503652

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      One-pot recipe! Pd-catalysed annulation reactions between indole derivatives and internal alkyne esters leading to various pyrrolo[1,2-a]indoles and pyrroloquinolines have been developed (see scheme). The strategy involves an intermolecular addition of the indole nitrogen on to the internal alkyne ester followed by an intramolecular insertion of a vinyl–palladium complex into the carbonyl group.

  16. Full Papers

    1. Coordination Chemistry

      You have full text access to this OnlineOpen article
      The Synthesis, Characterization and Dehydrogenation of Sigma-Complexes of BN-Cyclohexanes

      Amit Kumar, Jacob S. A. Ishibashi, Dr. Thomas N. Hooper, Tanya C. Mikulas, Prof. David A. Dixon, Prof. Shih-Yuan Liu and Prof. Andrew S. Weller

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201502986

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      Getting metalled down: The coordination chemistry and subsequent dehydrogenation/dehydrocoupling of the cyclic amine-boranes 2,2-R2-1,2-B,N-C4H10 (R2=H2, MeH, Me2) with Ir and Rh metal fragments is reported.

    2. Synthetic Methods

      Organocatalytic Asymmetric Conjugate Additions to Cyclopent-1-enecarbaldehyde: A Critical Assessment of Organocatalytic Approaches towards the Telaprevir Bicyclic Core

      Dr. Luca Bernardi, Dr. Mariafrancesca Fochi, Riccardo Carbone, Ada Martinelli, Dr. Martin E. Fox, Dr. Christopher J. Cobley, Bhaskar Kandagatla, Dr. Srinivas Oruganti, Dr. Vilas H. Dahanukar and Dr. Armando Carlone

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201503352

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      Organic bicycle: From a manufacturing perspective, eight organocatalytic approaches delivering advanced intermediates towards the challenging bicyclic amino acid core of telaprevir (see scheme) were identified and explored, highlighting the potential of organocatalytic technologies for a cost-effective preparation of pharmaceuticals.

    3. Luminescence

      Modular Synthesis of Spirocyclic Germafluorene–Germoles: A New Family of Tunable Luminogens

      Olena Shynkaruk, Dr. Gang He, Dr. Robert McDonald, Dr. Michael J. Ferguson and Prof. Dr. Eric Rivard

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201503377

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      Emissive Ge spirocycles were obtained by using a general zirconium-mediated synthetic route. Color-tunable luminescence (blue, green, and orange) was achieved by judicious placement of aromatic groups about the periphery of this new class of luminogen (see figure).

    4. Electrocatalysis | Hot Paper

      Titanium Dioxide-Grafted Copper Complexes: High-Performance Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

      Fei-Fei Wang, Dr. Ping-Jie Wei, Guo-Qiang Yu and Prof. Dr. Jin-Gang Liu

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201502589

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      Well grafted: An electrocatalyst consisting of a TiO2-grafted copper complex deposited on multiwalled carbon nanotubes shows surprisingly high selectivity for the 4 e reduction of O2 to water (≥97 %) in alkaline solution and demonstrates superior stability and excellent tolerance for the methanol crossover effect in comparison to a commercial Pt/C catalyst.

    5. Metallomesogens

      Polynuclear Silver(I) Triazole Complexes: Ion Conduction and Nanowire Formation in the Mesophase

      Dr. Padi Y. S. Su, Dr. S. J. Hsu, Jing C. W. Tseng, Prof. Hsiu-Fu Hsu, Prof. Wen-Jwu Wang and Prof. Ivan J. B. Lin

      Article first published online: 25 NOV 2015 | DOI: 10.1002/chem.201502823

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      Conducting assembly: Polynuclear silver(I) triazole metallomesogens in the mesophase exhibit ion conductivity through polymer-network channels and were employed as precursors for the thermolytic fabrication of silver nanowires by taking advantage of the assembled nature of the silver(I) ions (see figure).

    6. Alkaloid Synthesis | Hot Paper

      Collective Synthesis and Biological Evaluation of Tryptophan-Based Dimeric Diketopiperazine Alkaloids

      Shinji Tadano, Yukihiro Sugimachi, Prof. Dr. Michinori Sumimoto, Prof. Dr. Sachiko Tsukamoto and Prof. Dr. Hayato Ishikawa

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201503417

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      All in one: A concise synthesis of tryptophan-based dimeric diketopiperazine alkaloids (see scheme) is detailed based on a unique bioinspired dimerization reaction of tryptophan derivatives and a one-pot procedure for construction of diketopiperazine rings. Some of the synthetic alkaloids were discovered as new drug candidates for cancer or atherosclerosis therapy.

    7. Flow Microreactors

      Stereoselective Synthesis of 1,3-Diaminotruxillic Acid Derivatives: An Advantageous Combination of C[BOND]H-ortho-Palladation and On-Flow [2+2]-Photocycloaddition in Microreactors

      Dr. Elena Serrano, Dr. Alberto Juan, Angel García-Montero, Dr. Tatiana Soler, Francisco Jiménez-Márquez, Prof. Dr. Carlos Cativiela, Dr. M. Victoria Gomez and Dr. Esteban P. Urriolabeitia

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201503742

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      An advantageous combination: The stereoselective synthesis of ε-isomers of dimethyl esters of 1,3-diaminotruxillic acid is easily achieved in three steps (see scheme): 1) regioselective C[BOND]H-ortho-palladation of (Z)-2-aryl-4-aryliden-5(4H)-oxazolones; 2) efficient [2+2]-photocycloaddition of the C[DOUBLE BOND]C exocyclic bonds using LED light sources of different wavelengths in continuous flow microreactors; and 3) depalladation by hydrogenation in methanol.

    8. Nanostructures

      Rapid Non-Crosslinking Aggregation of DNA-Functionalized Gold Nanorods and Nanotriangles for Colorimetric Single-Nucleotide Discrimination

      Dr. Guoqing Wang, Dr. Yoshitsugu Akiyama, Dr. Tohru Takarada and Prof. Dr. Mizuo Maeda

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201503834

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      Anisotropic gold nanoparticles modified with DNA duplexes undergo rapid and highly sensitive aggregation at high ionic strength; namely, they can remain stably dispersed under the same conditions, provided that a single-nucleotide overhang exists at the outermost surface. This finding suggests their potential application to colorimetric single-nucleotide polymorphism (SNP) genotyping, which is based on redshifting in the inherent surface plasmon bands.

  17. Minireviews

    1. Cycloadditions

      Recent Progress in Dehydro(genative) Diels–Alder Reaction

      Dr. Wenbo Li, Liejin Zhou and Prof. Dr. Junliang Zhang

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201503571

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      DDAism: Dehydrogenative cycloadditions have attracted significant attention in synthetic chemistry. This Minireview highlights the recent efforts towards the development of dehydro or dehydrogenative Diels–Alder reactions to construct diverse aromatic compounds by a concerted pathway or a stepwise process.

  18. Communications

    1. Supramolecular Chemistry

      Supramolecular Alternating Polymer from Crown Ether and Pillar[5]arene-Based Double Molecular Recognition for Preparation of Hierarchical Materials

      Hui Li, Prof. Dr. Xiaodong Fan, Miao Qi, Zhen Yang, Haitao Zhang and Prof. Dr. Wei Tian

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201504012

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      Pillar talk: A novel supramolecular alternating polymer is formed through double molecular recognition of benzo-21-crown-7 with a secondary ammonium salt and pillar[5]arene with a neutral guest. It can be employed to obtain hierarchical materials, including 0D spherical aggregates, 1D nanofibers, 2D microstructured films, and 3D ordered glue.

    2. Heterocycle Synthesis

      Relayed Regioselective Alkynylation/Olefination of Unsymmetrical Cyclic Diaryliodonium Species Catalyzed by Cu and Pd: Affording Fluorescent Cytotoxic Benzoxazoles

      Daqian Zhu, Panpan Liu, Wenhua Lu, Haiwen Wang, Bingling Luo, Dr. Yumin Hu, Prof. Peng Huang and Dr. Shijun Wen

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201503791

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      Dual is good: Mediated by dual transition metal catalysts, Cu and Pd, amido groups in unsymmetrical cyclic diaryliodonium species dictate the order of reaction transformations. The resultant novel benzoxazole products exhibit unique structural features, fluorescence, and anticancer activity, enabling the tracking of a subcellular target.

  19. Full Papers

    1. Asymmetric Synthesis

      Accessing N-Stereogenicity through a Double Aza-Michael Reaction: Mechanistic Insights

      Sonja Kohrt, Dr. Nico Santschi and Dr. Ján Cvengroš

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201502670

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      TB or not TB: Cheap chiral esters of propiolic acid afford Tröger base (TB) analogues with a modified bridge in high yields and diastereomeric ratios of up to 74:26 in a diastereoselective double aza-Michael addition (DAMA) reaction to tetrahydrodiazocines. Mechanistic studies disclosed that a protic solvent as an additive facilitates the first intermolecular step, but acidic conditions proved unfavorable during the second intramolecular conjugate addition.

    2. Halogen Bonding

      Halogen-Bonding-Assisted Iodosylbenzene Activation by a Homogenous Iron Catalyst

      David P. de Sousa, Christina Wegeberg, Dr. Mads Sørensen Vad, Prof. Steen Mørup, Prof. Cathrine Frandsen, Dr. William A. Donald and Prof. Christine J. McKenzie

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201503112

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      Activation through halogen-bonding: Stabilization of an iron(III)–OIPh complex in the gas, solution, and solid phases is ascribed to strong intermolecular halogen-bonding. Two molecules of an iron(III) complex with a hexadentate ligand are proposed to work in unison to break the polymeric structure of [PhIO]n, concommitantly solubilizing and activating it to give a system that efficiently catalyzes the selective oxidation of electron-rich substrates.

    3. Homogeneous Catalysis

      Catalytic Activity of Cationic and Neutral Silver(I)–XPhos Complexes with Nitrogen Ligands or Tolylsulfonate for Mannich and Aza-Diels–Alder Coupling Reactions

      Dr. Abdessamad Grirrane, Dr. Eleuterio Álvarez, Prof. Dr. Hermenegildo García and Prof. Dr. Avelino Corma

      Article first published online: 24 NOV 2015 | DOI: 10.1002/chem.201503386

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      It’s Mannich! Cationic and neutral AgI–XPhos complexes with nitrogen or organosulfonate co-ligands are extremely active homogenous catalysts, far more active than analogous CuI and AuI complexes, in the promotion of Mannich and aza-Diels–Alder coupling reactions. Isolation of some AgI complexes has shed some light on the reaction mechanisms (see figure).

    4. Synthetic Methods

      Metal-Free Allene-Based Synthesis of Enantiopure Fused Polycyclic Sultones

      Prof. Dr. Benito Alcaide, Dr. Pedro Almendros, Dr. Cristina Aragoncillo, Dr. Israel Fernández and Gonzalo Gómez-Campillos

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201504045

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      A selective methodology for the preparation of fused δ-sultones from hydroxyallenynes involves a sulfonylation/rearrangement sequence followed by a cyclization/desaturation radical cascade, and a final intramolecular Diels–Alder reaction (see scheme). A DFT study has also been performed.

  20. Communications

    1. Silicon

      From an Isolable Acyclic Phosphinosilylene Adduct to Donor-Stabilized Si[DOUBLE BOND]E Compounds (E=O, S, Se)

      Kerstin Hansen, Dr. Tibor Szilvási, Dr. Burgert Blom, Dr. Elisabeth Irran and Prof. Dr. Matthias Driess

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201504113

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      Phosphino royale: A stable acyclic NHC-stabilized phosphinosilylene with different resonance structures was synthesized for the first time. The compound reacts with elemental sulfur, selenium, N2O, and CO2 to form unprecedented phosphino-substituted silanechalcogenones and silanechalcogenone-chalcogenophosphanchalcogenides, respectively.

    2. Asymmetric Catalysis

      Organocatalytic 1,4-Addition Reaction of 2-Formyl(thio)esters to Vinylketones: An Efficient Access to Acyclic Chiral Building Blocks with a Quaternary Carbon Stereocenter

      Toshifumi Tatsumi, Dr. Tomonori Misaki and Prof. Dr. Takashi Sugimura

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201504479

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      Chiral quaternary carbon stereocenters were constructed in an enantioselective 1,4-addition reaction of acyclic 2-formyl(thio)esters to vinylketones catalyzed by thiourea-tertiary amine containing a bulky chiral backbone with high enantioselectivity (up to 96 % ee). Derivatization of the adducts was also performed to obtain several less-accessible compounds bearing a chiral quaternary carbon stereocenter.

    3. Organic Synthesis

      Me2Zn-Mediated Catalytic Enantio- and Diastereoselective Addition of TosMIC to Ketones

      Abdul Raheem Keeri, Dr. Andrea Gualandi, Prof. Dr. Andrea Mazzanti, Prof. Dr. Janusz Lewinski and Prof. Dr. Pier Giorgio Cozzi

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201504362

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      Tos.MIC…and Turning… The highly diastereoselective and enantioselective addition of TosMIC to ketones is disclosed for the first time. A commercially available aminoalcohol and simple reaction conditions allowed the synthesis of oxazolines bearing a fully substituted stereocenter in high yields and ee values. The intermediates gave a rapid access to hydroxylaldehydes with no racemization.

    4. Organocatalysis

      Enantioselective NHC-Catalyzed Redox [2+2] Cycloadditions with Perfluoroketones: A Route to Fluorinated Oxetanes

      Alyn T. Davies, Prof. Alexandra M. Z. Slawin and Prof. Andrew D. Smith

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201504256

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      A tale of two rings: The N-heterocyclic carbene (NHC) catalyzed redox formal [2+2] cycloaddition between α-aroyloxyaldehydes and perfluoroketones, followed by ring-opening in situ delivers a variety of perfluorinated β-hydroxycarbonyl compounds in good yield, and excellent diastereo- and enantioselectivity. Through a reductive work-up and subsequent cyclization, this protocol offers access to highly substituted fluorinated oxetanes in two steps and in high ee.

  21. Full Papers

    1. Dual Catalysis

      Dual Lewis Acid–Lewis Base Catalyzed Acylcyanation of Aldehydes: A Mechanistic Study

      Dr. Anna Laurell Nash, Dr. Robin Hertzberg, Dr. Ye-Qian Wen, Björn Dahlgren, Prof. Tore Brinck and Prof. Christina Moberg

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503782

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      Two Lewis are better than one: Mechanistic studies have shed light on the mode of activation by the dual catalytic system used in the reaction between acyl cyanides and aldehydes, which provides highly enantioenriched O-acylated cyanohydrins. Different steps of the catalytic cycle are rate determining, depending on the electronic nature of the aldehydes (see scheme; RDS=rate-determining step, LB=Lewis base, LA=Lewis acid.

    2. Structure–Activity Relationships

      Reactivity Controlling Factors for an Aromatic Carbon-Centered σ,σ,σ-Triradical: The 4,5,8-Tridehydroisoquinolinium Ion

      Dr. Nelson R. Vinueza, Dr. Bartłomiej J. Jankiewicz, Vanessa A. Gallardo, Gregory Z. LaFavers, Dane DeSutter, Dr. John J. Nash and Prof. Hilkka I. Kenttämaa

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201502502

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      Pinning down reaction sites: Although both electron affinity (EA) and spin–spin coupling play major roles in controlling the overall reactivity of an aromatic carbon-centered σ,σ,σ-triradical with weakly interacting radical sites, spin–spin coupling determines the relative reactivity of each of the three radical sites (see scheme).

    3. Self-Assembly

      Nanoscale Platelet Formation by Monounsaturated and Saturated Sophorolipids under Basic pH Conditions

      Dr. Anne-Sophie Cuvier, Dr. Florence Babonneau, Jan Berton, Prof. Christian V. Stevens, Dr. Giulia C. Fadda, Gérard Péhau-Arnaudet, Patrick Le Griel, Dr. Sylvain Prévost, Dr. Javier Perez and Dr. Niki Baccile

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201502933

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      Micelles, plates, or aggregates? The self-assembly behavior of monounsaturated (C18:1) and fully saturated (C18:0) yeast-derived bolaamphiphile sophorolipids (SLs) under basic pH conditions has been studied by using TEM imaging under cryogenic conditions (see scheme).

    4. Single-Molecule Magnets

      Role of Magnetic Exchange Interactions in the Magnetization Relaxation of {3d–4f} Single-Molecule Magnets: A Theoretical Perspective

      Dr. Saurabh Kumar Singh, Mohammad Faizan Beg and Prof. Dr. Gopalan Rajaraman

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503102

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      Quantum tunneling: DFT and ab initio calculations suggest that both Ni⋅⋅⋅Dy and 1, 3 Ni⋅⋅⋅Ni (see figure) interactions help to quench the QTM behavior in {3d–4f} single-molecule magnets.

    5. Coordination Chemistry

      Multiple Cycloaddition Reactions of Ketones with a β-Diketiminate Al Compound

      Dr. Sankaranarayana Pillai Sarish, Dr. Prinson P. Samuel, Prof. Dr. Herbert W. Roesky, Prof. Dr. Carola Schulzke, Karikkeeriyil Nijesh, Dr. Susmita De and Dr. Pattiyil Parameswaran

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503137

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      Two molecules each of benzophenone and 2-benzoylpyridine undergo successive [4+2] cycloaddition with [L1AlMe]THF (L1=CH[C(CH2)](CMe)(2,6-iPr2C6H3N)2) to form bi- and triheterocyclic aluminium compounds, respectively (see scheme).

    6. Supramolecular Chemistry | Hot Paper

      Multifunctional Tricarbazolo Triazolophane Macrocycles: One-Pot Preparation, Anion Binding, and Hierarchical Self-Organization of Multilayers

      Dr. Semin Lee, Dr. Brandon E. Hirsch, Yun Liu, James R. Dobscha, David W. Burke, Dr. Steven L. Tait and Dr. Amar H. Flood

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503161

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      Many programmed behaviors: Macrocycles programmed their own synthesis, chelated non-traditional anions on their insides, and adhered to each other in a regular manner on surfaces. In all these functions, they took advantage of the repeating units of alternating carbazoles and triazoles running along the macrocycles’s backbone (see scheme).

    7. Synthesis Design

      Bottom-Up Fabrication of Single-Layered Nitrogen-Doped Graphene Quantum Dots through Intermolecular Carbonization Arrayed in a 2D Plane

      Dr. Rui Li, Dr. Yousong Liu, Dr. Zhaoqian Li, Dr. Jinpeng Shen, Dr. Yuntao Yang, Prof. Dr. Xudong Cui and Dr. Guangcheng Yang

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503191

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      One layer at a time: A single-layered intermolecular carbonization method was developed to synthesize single-layered nitrogen-doped graphene quantum dots with 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Symmetric intermolecular carbonization of TATB ensures small, uniform sizes (2–5 nm) of the resulting products, with high nitrogen-doping concentrations (see figure).

    8. Donor–Acceptor Systems

      Tuning the Electron Acceptor in Phthalocyanine-Based Electron Donor–Acceptor Conjugates

      Michael Sekita, Ángel J. Jiménez, Dr. M. Luisa Marcos, Dr. Esmeralda Caballero, Dr. M. Salomé Rodríguez-Morgade, Prof. Dr. Dirk M. Guldi and Prof. Dr. Tomás Torres

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503237

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      Long-lived charge separation: Perylenemonoimides (PMI), perylenemonoanhydrides (PMA), and perylene-monoimide-monoanhydrides (PMIMA) are studied as the oxidizing counterpart of phthalocyanines in electron donor–acceptor hybrids. The three systems show different degrees of orbital partitioning and generate long-lived charge-separation states upon photoexcitation.

    9. Natural Products

      Gold- or Silver-Catalyzed Syntheses of Pyrones and Pyridine Derivatives: Mechanistic and Synthetic Aspects

      Johannes Preindl, Dr. Kévin Jouvin, Daniel Laurich, Ing. Günter Seidel and Prof. Alois Fürstner

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503403

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      Dial-in: Upon proper choice of the ester terminus and the carbophilic catalyst, readily accessible 3-oxo-5-ynoate derivatives are converted either into 4-hydroxy-2-pyrones or 2-alkoxy-4-pyrones, as one desires. The conditions are unusually mild, as witnessed by a number of applications to delicate natural products. The underlying concept has also been extended to the preparation of N-heterocycles such as 2-alkoxypyridines or -isoquinolines.

    10. Hypervalent Compounds

      Expanding the Scope of Hypervalent Iodine Reagents for Perfluoroalkylation: From Trifluoromethyl to Functionalized Perfluoroethyl

      Dr. Václav Matoušek, Jiří Václavík, Peter Hájek, Julie Charpentier, Zsófia E. Blastik, Ewa Pietrasiak, Alena Budinská, Prof. Dr. Antonio Togni and Dr. Petr Beier

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503531

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      Fluoroalkylating agents: A series of new hypervalent iodine reagents that contain a functionalized tetrafluoroethyl group are prepared and used for electrophilic fluoroalkylations with S, O, P, and C nucleophiles (see scheme).

    11. Cyclization | Hot Paper

      Divergent Synthesis of Multisubstituted Tetrahydrofurans and Pyrrolidines via Intramolecular Aldol-type Trapping of Onium Ylide Intermediates

      Changcheng Jing, Dr. Dong Xing, Lixin Gao, Prof. Dr. Jia Li and Prof. Dr. Wenhao Hu

      Article first published online: 23 NOV 2015 | DOI: 10.1002/chem.201503621

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      Divergent strategy: A RhII-catalyzed synthesis of multisubstituted tetrahydrofurans and pyrrolidines has been realized (see scheme). This strategy utilizes easily accessible ketones and diazo compounds, and is proposed to proceed through an intramolecular aldol-type trapping of metal–carbene-induced oxonium ylide or ammonium ylide intermediates. Protein tyrosine phosphatase 1B inhibitory activities of the prepared heterocycles were also evaluated and shown to have good activities.

    12. Electrochemistry

      Improving the Analytical Performance of Graphene Oxide towards the Assessment of Polyphenols

      Kai Hwee Hui, Adriano Ambrosi, Martin Pumera and Alessandra Bonanni

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201503852

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      Reductio ergo sum: By electrochemically reducing graphene oxide material at increasingly negative potentials (from −0.25 to −1.50 V), eight electrochemically reduced graphene oxide (ERGO) platforms were obtained, carrying a decreasing amount of oxygen functionalities.

    13. Base Pairs

      Sequence-Dependent Duplex Stabilization upon Formation of a Metal-Mediated Base Pair

      Dr. Philipp Scharf, Biswarup Jash, Dr. Jissy A. Kuriappan, Dr. Mark P. Waller and Prof. Dr. Jens Müller

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201503405

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      Silver age: A strong effect of the neighboring base pairs and the next base pairs but one on the thermal stabilization induced by a novel metal-mediated base pair has been observed (see graphic). This effect has been rationalized with the aid of quantum mechanical/molecular mechanical (QM/MM) calculations.

    14. Synthesis Design

      Facile Installation of 2-Reverse Prenyl Functionality into Indoles by a Tandem N-Alkylation–Aza-Cope Rearrangement Reaction and Its Application in Synthesis

      Dr. Xiaobei Chen, Huaqiang Fan, Prof. Dr. Shilei Zhang, Chenguang Yu and Prof. Dr. Wei Wang

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201503355

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      Challenging synthesis: An operationally efficient N-alkylation, followed by microwave-irradiated ionic aza-Cope rearrangement–hydrolysis, process is reported (see scheme; Ms=mesyl). The tandem process serves as a powerful approach to the preparation of synthetically and biologically important, but challenging, 2-reverse quaternary-centered prenylated indoles with high efficiency.

    15. Mesoporous Bimetallic Nanocrystals

      Preparation of Mesoporous Bimetallic Au–Pt with a Phase-Segregated Heterostructure Using Mesoporous Silica

      Masaki Kitahara, Saori Kubara, Azusa Takai, Daisuke Takimoto, Shinpei Enomoto, Prof. Dr. Yusuke Yamauchi, Prof. Dr. Wataru Sugimoto and Prof. Dr. Kazuyuki Kuroda

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201503174

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      Interwoven precious metals: Mesoporous bimetallic Au–Pt with a phase-segregated heterostructure has been prepared by using mesoporous silica as a template. Stepwise deposition of Au and Pt resulted in successful formation of Au nanoparticles sandwiched between Pt nanowires (see graphic). All of the surfaces, including those near the heterojunctions and those of bulk Pt, were exposed (not covered with capping agents) and electrochemically active, which could be attributed to the mesoporous structure.

  22. Reviews

    1. Solar Energy

      Solar Electricity and Solar Fuels: Status and Perspectives in the Context of the Energy Transition

      Dr. Nicola Armaroli and Prof. Dr. Vincenzo Balzani

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201503580

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      On the move: The energy transition to renewables has started and the development of solar electricity is much more consolidated than that of solar fuels. The transition process suffers two key constraints, that is, relatively low net energy gains and the limited availability of mineral resources to manufacture converters and accumulators.

  23. Communications

    1. Synthetic Methods

      A Robust, Eco-Friendly Access to Secondary Thioamides through the Addition of Organolithium Reagents to Isothiocyanates in Cyclopentyl Methyl Ether (CPME)

      Dr. Vittorio Pace, Laura Castoldi, Serena Monticelli, Sandra Safranek, Alexander Roller, Prof. Dr. Thierry Langer and Prof. Dr. Wolfgang Holzer

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201504247

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      Not so stinky! A robust and highly efficient method to access a variety of functionalized secondary thioamides through the addition of organolithium reagents to isothiocyanates has been developed (see scheme; CPME=cyclopentyl methyl ether). This high yielding and simple methodology was also applicable for the synthesis of unprecedented bulkier thioamides under mild conditions. A complete retention of the enantiopurity was observed when chiral reagents were employed.

    2. Halogen Bonding Host–Guest System

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      Active-Metal Template Synthesis of a Halogen-Bonding Rotaxane for Anion Recognition

      Dr. Matthew J. Langton, Yaoyao Xiong and Prof. Paul D. Beer

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201504236

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      Be active! A macrocycle containing a bis-iodotriazole ligand is used to construct a halogen-bonding rotaxane by active-metal templation. An endo-complexed copper(I) cation (M1) bound within the flexible macrocycle templates rotaxane formation. Following copper-metal removal, exo-coordination of a larger rhenium(I) complex (M2) inverts the conformation of the rotaxane’s macrocycle component to facilitate halogen-bond-mediated anion recognition (see scheme, B=Lewis base, X=Lewis acid, halogen bond donor).

  24. Full Papers

    1. Computer Chemistry

      Binding of Reactive Oxygen Species at Fe[BOND]S Cubane Clusters

      Dr. Marta K. Bruska, Dr. Martin T. Stiebritz and Prof. Dr. Markus Reiher

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201503008

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      A quantum chemical study of the relative energetics for the binding of the most relevant reactive oxygen species (ROS) to [Fe4S4] clusters (see figure) is presented. The thermodynamic picture of ROS binding to iron[BOND]sulfur clusters established here can serve as a starting point for studying reactivity-modulating effects of the cluster-embedding protein environment on ROS-induced decomposition of iron[BOND]sulfur proteins.

    2. Luminescence

      The Control of Conjugation Lengths and Steric Hindrance to Modulate Aggregation-Induced Emission with High Electroluminescence Properties and Interesting Optical Properties

      Miao-Miao Xue, Yue-Min Xie, Lin-Song Cui, Xiang-Yang Liu, Xiao-Dong Yuan, Dr. Yong-Xi Li, Dr. Zuo-Quan Jiang and Prof. Dr. Liang-Sheng Liao

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201503041

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      Luminophores for organic LEDs: A series of new molecules, named SAF-2-TriPE, SAF-3-TriPE, and SAF-4-TriPE, that contain a quasi-TPE (tetraphenylethene) subunit were developed (see figure). These compounds displayed typical AIE (aggregation-induced emission) properties, with the exception of the more weakly emitting SAF-4-TriPE. Additionally, non-doped devices based on luminogens SAF-2-TriPE, SAF-3-TriPE, and SAF-4-TriPE were fabricated, and they displayed different electroluminescence properties with quantum efficiencies of 4.22, 1.71, and 1.42 %, respectively.

    3. Porous Materials

      Significant Gas Adsorption and Catalytic Performance by a Robust CuII–MOF Derived through Single-Crystal to Single-Crystal Transmetalation of a Thermally Less-Stable ZnII–MOF

      Tapan K. Pal, Dinesh De, Dr. Subhadip Neogi, Pradip Pachfule, S. Senthilkumar, Prof. Qiang Xu and Prof. Parimal K. Bharadwaj

      Article first published online: 20 NOV 2015 | DOI: 10.1002/chem.201503163

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      A change for the better: A 3D, thermally less-stable ZnII-framework undergoes single-crystal to single-crystal transmetalation with CuII to give an isostructural analogue. Unlike the initial structure, the CuII analogue is very stable. The activated CuII analogue exhibits significant selectivity for CO2 adsorption over N2 and H2 and catalyses size-selective Knoevenagel condensation reactions (see figure).

    4. Kinases

      Addressing the Glycine-Rich Loop of Protein Kinases by a Multi-Facetted Interaction Network: Inhibition of PKA and a PKB Mimic

      Dr. Birgit S. Lauber, Dr. Leo A. Hardegger, Alam K. Asraful, Bjarte A. Lund, Oliver Dumele, Dr. Michael Harder, Dr. Bernd Kuhn, Prof. Dr. Richard A. Engh and Prof. Dr. François Diederich

      Article first published online: 18 NOV 2015 | DOI: 10.1002/chem.201503552

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      The forgotten pocket: A new family of enantiopure inhibitors for protein kinase A (PKA) is reported. They complex to the ATP site, with inhibitory activities (Ki) down to the low single-digit nanomolar range. Besides binding to the hinge and the ribose pocket, the ligands also interact in a multi-facetted interaction network with the glycine-rich loop, which has been neglected in kinase inhibitor design. This network of orthogonal dipolar interactions, dispersive contacts, amide–π stacking, together with water replacement makes an important contribution to the overall ligand binding affinity.

    5. Total Synthesis

      Synthesis and Biological Evaluation of Lactimidomycin and Its Analogues

      Brian J. Larsen, Dr. Zhankui Sun, Eric Lachacz, Dr. Yaroslav Khomutnyk, Prof. Dr. Matthew B. Soellner and Prof. Dr. Pavel Nagorny

      Article first published online: 18 NOV 2015 | DOI: 10.1002/chem.201503527

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      Culminated effort: The total synthesis and in vitro biological studies of glutarimide-containing eukaryote translation elongation inhibitor lactimidomycin and its extended chain analogue are described.

    6. Metal–Organic Frameworks

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      Reversed Crystal Growth of RHO Zeolitic Imidazolate Framework (ZIF)

      Katherine Self, Michael Telfer, Dr. Heather F. Greer and Prof. Wuzong Zhou

      Article first published online: 18 NOV 2015 | DOI: 10.1002/chem.201503437

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      Core–shell structures: Non-classical reversed crystal growth of RHO ZIF with a rhombic dodecahedral morphology was revealed. The growth process includes aggregation of precursor materials to form disordered particles, surface re-crystallization forming a core–shell structure, extension of crystallisation from the shell to the core (see figure).

    7. Imaging Agents

      Multi-Functionalized Carbon Nano-onions as Imaging Probes for Cancer Cells

      Dr. Marco Frasconi, Dr. Roberto Marotta, Dr. Lyn Markey, Dr. Kevin Flavin, Dr. Valentina Spampinato, Dr. Giacomo Ceccone, Prof. Dr. Luis Echegoyen, Dr. Eoin M. Scanlan and Prof. Dr. Silvia Giordani

      Article first published online: 18 NOV 2015 | DOI: 10.1002/chem.201503166

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      Class onion: Surface functionalization of small multi-shell fullerenes (diameter of 5 nm) with imaging and cell recognition capabilities was accomplished. This integrated system allows the targeting of cancer cells and the detailed analysis of its pathway. The localization of the imaging probe in the cell environment was analysed by correlation of confocal and electron microscopy (see figure).

    8. Mesoporous Materials

      Oxygen-Assisted Synthesis of Mesoporous Palladium Nanoparticles as Highly Active Electrocatalysts

      Dr. Cuiling Li, Bo Jiang, Dr. Masataka Imura, Prof. Dr. Naoto Umezawa, Dr. Victor Malgras and Prof. Dr. Yusuke Yamauchi

      Article first published online: 18 NOV 2015 | DOI: 10.1002/chem.201503129

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      Taking advantage of successive oxygen adsorption and desorption caused by the oxidative etching effect, mesoporous Pd nanoparticles (MPNs; see high-resolution TEM image) enclosed by high-index facets are successfully prepared. The as-prepared MPNs exhibit excellent performance toward formic acid electro-oxidation, which is due to the synergetic effect between the diffusion-feasible tubular mesochannels and the high-index facets.

    9. Spin Crossover

      Stabilization of the Low-Spin State in a Mononuclear Iron(II) Complex and High-Temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding

      Dr. Sipeng Zheng, Niels R. M. Reintjens, Dr. Maxime A. Siegler, Dr. Olivier Roubeau, Prof. Elisabeth Bouwman, Andrii Rudavskyi, Prof. Remco W. A. Havenith and Dr. Sylvestre Bonnet

      Article first published online: 18 NOV 2015 | DOI: 10.1002/chem.201503119

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      All in a spin! A tetrapyridyl ligand bbpya (bbpya=N,N-bis(2,2′-bipyrid-6-yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)2] (1) have been prepared (see figure). This highly cooperative spin-crossover material displays one of the highest transition temperatures for mononuclear spin-crossover complexes (418 K). The strong stabilization of the low-spin state in this compound is confirmed by theoretical calculations.

    10. Chemical Biology | Hot Paper

      Dioxygen Binding in the Active Site of Histone Demethylase JMJD2A and the Role of the Protein Environment

      Wilian A. Cortopassi, Robert Simion, Charles E. Honsby, Prof. Tanos C. C. França and Prof. Robert S. Paton

      Article first published online: 18 NOV 2015 | DOI: 10.1002/chem.201502983

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      Environmental appreciation: The consideration of protein residues during QM/MM calculations for the O2 binding in lysine’s demethylation inside JMJD2A resulted in an energetically favourable process (see figure), with the oxidation of FeII to FeIII in the quintet overall spin state, driven by dispersion effects and electrostatic and van der Waals interactions. These contributions ensure exergonic O2 binding in the family of demethylase proteins.

  25. Communications

    1. Enantiomeric Separation

      Crystallisation from a Water-in-Oil Emulsion as a Route to Enantiomer Separation: The Case of dl-Threonine

      Sara E. Gilks and Roger J. Davey

      Article first published online: 18 NOV 2015 | DOI: 10.1002/chem.201503061

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      Enantiomerically pure crystals were formed by seeded emulsion crystallisation. This method demonstrates how the combination of colloid science and crystal chemistry can lead to an emulsion based process yielding robust separation of a purified solid and impure liquid phases with ultimate product ee of up to 90 %.

  26. Full Papers

    1. Hydrogenation | Hot Paper

      Fabrication of Ruthenium Nanoparticles in Porous Organic Polymers: Towards Advanced Heterogeneous Catalytic Nanoreactors

      Dr. John Mondal, Sudipta K. Kundu, Dr. Wilson Kwok Hung Ng, Ramana Singuru, Dr. Parijat Borah, Prof. Dr. Hajime Hirao, Prof. Dr. Yanli Zhao and Prof. Dr. Asim Bhaumik

      Article first published online: 17 NOV 2015 | DOI: 10.1002/chem.201504055

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      This way or that? A strategy has been adopted to develop a benzene–benzylamine-1 (BBA-1) porous organic polymer (POP) by Friedel–Crafts alkylation. Ru@POP behaves as a heterogeneous catalytic nanoreactor for the catalytic transfer hydrogenation of nitroarenes at RT through a direct reaction pathway, as supported by DFT computational calculations (see figure).

  27. Communications

    1. Synthetic Methods

      Ligand-Controlled Synthesis of [3]- and [4]Cyclo-9,9-dimethyl-2,7-fluorenes through Triangle- and Square-Shaped Platinum Intermediates

      Dr. Eiichi Kayahara, Rui Qu, Mitsuru Kojima, Dr. Takahiro Iwamoto, Prof. Dr. Toshiyasu Suzuki and Prof. Dr. Shigeru Yamago

      Article first published online: 17 NOV 2015 | DOI: 10.1002/chem.201504369

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      Electronic structures: Syntheses of [3]- and [4]cyclo-9,9-dimethyl-2,7-fluorenes, cyclic trimer, and tetramers of 9,9-dimethyl-2,7-fluorene (FR), respectively, were achieved by the platinum-mediated assembly of FR units and subsequent reductive elimination of platinum through a triangle-shaped tris-platinum and a square-shaped tetra-platinum complex, respectively. The physical properties of the products were also investigated theoretically and experimentally (see scheme).

    2. Direct Photoredox-Catalyzed Reductive Difluoromethylation of Electron-Deficient Alkenes

      Dr. Xiao-Jun Tang, Zuxiao Zhang and Prof. Dr. William R. Dolbier Jr.

      Article first published online: 17 NOV 2015 | DOI: 10.1002/chem.201504363

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      Nucleophilic fluorinated radicals: Photoredox-catalyzed reductive difluoromethylation of electron-deficient alkenes was achieved in one step under tin-free, mild and neutral conditions (see scheme).

  28. Full Papers

    1. N-Heterocycles

      Diastereo-Divergent Synthesis of Saturated Azaheterocycles Enabled by tBuOK-Mediated Hydroamination of Alkenyl Hydrazones

      Atsushi Kaga, Dr. Xingao Peng, Prof. Dr. Hajime Hirao and Prof. Dr. Shunsuke Chiba

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201504160

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      cis­ or­ trans? that is the question! Diastereo-divergent synthesis of saturated azaheterocycles has been achieved by tBuOK-mediated hydroamination of alkenyl hydrazones (see scheme). DFT calculations suggested that the cation–π interactions give rise to 2,5-cis selectivities in pyrrolidines, which were synthesized using γ,δ-unsaturated N-benzyl hydrazones. An unusual 2,6-trans selectivity in piperidine formation was also realized using the present strategy.

  29. Communications

    1. Natural Products

      Total Synthesis and Stereochemical Revision of Phacelocarpus 2-Pyrone A

      Thomas O. Ronson, Dr. Michael J. Burns, Martin H. H. Voelkel, Kieren J. Evans, Dr. Jason M. Lynam, Prof. Richard J. K. Taylor and Prof. Ian J. S. Fairlamb

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201504089

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      Phacelocarpus 2-pyrone A has been synthesised using Au-mediated vinyl ether methodology, and successive C(sp3)[BOND]H lithiation/alkylation, Wittig and Stille cross-coupling reactions. Data for the synthetic product, containing a Z-vinyl ether, matches the structural NMR data for the reported natural product.

    2. Supramolecular Chemistry | Hot Paper

      Concise Synthesis and Facile Nanotube Assembly of a Symmetrically Multifunctionalized Cycloparaphenylene

      Yuta Miyauchi, Dr. Kohei Johmoto, Dr. Nobuhiro Yasuda, Prof. Dr. Hidehiro Uekusa, Dr. Shintaro Fujii, Prof. Dr. Manabu Kiguchi, Dr. Hideto Ito, Prof. Dr. Kenichiro Itami and Prof. Dr. Ken Tanaka

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201504185

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      Rhod to nanotubes! The concise synthesis of a symmetrically multifunctionalized cycloparaphenylene (CPP), C3-symmetrical [12]CPP-hexacarboxylate, has been achieved by the rhodium-catalyzed macrocyclization and subsequent reductive aromatization (see scheme). C3-Symmetrical functionalization of CPP with highly polar alkoxycarbonyl groups enabled the facile nanotube assembly on the flat solid surface as well as in the crystalline state.

    3. Organocatalysis

      Preparation of Poly(ionic liquid)s-Supported Recyclable Organocatalysts for the Asymmetric Nitroaldol (Henry) Reaction

      Julia Großeheilmann, Dr. Jenny Bandomir and Prof. Dr. Udo Kragl

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201504290

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      “Gummy bear”-like hydrogels for the immobilization of organocatalysts: With embedding of benzoylcupreine in a PIL-based hydrogel, the catalyst was reused for four cycles after the Henry reaction without loss of enantioselectivity (up to 91 % ee).

  30. Full Papers

    1. Fluorescent Probes

      A Ratiometric Fluorescent Probe Based on a Through-Bond Energy Transfer (TBET) System for Imaging HOCl in Living Cells

      Dr. Yan-Ru Zhang, Dr. Ning Meng, Prof. Dr. Jun-Ying Miao and Prof. Dr. Bao-Xiang Zhao

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201503500

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      Selective and sensitive: A simple ratiometric probe (Naph-Rh) has been designed and synthesized based on a through-bond energy transfer (TBET) system for sensing HOCl. As the first TBET probe for HOCl, Naph-Rh showed excellent selectivity and sensitivity toward HOCl over other reactive oxygen species (ROS)/reactive nitrogen species (RNS), and could respond fast to a low concentration of HOCl in the real sample (see scheme).

  31. Communications

    1. Metalloenzymes

      O2 Inhibition of Ni-Containing CO Dehydrogenase Is Partly Reversible

      Meriem Merrouch, Jessica Hadj-Saïd, Lilith Domnik, Holger Dobbek, Christophe Léger, Sébastien Dementin and Vincent Fourmond

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201502835

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      More resistant than expected: NiFe CO dehydrogenases (CODHs), which catalyze the interconversion between CO2 and CO, have always been considered as extremely sensitive to O2. In contrast, the results presented here show that they are reductively reactivated after aerobic inhibition. Oxygen sensitivity varies greatly between the two CODHs that were characterized; suggesting that oxygen-tolerant CODHs may exist.

  32. Full Papers

    1. Self-Assembly

      Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells

      Yunyi Gao, Fadi Haso, Jennifer E. S. Szymanowski, Jing Zhou, Lang Hu, Prof. Dr. Peter C. Burns and Prof. Dr. Tianbo Liu

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201503773

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      U60 thing: U60 clusters can selectively let Na+/K+ pass through the surface nanopores while blocking Rb+/Cs+ outside under the co-effect of hydration shell and surface pores. This ion-transport process is proved to be entropy controlled. The resulting U60 surface charge density change will influence the size of their assemblies (see figure).

    2. Polymerization

      PPV Polymerization through the Gilch Route: Diradical Character of Monomers

      Dr. Jelena D. Nikolić, Dr. Sebastian Wouters, Dr. Julia Romanova, Dr. Akihiro Shimizu, Prof. Dr. Benoît Champagne, Prof. Dr. Thomas Junkers, Prof. Dr. Dirk Vanderzande, Prof. Dr. Dimitri Van Neck, Prof. Dr. Michel Waroquier, Prof. Dr. Veronique Van Speybroeck and Prof. Dr. Saron Catak

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201501900

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      Poly-calculations: The radical polymerization of poly(p-phenylene vinylene) (PPV) is of high interest due to its excellent properties for application in electronic devices. A mechanistic study was performed to gain insight into the mechanism of the Gilch route. Different steps in the radical polymerization were analyzed, including side-product formation (see scheme).

    3. Stacking Interactions

      Competition Between π–π and C[BOND]H/π Interactions: A Comparison of the Structural and Electronic Properties of Alkoxy-Substituted 1,8-Bis((propyloxyphenyl)ethynyl)naphthalenes

      Dr. Bradley E. Carson, Trent M. Parker, Dr. Edward G. Hohenstein, Dr. Glen L. Brizius, Whitney Komorner, Prof. Rollin A. King, Prof. David M. Collard and Prof.  C. David Sherrill

      Article first published online: 16 NOV 2015 | DOI: 10.1002/chem.201502363

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      Delicately balanced stack: Many reports on conjugated polymers in thin-film devices assume that alkyl chains facilitate solvation and also π-stacking. In this study, two models for alkoxy substituted phenylene ethynylenes are developed (see figure). Crystal structure analysis shows that arenes with 1,4-alkoxy substitution deviate from a π-stacking geometry, whereas π-stacking interactions were favored when C[BOND]H/π interactions were absent.