Chemistry - A European Journal

Cover image for Vol. 20 Issue 1

January 3, 2014

Volume 20, Issue 1

Pages 1–333

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Concepts
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Cover Picture: (Chem. Eur. J. 1/2014) (page 1)

      Article first published online: 23 DEC 2013 | DOI: 10.1002/chem.201390210

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      Let's celebrate the 20th volume of Chemistry–A European Journal. What started as a Full Paper journal, has now evolved and publishes not only Full Papers, but also Communications, Concepts, and Review-type articles, providing authors and readers a chance to experience chemistry in its various forms. Following the red thread on the cover picture you can see the covers of the first issue of each year, from the work by Anthony C. Legon et al. on the nature of the initial interaction between ethene and chlorine (Volume 1, 1995) to that of Matthias Driess (Volume 19, 2013) et al. highlighting a Concept article on N-heterocyclic silylenes.

    2. You have free access to this content
      Inside Cover: Rational Design of Carboxyl Groups Perpendicularly Attached to a Graphene Sheet: A Platform for Enhanced Biosensing Applications (Chem. Eur. J. 1/2014) (page 2)

      Dr. Alessandra Bonanni, Dr. Chun Kiang Chua and Prof. Martin Pumera

      Article first published online: 23 DEC 2013 | DOI: 10.1002/chem.201390212

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      Landscape by intelligent design  Rational grafting of graphenic terraces with COOH groups leads to high-performance biosensors; in a similar way, careful grafting of rice fields in the landscape of Bali island leads into large harvest. For more details, see Full Paper by M. Pumera at al. on page 217 ff.

    3. You have free access to this content
      Back Cover: A Supramolecular Photosynthetic Model Made of a Multiporphyrinic Array Constructed around a C60 Core and a C60–Imidazole Derivative (Chem. Eur. J. 1/2014) (page 336)

      Dr. K. Yoosaf, Dr. Julien Iehl, Dr. Iwona Nierengarten, Dr. Mohamed Hmadeh, Dr. Anne-Marie Albrecht-Gary, Dr. Jean-François Nierengarten and Dr. Nicola Armaroli

      Article first published online: 23 DEC 2013 | DOI: 10.1002/chem.201390214

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      C60 is a scaffold or an electron acceptor  depending on the number of addends. The role of different fullerene subunits is dramatically different in a supramolecular photosynthetic model obtained from a C60 monoadduct bearing an imidazole moiety and a C60 hexa-adduct decorated with 12 peripheral metalloporphyrins. In their Full Paper on page 223 ff., J. -F. Nierengarten, N. Armaroli et al. show that only the monosubstituted C60 derivative plays an active role (electron acceptor) in the cascade of photoinduced events.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Concepts
    7. Communications
    8. Full Papers
    1. Editorial

      You have free access to this content
      Editorial: Fresh-Faced Chemistry (pages 5–15)

      Dr. Neville Compton

      Article first published online: 23 DEC 2013 | DOI: 10.1002/chem.201304737

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Concepts
    7. Communications
    8. Full Papers
    1. Graphical Abstract: Chem. Eur. J. 1/2014 (pages 17–27)

      Article first published online: 23 DEC 2013 | DOI: 10.1002/chem.201390211

  4. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Concepts
    7. Communications
    8. Full Papers
  5. Concepts

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Concepts
    7. Communications
    8. Full Papers
    1. Chemoselective Bioconjugation

      Oxime Ligation: A Chemoselective Click-Type Reaction for Accessing Multifunctional Biomolecular Constructs (pages 34–41)

      Dr. Sébastien Ulrich, Dr. Didier Boturyn, Prof. Dr. Alberto Marra, Prof. Dr. Olivier Renaudet and Prof. Dr. Pascal Dumy

      Article first published online: 2 DEC 2013 | DOI: 10.1002/chem.201302426

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      Piecing the puzzle together: Chemoselective and biocompatible click reactions are important tools for the preparation of complex bioconjugates. Oxime ligation has recently emerged as a powerful click-type methodology (see scheme) for the effective engineering of multifunctional constructs, since it takes place in aqueous systems under mild acidic conditions, is compatible with most of the biomolecule functionalities, and generates only water as a side-product.

    2. Natural Products

      Heathcock-Inspired Strategies for the Synthesis of Fawcettimine-Type Lycopodium Alkaloids (pages 42–56)

      Rebecca A. Murphy and Prof. Richmond Sarpong

      Article first published online: 5 DEC 2013 | DOI: 10.1002/chem.201303975

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      I want to make a tricycle! The Heathcock 6-5-9 tricycle represents an elegant and powerful intermediate that is often employed in the synthesis of the fawcettimine-type Lycopodium alkaloids (see scheme). A review is given of methods used for the synthesis of densely functionalized cis-fused 6-5 bicycles and their elaboration to a variety of similar 6-5-9 tricycles. While this is a very worthwhile effort given the beautiful structural complexity and fascinating biological activities of these molecules, room remains for the development of other novel disconnections.

  6. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Concepts
    7. Communications
    8. Full Papers
    1. Synthetic Methods

      A General Method for N-Methylation of Amines and Nitro Compounds with Dimethylsulfoxide (pages 58–63)

      Xue Jiang, Prof. Dr. Chao Wang, Yawen Wei, Prof. Dr. Dong Xue, Prof. Dr. Zhaotie Liu and Prof. Dr. Jianliang Xiao

      Article first published online: 10 DEC 2013 | DOI: 10.1002/chem.201303802

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      Not just a solvent: DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst.

    2. Organocatalysis

      On the Mechanism of the Organocatalytic Asymmetric Epoxidation of α,β-Unsaturated Aldehydes (pages 64–67)

      Dr. Rebecca L. Davis, Dr. Kim L. Jensen, Dr. Björn Gschwend and Prof. Dr. Karl Anker Jørgensen

      Article first published online: 2 DEC 2013 | DOI: 10.1002/chem.201303942

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      Self-promotion: Mechanistic studies on the organocatalytic epoxidation of α,β-unsaturated aldehydes reveal the autoinductive behavior and establish that the hydrate/peroxyhydrate of the product is acting as a phase-transfer catalyst. Based on these results, an improved methodology that provides high selectivities and decreased catalyst loading, through the addition of chloral hydrate, has been developed (see scheme).

    3. Natural Product Synthesis

      Direct Aldol Strategy in Enantioselective Total Synthesis of Thuggacin B (pages 68–71)

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

      Article first published online: 2 DEC 2013 | DOI: 10.1002/chem.201304297

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      Antibiotic activity against Mycobacterium tuberculosis is exhibited by the natural product thuggacin B, the enantioselective total synthesis of which is described. Catalytic asymmetric direct aldol reactions promoted by Cu and Zn catalysts played a pivotal role in constructing four stereogenic centers. The execution of direct aldol reactions as the initial steps for the synthesis of two key fragments allowed the construction of the other stereogenic centers through chirality transfer. PG=protecting group.

    4. Magnetic Ionic Liquids

      A Magnetic Ionic Liquid Based on Tetrachloroferrate Exhibits Three-Dimensional Magnetic Ordering: A Combined Experimental and Theoretical Study of the Magnetic Interaction Mechanism (pages 72–76)

      Abel García-Saiz, Dr. Pedro Migowski, Dr. Oriol Vallcorba, Prof. Javier Junquera, Prof. Jesús Angel Blanco, Prof. Jesús Antonio González, Dr. María Teresa Fernández-Díaz, Prof. Jordi Rius, Prof. Jairton Dupont, Prof. Jesús Rodríguez Fernández and Dr. Imanol de Pedro

      Article first published online: 10 DEC 2013 | DOI: 10.1002/chem.201303602

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      Liquid attraction: The crystal structure, DFT calculations and magnetic properties of a new magnetic ionic liquid (MIL), Dimim[FeCl4], which displays 3 D magnetic ordering below 6 K, is presented. The study of its magnetostructural correlations points to the relative importance of two influential factors on the strength of the magnetic interaction of MILs: the spin population into the metal complex anion and the distances and angles between the superexchange pathways, type M-X-X-M (M=Metal and X=halide).

    5. Photoelectrochemistry

      Enhancing the Water Splitting Efficiency of Sn-Doped Hematite Nanoflakes by Flame Annealing (pages 77–82)

      Dr. Lei Wang, Dr. Chong-Yong Lee, Dr. Anca Mazare, Dr. Kiyoung Lee, Julian Müller, Prof. Dr. Erdmann Spiecker and Prof. Dr. Patrik Schmuki

      Article first published online: 11 DEC 2013 | DOI: 10.1002/chem.201303427

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      Going up in flames: The effect of flame annealing on the water-splitting properties of Sn decorated hematite nanoflakes was investigated (see figure). Flame annealing can yield a considerable enhancement in the maximum photocurrent under AM 1.5 (100 mW cm−2) conditions compared to classic furnace annealing. This is attributed to the fast direct heating that maintains the nanoscale morphology, leads to optimized Sn decoration, and minimizes detrimental substrate effects (AM=air mass).

    6. Asymmetric Synthesis

      Catalytic and Asymmetric Fluorolactonisations of Carboxylic Acids through Anion Phase Transfer (pages 83–86)

      Dr. Dixit Parmar, Dr. Modhu Sudan Maji and Prof. Dr. Magnus Rueping

      Article first published online: 4 DEC 2013 | DOI: 10.1002/chem.201303385

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      Don't fluoro-get me! An almost forgotten mode of halolactonisation, namely the fluorolactonisation has been developed with aryl carboxylic acids to give fluorinated isobenzofurans (see scheme). This mild and simple procedure can be conducted in non-polar solvents. In addition the first example of an asymmetric variant is also presented.

    7. Chlorophyll Breakdown

      You have full text access to this OnlineOpen article
      Hydroxymethylated Phyllobilins: A Puzzling New Feature of the Dioxobilin Branch of Chlorophyll Breakdown (pages 87–92)

      Iris Süssenbacher, Dr. Bastien Christ, Prof. Dr. Stefan Hörtensteiner and Prof. Dr. Bernhard Kräutler

      Article first published online: 2 DEC 2013 | DOI: 10.1002/chem.201303398

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      Turning pale: In senescent, yellow leaves of Arabidopsis thaliana (see photograph) colorless tetrapyrroles accumulate, which mostly belong to the dioxobilin-type chlorophyll catabolites (DCCs). In an Arabidopsis mutant several DCCs could be identified that carried an extra hydroxymethyl group, indicating an addition to the carbon skeleton during chlorophyll breakdown.

    8. Asymmetric Catalysis

      Copper–Boxmi Complexes as Highly Enantioselective Catalysts for Electrophilic Trifluoromethylthiolations (pages 93–97)

      Dr. Qing-Hai Deng, Christoph Rettenmeier, Prof. Dr. Hubert Wadepohl and Prof. Dr. Lutz H. Gade

      Article first published online: 11 DEC 2013 | DOI: 10.1002/chem.201303641

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      Pincer with the right twist: The highly enantioselective trifluoromethylthiolation of β-ketoesters using chiral copper–boxmi complexes is reported. A number of α-SCF3-substituted β-ketoesters have been obtained with up to >99 % enantiomeric excess (ee), and the trifluoromethylthiolated products were then transformed diastereoselectively to α-SCF3-β-hydroxyesters with two adjacent quaternary stereocenters (see scheme).

    9. Catalysis

      An Unusual Triphenylphosphine Oxide Catalyzed Stereoselective 1,3-Dichlorination of Unsaturated Ketoesters (pages 98–101)

      Tian-Yang Yu, Yao Wang and Peng-Fei Xu

      Article first published online: 28 NOV 2013 | DOI: 10.1002/chem.201303688

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      Finding the missing piece: An unusual Ph3PO-catalyzed stereoselective 1,3-dicholorination of an unsaturated ketoester has been developed (see scheme, MS = molecular sieves). The novel activation mode involved in this cascade reaction can promote consecutively elusive transformations. The products were obtained with good yields and excellent stereoselectivities.

    10. N-Heterocyclic Carbenes

      From Diphosphino-Functionalized 1,3-Dialkylimidazolium Cations to Imidazolones through Dehydrogenative C[BOND]N Coupling (pages 102–105)

      Prof. Javier Ruiz and Alejandro F. Mesa

      Article first published online: 28 NOV 2013 | DOI: 10.1002/chem.201303773

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      Breaking and reforming the imidazolium ring! Diphosphino-functionalized 1,3-dialkylimidazolium salts react with KOH affording amine/formamide open-chain products, which fully revert to the imidazolium cation by treatment with a variety of acids or are converted to 2-imidazolones by noncatalyzed intramolecular dehydrogenative C[BOND]N coupling (see scheme, Tf = triflate).

  7. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Concepts
    7. Communications
    8. Full Papers
    1. Carbohydrate Mimetics

      Tetrafluorination of Sugars as Strategy for Enhancing Protein–Carbohydrate Affinity: Application to UDP-Galp Mutase Inhibition (pages 106–112)

      Inès N'Go, Samuel Golten, Dr. Ana Ardá, Prof. Javier Cañada, Prof. Jesús Jiménez-Barbero, Dr. Bruno Linclau and Prof. Stéphane P. Vincent

      Article first published online: 5 DEC 2013 | DOI: 10.1002/chem.201303693

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      On all fours: Tetrafluorinated analogues of UDP-galactopyranose and UDP-galactofuranose were synthesized and assayed against UDP-galactopyranose mutase (UGM), a key enzyme in Mycobacterium tuberculosis cell wall biosynthesis. The tetrafluorinated sugar analogue was found to bind the enzyme more effectively than the unfluorinated natural substrate.

    2. Single-Molecule Magnets

      Can Anisotropic Exchange Be Reliably Calculated Using Density Functional Methods? A Case Study on Trinuclear MnIII-MIII-MnIII (M=Fe, Ru, and Os) Cyanometalate Single-Molecule Magnets (pages 113–123)

      Saurabh Kumar Singh and Prof. Gopalan Rajaraman

      Article first published online: 29 NOV 2013 | DOI: 10.1002/chem.201303489

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      Singles club: The role of anisotropic exchange in trinuclear single-molecule magnets (SMMs) has been explored using DFT calculations and ab initio studies (see figure).

    3. Carbohydrates

      Significant Substituent Effect on the Anomerization of Pyranosides: Mechanism of Anomerization and Synthesis of a 1,2-cis Glucosamine Oligomer from the 1,2-trans Anomer (pages 124–132)

      Dr. Shino Manabe, Prof. Hiroko Satoh, Prof. Jürg Hutter, Dr. Hans Peter Lüthi, Dr. Teodoro Laino and Dr. Yukishige Ito

      Article first published online: 4 DEC 2013 | DOI: 10.1002/chem.201303474

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      Many bonds make light work! The N-acetyl group on the carbamate affects the trans/cis anomerization of aminoglycosides with 2,3-trans carbamate groups, under mild acidic conditions through endocyclic cleavage (see scheme). DFT calculations revealed that the acetyl carbonyl is close to the anomeric position. Oligoaminoglycosides with multiple 1,2-cis glycosidic bonds were generated in one step from 1,2-trans glycosides.

    4. Sensors

      Effect of the Counterion on Light Emission: A Displacement Strategy to Change the Emission Behaviour from Aggregation-Caused Quenching to Aggregation-Induced Emission and to Construct Sensitive Fluorescent Sensors for Hg2+ Detection (pages 133–138)

      Dr. Na Zhao, Dr. Jacky W. Y. Lam, Dr. Herman H. Y. Sung, Dr. Hui Min Su, Prof. Ian D. Williams, Prof. Kam Sing Wong and Prof. Ben Zhong Tang

      Article first published online: 4 DEC 2013 | DOI: 10.1002/chem.201303251

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      From darkness to light! A series of tetraphenylethene-functionalised benzothiazolium salts with different counteranions (TPEBe[BOND]X) was developed. By varying the counteranion from I to ClO4 or PF6, TPEBe[BOND]X changes its emission behaviour from aggregation-caused quenching to aggregationinduced emission (see figure). TPEBE[BOND]I shows a light-up response to Hg2+.

    5. Li-Ion Batteries

      Confined Nanospace Pyrolysis for the Fabrication of Coaxial Fe3O4@C Hollow Particles with a Penetrated Mesochannel as a Superior Anode for Li-Ion Batteries (pages 139–145)

      Cheng Lei, Fei Han, Qiang Sun, Prof. Dr. Wen-Cui Li and Prof. Dr. An-Hui Lu

      Article first published online: 22 NOV 2013 | DOI: 10.1002/chem.201303175

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      Recharge your batteries: Confined nanospace pyrolysis was used to fabricate coaxial Fe3O4@C hollow particles with a penetrated mesochannel with an inner diameter of 18 nm and a continuous carbon shell. When evaluated as an anode material for lithium-ion batteries, such hollow particles with an open interior cavity deliver high specific capacity and excellent cycling stability, accompanied by high Coulombic efficiency (see scheme).

    6. Fluorescent Probes

      Polar Red-Emitting Rhodamine Dyes with Reactive Groups: Synthesis, Photophysical Properties, and Two-Color STED Nanoscopy Applications (pages 146–157)

      Dr. Kirill Kolmakov, Dr. Christian A. Wurm, M. Sc. Dirk N. H. Meineke, Dipl.-Biol. Fabian Göttfert, Prof. Vadim P. Boyarskiy, Dr. Vladimir N. Belov and Prof. Stefan W. Hell

      Article first published online: 11 DEC 2013 | DOI: 10.1002/chem.201303433

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      STEDy dyes: Design of photostable red-emitting rhodamines with polar groups resulted in two bright dyes with absorption/emission bands at 579/609 and 635/655 nm. They were used in two-color optical microscopy. Images with 40 nm optical resolution, low cross-talk and negligible background were obtained using stimulated emission depletion (STED; see figure; scale bar: 2 μm).

    7. Dual-Responsive Bioprobes

      Tetraphenylethylene Conjugated with a Specific Peptide as a Fluorescence Turn-On Bioprobe for the Highly Specific Detection and Tracing of Tumor Markers in Live Cancer Cells (pages 158–164)

      Dr. Yanyan Huang, Fang Hu, Prof. Rui Zhao, Dr. Guanxin Zhang, Dr. Hua Yang and Prof. Deqing Zhang

      Article first published online: 25 NOV 2013 | DOI: 10.1002/chem.201303679

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      Double detection: A fluorescence turn-on probe, TPE-AP2H (see structure), was developed by incorporating an aggregation-induced emission (AIE) fluorophore into a specific peptide, which can simultaneously discriminate the expression level of the LAPTM4B protein and the low-pH microenvironment of tumor cells. This dual-responsive AIE bioprobe allows the real-time tracing of the cancer biomarker at the subcellular level in live cancer cells.

    8. Single-Ion Magnets

      Identification of the Chromophore in the Apatite Pigment [Sr10(PO4)6(CuxOH1−xy)2]: Linear OCuO Featuring a Resonance Raman Effect, an Extreme Magnetic Anisotropy, and Slow Spin Relaxation (pages 165–178)

      Prof. Pavel E. Kazin, Mikhail A. Zykin, Dr. Yan V. Zubavichus, Oxana V. Magdysyuk, Dr. Robert E. Dinnebier and Prof. Dr. Martin Jansen

      Article first published online: 25 NOV 2013 | DOI: 10.1002/chem.201303136

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      Chromophore and SIM in one pot: The paramagnetic chromophore OCuO anion has been found in the phosphate apatite pigment covering the magenta/violet/blue color range. Being the first example of a linear coordinated Cu3+ in a crystal lattice, it exhibits unusual properties: it coexists with a Cu1+ species and shows unprecedentedly large magnetic anisotropy for d ions, which induces slow spin relaxation, relating the pigment to single-ion magnets (SIMs; see figure).

    9. Self-Assembly

      Self-Assembly of a Highly Organized, Hexameric Supramolecular Architecture: Formation, Structure and Properties (pages 179–186)

      Dr. Gaël Schaeffer, Dr. Olaf Fuhr, Prof. Dieter Fenske and Prof. Jean-Marie Lehn

      Article first published online: 11 DEC 2013 | DOI: 10.1002/chem.201303186

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      New news on old compounds: Compounds, known for more than a decade, have been found, in the solid state as well as in solvents of low polarity at room temperature, to exist not as the monomers previously characterized, but to undergo a remarkable self-assembly into a complex supramolecular species (see figure).

    10. Graphene

      N-Doped Graphene Derived from Biomass as a Visible-Light Photocatalyst for Hydrogen Generation from Water/Methanol Mixtures (pages 187–194)

      Cristina Lavorato, Dr. Ana Primo, Prof. Raffaele Molinari and Prof. Hermenegildo Garcia

      Article first published online: 10 DEC 2013 | DOI: 10.1002/chem.201303689

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      Generation (N)G: In contrast to graphene, N-doped graphene ((N)G) behaves as a semiconductor and exhibits high efficiency for the photocatalytic generation of hydrogen from water/methanol mixtures without Pt or any other metal with a similar efficiency (see figure). Unlike graphene oxide, which is only active under UV light, this photocatalysis proceeds under UV or visible light and is influenced by the crystallinity and pyrolysis temperature.

    11. Sensors

      Highly Sensitive and Selective Detection of Nitrophenolic Explosives by Using Nanospheres of a Tetraphenylethylene Macrocycle Displaying Aggregation-Induced Emission (pages 195–201)

      Hai-Tao Feng and Yan-Song Zheng

      Article first published online: 27 NOV 2013 | DOI: 10.1002/chem.201302638

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      AIE-based detection: A tetraphenylethylene Schiff-base macrocycle (see scheme) displaying aggregation-induced emission shows a sensitive and selective response to 2,4,6-trinitrophenol (TNP) and 2,4-dinitrophenol (DNP). This response can be exploited to detect TNP and DNP at nanomolar levels. Moreover, the macrocycle exhibits a superamplified quenching effect with DNP but not with TNP, providing a possible means of discriminating these compounds (AIE = aggregation induced emission).

    12. Electron Transfer

      Cyanobuta-1,3-dienes as Novel Electron Acceptors for Photoactive Multicomponent Systems (pages 202–216)

      Dr. Francesca Tancini, Dr. Filippo Monti, Dr. Kara Howes, Dr. Abdelhalim Belbakra, Dr. Andrea Listorti, Dr. W. Bernd Schweizer, Dr. Philippe Reutenauer, Dr. José-Lorenzo Alonso-Gómez, Dr. Claudio Chiorboli, Lorenz M. Urner, Dr. Jean-Paul Gisselbrecht, Prof. Dr. Corinne Boudon, Dr. Nicola Armaroli and Prof. Dr. François Diederich

      Article first published online: 12 DEC 2013 | DOI: 10.1002/chem.201303284

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      Catch the electron: Strongly electron-accepting multicyanobuta-1,3-dienes provide a new class of electron acceptors for incorporation into photoactive multicomponent systems. Photophysical and electrochemical investigations revealed photoinduced intramolecular electron transfer (PET) from a ZnII porphyrin to 1,1,4,4-tetracyanobuta-1,3-diene acceptor sites appended by an insulating spacer, with a long-lived charge-separated excited state of 2.3 μs in benzonitrile.

    13. Biosensors

      Rational Design of Carboxyl Groups Perpendicularly Attached to a Graphene Sheet: A Platform for Enhanced Biosensing Applications (pages 217–222)

      Dr. Alessandra Bonanni, Dr. Chun Kiang Chua and Prof. Martin Pumera

      Article first published online: 5 DEC 2013 | DOI: 10.1002/chem.201303582

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      Superior properties: It was demonstrated that it is possible to considerably increase the amount of carboxyl groups on graphene oxide by grafting carboxyl groups perpendicularly to the graphene sheets by free-radical addition. Such reactive carboxyl groups can be used as anchoring points for biomolecule attachment by carbodiimide chemistry (see figure).

    14. Artificial Photosynthesis

      A Supramolecular Photosynthetic Model Made of a Multiporphyrinic Array Constructed around a C60 Core and a C60–Imidazole Derivative (pages 223–231)

      Dr. K. Yoosaf, Dr. Julien Iehl, Dr. Iwona Nierengarten, Dr. Mohamed Hmadeh, Dr. Anne-Marie Albrecht-Gary, Dr. Jean-François Nierengarten and Dr. Nicola Armaroli

      Article first published online: 6 DEC 2013 | DOI: 10.1002/chem.201303481

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      Photosynthetic mimics: A self-assembled photosynthetic model resulting from the association of a C60–imidazole derivative with a multimetalloporphyrin array constructed around a hexasubstituted C60 core is presented (see figure). Whereas the fullerene hexa-adduct core does not play an active role in the cascade of photoinduced events of the supramolecular ensemble, the guest fullerene monoadduct acts as an electron acceptor, leading to a long-lived charge-separated state in benzonitrile.

    15. Polymerisation Catalysts

      NMR Spectroscopy and X-Ray Characterisation of Cationic N-Heteroaryl-Pyridylamido ZrIV Complexes: A Further Level of Complexity for the Elusive Active Species of Pyridylamido Olefin Polymerisation Catalysts (pages 232–244)

      Dr. Gang Li, Dr. Cristiano Zuccaccia, Dr. Consiglia Tedesco, Dr. Ilaria D'Auria, Prof. Dr. Alceo Macchioni and Prof. Dr. Claudio Pellecchia

      Article first published online: 28 NOV 2013 | DOI: 10.1002/chem.201303021

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      Expect the unexpected! Zirconium dialkyl pre-catalysts with pyrrolyl- or indolyl-pyridyl-amido ligands (see structure) undergo unexpected behaviour in the polymerisation of olefins that seems to be related to the formation of an unprecedented dimeric cationic species, in which the pyrrolyl or indolyl moiety of one unit interacts with the metal centre of the other. The dimeric species were characterised using advanced 1D and 2D NMR spectroscopic techniques and X-ray diffraction.

    16. Catalysis

      Primary Amines by Transfer Hydrogenative Reductive Amination of Ketones by Using Cyclometalated IrIII Catalysts (pages 245–252)

      Dinesh Talwar, Noemí Poyatos Salguero, Dr. Craig M. Robertson and Prof. Jianliang Xiao

      Article first published online: 25 NOV 2013 | DOI: 10.1002/chem.201303541

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      Reduce the work! A broad range of ketones have been successfully aminated to afford primary amines under transfer-hydrogenation conditions by using ammonium formate as the amine source and 0.1 mol % of a cyclometalated IrIII catalyst (see scheme).

    17. Natural Products

      Total Synthesis of (+/−)-Frondosin B and (+/−)-5-epi-Liphagal by Using a Concise (4+3) Cycloaddition Approach (pages 253–262)

      Duchan R. Laplace, Bart Verbraeken, Prof. Dr. Kristof Van Hecke and Prof. Dr. Johan M. Winne

      Article first published online: 28 NOV 2013 | DOI: 10.1002/chem.201303273

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      Cycloheptanes: Furfuryl alcohols serve as effective three-carbon dienophiles for a wide range of dienes in stereoselective cycloaddition reactions. This efficient reaction has been used to prepare two cycloheptanoid natural products, offering a conceptually straightforward and short synthetic entry into a biologically interesting class of polycyclic meroterpenoids (see scheme; TFA = trifluoroacetic acid).

    18. Flow Chemistry

      Investigation of a Lithium–Halogen Exchange Flow Process for the Preparation of Boronates by Using a Cryo-Flow Reactor (pages 263–271)

      Dr. James A. Newby, Lena Huck, Dr. D. Wayne Blaylock, Dr. Paul M. Witt, Prof. Steven V. Ley and Dr. Duncan L. Browne

      Article first published online: 11 DEC 2013 | DOI: 10.1002/chem.201303736

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      A cool setup: A small footprint, modular setup based around a cryo-flow reactor is reported for the preparation of gram quantities of boronic esters. With minimum alteration, including the addition of a data logger with thermocouples and a liquid–liquid separator, the same equipment can be used to scale the process, inclusive of an in-line extraction.

    19. Stereocontrolled Synthesis

      Synthesis of Cyclobakuchiols A, B, and C by Using Conformation-Controlled Stereoselective Reactions (pages 272–278)

      Hidehisa Kawashima, Yuki Kaneko, Masahiro Sakai and Prof. Dr. Yuichi Kobayashi

      Article first published online: 22 NOV 2013 | DOI: 10.1002/chem.201303538

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      Control is key! Synthesis of cyclobakuchiols A and C was stereoselectively accomplished by conformation-controlled substitution of allylic picolinate with Me2CuMgBr⋅MgBr2/ZnI2. On the other hand, cyclobakuchiol B was synthesized by stereoselective addition of the cyclohexanecarboxylate enolate to CH2[DOUBLE BOND]CHSOPh (see scheme).

    20. Supramolecular Gels

      You have full text access to this OnlineOpen article
      Blending Gelators to Tune Gel Structure and Probe Anion-Induced Disassembly (pages 279–291)

      Dr. Jonathan A. Foster, Dr. Robert M. Edkins, Gary J. Cameron, Dr. Neil Colgin, Dr. Katharina Fucke, Sam Ridgeway, Dr. Andrew G. Crawford, Prof. Todd B. Marder, Prof. Andrew Beeby, Dr. Steven L. Cobb and Prof. Jonathan W. Steed

      Article first published online: 2 DEC 2013 | DOI: 10.1002/chem.201303153

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      It all adds up: Low molecular weight gelators containing a common bis-urea motif have been blended together to produce both orthogonal assemblies and new mixed gelator structures with distinct morphologies and packing arrangements (see graphic). The use of fluorescent gel blends provides new insights into gel formation and anion-mediated gel dissolution.

    21. Gold Catalysis

      Synthesis of Polycyclic Indole Skeletons by a Gold(I)-Catalyzed Cascade Reaction (pages 292–296)

      Tao Wang, Shuai Shi, Daniel Pflästerer, Eva Rettenmeier, Dr. Matthias Rudolph, Dr. Frank Rominger and Prof. Dr. A. Stephen K. Hashmi

      Article first published online: 20 DEC 2013 | DOI: 10.1002/chem.201303539

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      Domino addition/substitution: 1H-Imidazo[1, 5-a]indol-3(2 H)-ones were prepared in a new anellation reaction from simple, easily available urea-substituted 3-phenylpropargyl alcohols (see scheme).

    22. Carbene Chemistry

      Chemical Behaviour of a Prototype Boryl(phosphino)carbene (pages 297–303)

      Dr. Florie Lavigne, Dr. Eddy Maerten, Dr. Gilles Alcaraz, Dr. Nathalie Saffon-Merceron and Dr. Antoine Baceiredo

      Article first published online: 28 NOV 2013 | DOI: 10.1002/chem.201303039

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      The reactivity of stable boryl(phosphino)carbene 1 has been investigated. It showed the typical reactivity of transient singlet carbenes (1,2-migration and [2+1] cycloaddition), together with marked α,β-ambiphilic character (see scheme). Due to its specific electronic properties, carbene 1 enabled the formation of an original bicyclo[1.1.0]phosphetanium salt and a borylcyclopropene.

    23. Gold Chemistry

      Hexanuclear Gold(I) Phosphide Complexes as Platforms for Multiple Redox-Active Ferrocenyl Units (pages 304–310)

      Dr. Terence Kwok-Ming Lee, Dr. Eddie Chung-Chin Cheng, Dr. Nianyong Zhu and Prof. Dr. Vivian Wing-Wah Yam

      Article first published online: 20 DEC 2013 | DOI: 10.1002/chem.201301948

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      Batteries of gold? The synthesis, X-ray crystal structures, electrochemical, and spectroscopic studies of a series of hexanuclear AuI cluster complexes (see figure), stabilized by bridging phosphine ligands as platforms for multiple redox-active ferrocenyl units, are reported. These complexes may serve as an ideal system for the design of multi-electron reservoir and molecular battery systems.

    24. Photocatalysis

      Construction of Shallow Surface States through Light Ni Doping for High-Efficiency Photocatalytic Hydrogen Production of CdS Nanocrystals (pages 311–316)

      Shuo Li, Lijing Zhang, Tengfei Jiang, Liping Chen, Prof.Dr. Yanhong Lin, Prof. Dr. Dejun Wang and Prof. Dr. Tengfeng Xie

      Article first published online: 28 NOV 2013 | DOI: 10.1002/chem.201302679

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      Ni-doped CdS nanowires were synthesized by a one-step method. Light and heavy Ni doping can form shallow and deep surface states, respectively (figure: CB, conduction band; VB, valence band). The shallow surface states can prolong the lifetime of photogenerated charge carriers, whereas the deep surface states lead to their recombination. The enhanced density of shallow surface states significantly promote photocatalytic H2 production.

    25. Organic Synthesis

      Rhodium-Catalyzed Intramolecular Hydroarylation of 1-Halo-1-alkynes: Regioselective Synthesis of Semihydrogenated Aromatic Heterocycles (pages 317–322)

      Hirohiko Murase, Kousuke Senda, Masato Senoo, Prof. Dr. Takeshi Hata and Prof. Dr. Hirokazu Urabe

      Article first published online: 2 DEC 2013 | DOI: 10.1002/chem.201303008

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      Ring a rhodium! Regioselective intramolecular hydroarylation of haloacetylenes efficiently catalyzed by [Rh2(tfa)4] (see scheme; tfa=OCOCF3) gave semihydrogenated aromatic heterocycles in good to excellent yields.

    26. C[BOND]H Activation

      Microwave-Assisted, Rhodium(III)-Catalyzed N-Annulation Reactions of Aryl and α,β-Unsaturated Ketones with Alkynes (pages 323–333)

      Hyejeong Lee, Yong-Kyun Sim, Dr. Jung-Woo Park and Prof. Dr. Chul-Ho Jun

      Article first published online: 25 NOV 2013 | DOI: 10.1002/chem.201302699

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      Ring road: One-pot N-annulation reactions of aryl and α,β-unsaturated ketones with alkynes in the presence of NH4OAc under microwave (MW) irradiation conditions have been developed (see scheme). These processes lead to the rapid formation of the respective isoquinoline and pyridine derivatives. In addition, an approach for the synthesis of pyridines that involves four-component reactions is presented.

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