Chemistry - A European Journal

Cover image for Chemistry - A European Journal

November 5, 2012

Volume 18, Issue 45

Pages 14213–14538

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: Enantiomerization Mechanism of Thalidomide and the Role of Water and Hydroxide Ions (Chem. Eur. J. 45/2012) (page 14213)

      Dr. Chuanjin Tian, Dr. Peng Xiu, Yan Meng, Dr. Wenyan Zhao, Prof. Zhigang Wang and Prof. Ruhong Zhou

      Article first published online: 25 OCT 2012 | DOI: 10.1002/chem.201290195

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      Quantum-mechanics calculations show that the chiral interconversion of the thalidomide-drug molecule can be greatly enhanced in the presence of water and base. Proton transfer and rotation of the glutarimide ring are important steps in the enantiomerization, and water and hydroxide ions can effectively catalyze the interconversion reaction. For more details, see the Full Paper by Z. Wang, R. Zhou et al. on page 14305 ff.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Communications
    7. Full Papers
  3. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Communications
    7. Full Papers
    1. You have free access to this content
  4. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Communications
    7. Full Papers
  5. Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Communications
    7. Full Papers
    1. Coupling Reactions

      Transition-Metal-Free Atropo-Selective Synthesis of Biaryl Compounds Based on Arynes (pages 14232–14236)

      Dr. Frédéric R. Leroux, Anaïs Berthelot, Dr. Laurence Bonnafoux, Dr. Armen Panossian and Prof. Françoise Colobert

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201202739

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      A modular way towards biaryls: Highly enantioenriched biphenyls can be prepared based on a transition-metal-free aryl–aryl coupling followed by efficient desymmetrization or deracemization and chemoselective functionalization (see scheme).

    2. Metathesis

      A New Family of Halogen-Chelated Hoveyda–Grubbs-Type Metathesis Catalysts (pages 14237–14241)

      Dr. Michał Barbasiewicz, Dr. Michał Michalak and Prof. Karol Grela

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202817

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      Coordination, not insertion: New ruthenium benzylidenes with a chelating halogen atom were easily prepared and showed excellent stability and activity as metathesis catalysts (see figure). Structure–activity studies reveal that strength of the ruthenium–halogen interaction can be tuned across a wide range to set up a family of latent to active catalysts.

    3. Synthetic Methods

      General One-Pot Synthesis of Alkynyliodonium Salts and Alkynyl Benziodoxolones from Aryl Iodides (pages 14242–14245)

      Dr. Marinus J. Bouma and Prof. Berit Olofsson

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202977

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      I: hyperfond of a triple bond! The first one-pot synthesis of alkynyl(aryl)iodonium salts directly from aryl iodides has been developed. The reaction is fast and high yielding, and can be extended to the synthesis of alkynyl benziodoxolones (see scheme). The developed methodology is expected to greatly facilitate the access to this interesting class of hypervalent iodine reagents, and many new application areas are foreseen.

    4. Fullerenes

      Access to an Unexplored Chiral C82 Cage by Encaging a Divalent Metal: Structural Elucidation and Electrochemical Studies of Sm@C2(5)-C82 (pages 14246–14249)

      Dr. Wei Xu, Ben Niu, Prof. Dr. Lai Feng, Prof. Dr. Zujin Shi and Prof. Yongfu Lian

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202897

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      Access to a chiral C82 cage: Encaging a divalent samarium atom has provided access to an unexplored chiral cage of C2(5)-C82 that has never been reported for trivalent M@C82 or empty fullerenes. Inside this cage, a wandering Sm atom has been identified using crystallographic methods. In addition, electrochemical studies of Sm@C2(5)-C82 have been performed to explore its oxidation properties (see figure).

    5. Total Synthesis

      Synthesis of the Originally Proposed Structure of Palmerolide C (pages 14250–14254)

      Dr. Gordon J. Florence and Joanna Wlochal

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201203067

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      A stereoselective synthesis of the proposed structure of palmerolide C (1), a cytotoxic marine macrolide isolated from the Antarctic tunicate Synoicum adareanum, utilizes a convergent carbonyl-based coupling strategy to construct the C1–C24 carbon skeleton (see scheme). Compound 1 was shown to be a diastereomer of palmerolide C, and the structural revision of the natural product is proposed.

    6. Organocatalysis

      Highly Diastereo- and Enantioselective Organocatalytic One-Pot Sequential 1,4-Addition/Dearomative-Fluorination Transformation (pages 14255–14260)

      Feng Li, Long Sun, Yuou Teng, Prof. Peng Yu, Prof. John Cong-Gui Zhao and Prof. Jun-An Ma

      Article first published online: 9 OCT 2012 | DOI: 10.1002/chem.201202636

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      Fluorination: A wide range of nitroolefins and pyrazol-5-ones undergo a sequential 1,4-addition/dearomative-fluorination transformation when treated with a catalytic amount of a tertiary-amine—thiourea compound and the terminal electrophile, N-fluorobenzenesulfonimide, to give fluorinated products in 72–95 % yield with up to 99:1 d.r. and 98 % ee. Notably, these products contain adjacent tertiary and α-fluoro quaternary stereocenters (see scheme).

    7. Nanostructures

      A Facile Top-Down Etching To Create a Cu2O Jagged Polyhedron Covered with Numerous {110} Edges and {111} Corners with Enhanced Photocatalytic Activity (pages 14261–14266)

      Dr. Yang Shang, Du Sun, Yiming Shao, Dongfeng Zhang, Prof. Lin Guo and Prof. Shihe Yang

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201201882

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      Cutting edge: A Cu2O jagged polyhedron, with numerous {110} edges and {111} corners, has been developed through a top-down selective oxidative etching process at the expense of the original {111} facet (see figure). The as-prepared nanocrystals exhibited higher photocatalytic activities for the degradation of methylene orange, which may be primarily ascribed to the increased edges and corners.

    8. Synthetic Methods

      A Convergent Approach to (−)-Callystatin A Based on Local Symmetry (pages 14267–14271)

      Dr. Mathieu Candy, Dr. Loïc Tomas, Dr. Sabrina Parat, Dr. Virginie Heran, Dr. Hugues Bienaymé, Prof. Dr. Jean-Marc Pons and Dr. Cyril Bressy

      Article first published online: 25 SEP 2012 | DOI: 10.1002/chem.201202701

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      The key is symmetry! A convergent synthetic approach of the highly cytotoxic natural product (−)-callystatin A was developed assembling three fragments through Julia–Kocienski olefination and Stille cross-coupling. The new strategy relies on a pivotal local symmetry of the target molecule. In this preliminary study, particular attention was devoted to facilitate the catalytic enantiocontrol of strategic stereogenic centers present in each of the fragments (see scheme).

    9. Photocatalysis

      Selective Growth of Metallic Ag Nanocrystals on Ag3PO4 Submicro-Cubes for Photocatalytic Applications (pages 14272–14275)

      Prof. Yingpu Bi, Hongyan Hu, Dr. Shuxin Ouyang, Dr. Zhengbo Jiao, Prof. Gongxuan Lu and Prof. Jinhua Ye

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201201435

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      Thinking outside the box: The position- and number-selective growth of Ag nanocrystals on Ag3PO4 submicro-cubes by an in situ reduction technique is demonstrated (see figure). These new Ag/Ag3PO4 heterocubes exhibit higher photocatalytic activities than pure Ag3PO4 cubes for the degradation of organic dyes under visible-light irradiation.

    10. Anticancer Agents

      Nitric Oxide Donor-Based Platinum Complexes as Potential Anticancer Agents (pages 14276–14281)

      Jian Zhao, Prof. Dr. Shaohua Gou, Yanyan Sun, Dr. Runting Yin and Zhimei Wang

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201201605

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      Joining forces: Platinum complexes containing organic nitrate ligands were investigated as anticancer agents. The complexes, which were stable in aqueous solution, showed cytotoxicity that was superior to that of the corresponding parent compound (carboplatin), thus suggesting an interesting synergy between the ability of the nitrate-based ligands to release nitric oxide and the ability of the platinum moiety to inhibit DNA synthesis (see scheme).

    11. Photoswitching

      Sterically Crowding the Bridge of Dithienylcyclopentenes for Enhanced Photoswitching Performance (pages 14282–14285)

      Robert Göstl, Björn Kobin, Dr. Lutz Grubert, Dr. Michael Pätzel and Prof. Stefan Hecht

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201203111

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      Better switching: The introduction of bulky substituents into the bridge moiety of dithienylethenes led to derivatives exhibiting high photocyclization quantum yields. This novel and versatile form of substitution facilitated tuning of the switching performance without compromising on the optical and redox properties of the ring-open and ring-closed forms (see scheme).

    12. Donor–Acceptor Systems

      Supramolecular Alternate Co-Assembly through a Non-Covalent Amphiphilic Design: Conducting Nanotubes with a Mixed D–A Structure (pages 14286–14291)

      K. Venkata Rao and Dr. Subi J. George

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202168

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      Mixing it up! The supramolecular alternate co-assembly of extended π-conjugated donor (D) and acceptor (A) molecules (i.e., oligo(phenylenevinylene) and perylenebisimide, respectively), to 1-D nanotubes with an unprecedented mixed stack D–A molecular structure is presented, through a non-covalent amphiphilic design strategy, which results in the formation of hydrogels with remarkable mechanical properties (see scheme).

  6. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Communications
    7. Full Papers
    1. Boroles

      Oligo(borolyl)benzenes—Synthesis and Properties (pages 14292–14304)

      Prof. Dr. Holger Braunschweig, Prof. Ching-Wen Chiu, Alexander Damme, Prof. Dr. Bernd Engels, Dr. Daniela Gamon, Christian Hörl, Dr. Thomas Kupfer, Dr. Ivo Krummenacher, Dr. Krzysztof Radacki and Christof Walter

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201202345

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      A bunch of boroles: Two and three borolyl units were attached to a benzene ring (see figure). The adduct chemistry of these oligoboroles was found to be strongly dependent on the electronic and steric properties of the pyridine base that was employed. The degree of Lewis acidity of the oligoboroles was examined by base-transfer reactions.

    2. Thalidomide

      Enantiomerization Mechanism of Thalidomide and the Role of Water and Hydroxide Ions (pages 14305–14313)

      Dr. Chuanjin Tian, Dr. Peng Xiu, Yan Meng, Dr. Wenyan Zhao, Prof. Zhigang Wang and Prof. Ruhong Zhou

      Article first published online: 12 OCT 2012 | DOI: 10.1002/chem.201202651

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      Changing hands: First-principle density function theory (DFT) is used to explore the enantiomerization mechanism of thalidomide (see figure). It was found that the proton transfer and rotation of the glutarimide ring are important steps in the enantiomerization, and that water and hydroxide ions can effectively catalyze the interconversion reaction.

    3. Reaction Mechanisms

      Iridium-Catalyzed Allylic Substitutions with Cyclometalated Phosphoramidite Complexes Bearing a Dibenzocyclooctatetraene Ligand: Preparation of (π-Allyl)Ir Complexes and Computational and NMR Spectroscopic Studies (pages 14314–14328)

      Dr. Jevgenij A. Raskatov, Mascha Jäkel, Prof. Dr. Bernd F. Straub, Dr. Frank Rominger and Prof. Dr. Günter Helmchen

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201201772

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      Bigger is better: The replacement of cod by dibenzo-cot is worth the effort because (allyl)Ir complexes of the latter compound are catalysts that give rise to improved regioselectivity and stability in iridium-catalyzed allylic aminations and alkylations (see figure).

    4. Porphyrinoids

      Photophysical Analysis of 1,10-Phenanthroline-Embedded Porphyrin Analogues and Their Magnesium(II) Complexes (pages 14329–14341)

      Dr. Masatoshi Ishida, Jong Min Lim, Byung Sun Lee, Prof. Dr. Fumito Tani, Prof. Dr. Jonathan L. Sessler, Prof. Dr. Dongho Kim and Prof. Dr. Yoshinori Naruta

      Article first published online: 24 SEP 2012 | DOI: 10.1002/chem.201201793

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      Anything can H-Pn: A new series of tetraaza porphyrin analogues (H[BOND]Pn: n=1–4) containing a dipyrrin subunit and an embedded 1,10-phenanthroline subunit have been developed as Mg2+-responsive fluorescent sensors. Upon complexation with Mg2+ ions, a structure-dependent emission enhancement is seen that is partially governed by donor-excited photoinduced electron-transfer (d-PET) events (see figure).

    5. Natural Products

      Andhraxylocarpins A–E: Structurally Intriguing Limonoids from the True Mangroves Xylocarpus granatum and Xylocarpus moluccensis (pages 14342–14351)

      Jun Li, Dr. Min-Yi Li, Dr. Torsten Bruhn, Dr. Daniel C. G. Götz, Prof. Dr. Qiang Xiao, Tirumani Satyanandamurty, Prof. Dr. Jun Wu and Prof. Dr. Gerhard Bringmann

      Article first published online: 24 SEP 2012 | DOI: 10.1002/chem.201202356

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      If a tree falls in the woods… Three new limonoid motifs (see figure) were identified by extensive NMR investigations, single-crystal X-ray diffraction analysis, and by quantum-chemical circular dichroism and optical rotatory dispersion calculations. These results indicate that environmental factors might play a leading role in the generation of the structural diversity of limonoids in true mangroves.

    6. Polyoxometalates

      Pickering Emulsion Stabilized by Catalytic Polyoxometalate Nanoparticles: A New Effective Medium for Oxidation Reactions (pages 14352–14358)

      Dr. Loïc Leclercq, Adrien Mouret, Prof. Dr. Anna Proust, Dr. Véronique Schmitt, Dr. Pierre Bauduin, Prof. Dr. Jean-Marie Aubry and Prof. Dr. Véronique Nardello-Rataj

      Article first published online: 20 SEP 2012 | DOI: 10.1002/chem.201201799

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      Mixing it up a bit: Spherical nanoparticles of decyl- and dodecyltrimethylammonium cations with [PW12O40]3− formed stable Pickering emulsions in the presence of an aromatic solvent and water. This system is an efficient medium for epoxidation (see figure).

    7. Photocatalysts

      One-Pot Synthesis, Characterization, and Enhanced Photocatalytic Activity of a BiOBr–Graphene Composite (pages 14359–14366)

      Dr. Xinman Tu, Prof. Dr. Shenglian Luo, Guixiang Chen and Prof. Jinghong Li

      Article first published online: 20 SEP 2012 | DOI: 10.1002/chem.201200892

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      Competent composite! A chemically bonded BiOBr–RG photocatalyst with high performance has been successfully and directly produced by using a one-pot solvothermal method. This composite simultaneously possesses great adsorptivity toward dyes, an extended photoresponse range, and enhanced charge separation and transportation properties (see scheme).

    8. Conformation Analysis

      Structural Changes in a Protein Fragment from Abalone Shell during the Precipitation of Calcium Carbonate (pages 14367–14374)

      Dr. Alessio Adamiano, Dr. Sara Bonacchi, Dr. Natalia Calonghi, Prof. Daniele Fabbri, Prof. Giuseppe Falini, Dr. Simona Fermani, Dr. Damiano Genovese, Dr. Damir Kralj, Dr. Marco Montalti, Dr. Branka Njegić Džakula, Prof. Luca Prodi and Prof. Giorgio Sartor

      Article first published online: 20 SEP 2012 | DOI: 10.1002/chem.201201863

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      Coming out of your shell: A natural protein fragment in the shells of abalone (see figure), which has fluorescent properties, is used to probe the conformational changes that occur when it moves from solution into a calcite crystal. This fragment is mainly unfolded in solution and only changes its conformation when entrapped inside the crystal.

    9. Photogenerated Proton Pumps

      Energy Propagation Through a Protometabolism Leading to the Local Emergence of Singular Stationary Concentration Profiles (pages 14375–14383)

      Dr. Matthieu Emond, Dr. Thomas Le Saux, Prof. Jean-Francois Allemand, Dr. Philippe Pelupessy, Dr. Raphaël Plasson and Prof. Ludovic Jullien

      Article first published online: 25 SEP 2012 | DOI: 10.1002/chem.201201974

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      Chain of energy transfer: Living systems rely on chains of energy transfer (e.g., photosynthesis) from an energy source (e.g., light) to maintain their metabolism. For the first time, by using a photoacid shuttle and light patterning, the spatial propagation of energy from light at a steady state through a chain of proton-exchange reactions has been achieved (see scheme). Energy propagation is accompanied by the spontaneous local emergence of singular stationary concentration profiles.

    10. Graphene

      Poly(9,9′-diheylfluorene carbazole) Functionalized with Reduced Graphene Oxide: Convenient Synthesis using Nitrogen-Based Nucleophiles and Potential Applications in Optical Limiting (pages 14384–14391)

      Xiujuan Xu, Jun Chen, Xiaoliang Luo, Jingjing Lu, Haixin Zhou, Wenbo Wu, Prof. Hongbing Zhan, Prof. Yongqiang Dong, Prof. Shouke Yan, Prof. Jingui Qin and Prof. Zhen Li

      Article first published online: 24 SEP 2012 | DOI: 10.1002/chem.201201360

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      Graphene modification: A nucleophilic reaction between graphene oxide and poly(9,9′-diheylfluorene carbazole) leads to a chemically modified reduced graphene oxide sheet (see scheme). Other products with different size and solubility could be separated by simple centrifugation. The soluble part showed good solubility in water, while the insoluble part displayed good optical-limiting response.

    11. Polysaccharides

      Studies Related to Norway Spruce Galactoglucomannans: Chemical Synthesis, Conformation Analysis, NMR Spectroscopic Characterization, and Molecular Recognition of Model Compounds (pages 14392–14405)

      Dr. Filip S. Ekholm, Dr. Ana Ardá, Dr. Patrik Eklund, Priv.-Doz. Dr. Sabine André, Prof. Dr. Hans-Joachim Gabius, Prof. Dr. Jesús Jiménez-Barbero and Prof. Dr. Reko Leino

      Article first published online: 24 SEP 2012 | DOI: 10.1002/chem.201200510

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      Modeling behavior: Detailed studies on the chemical synthesis, NMR spectroscopic characterization, conformation analysis, and molecular recognition of molecular models of oligosaccharide fragments present in the backbone of galactoglucomannan polysaccharides found in natural Norway spruce are reported (see figure). A tetrasaccharide fragment was further utilized in a binding study with the galactose-binding protein viscumin to test bioaffinity.

    12. Anion Recognition

      Sulfate-Selective Binding and Sensing of a Fluorescent [3]Rotaxane Host System (pages 14406–14412)

      Matthew J. Langton and Prof. Paul D. Beer

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202204

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      Selective sensing of sulfate: The chloride-templated synthesis of a novel [3]rotaxane, capable of binding anionic guests, and incorporating a naphthalene group for fluorescence sensing is reported. Extensive 1H NMR anion titration studies revealed the rotaxane to selectively recognise sulfate, by undergoing a conformational change to form a 1:1 stoichiometric sandwich-type complex, concomitant with significant quenching of the naphthalene emission (see scheme).

    13. Molecular Recognition

      Synthesis and Supramolecular Studies of Chiral Boronated Platinum(II) Complexes: Insights into the Molecular Recognition of Carboranes by β-Cyclodextrin (pages 14413–14425)

      Dr. H. Y. Vincent Ching, Dr. Sarah Clifford, Dr. Mohan Bhadbhade, Dr. Ronald J. Clarke and Prof. Louis M. Rendina

      Article first published online: 25 SEP 2012 | DOI: 10.1002/chem.201201746

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      Catching a carborane: The synthesis of a novel isomeric family of closo- and nido-carborane-containing PtII complexes and corresponding β-cyclodextrin (β-CD) supramolecular host–guest adducts of the former is described (see scheme). The molecular recognition of these closo-carborane derivatives by β-CD was comprehensively investigated by isothermal titration calorimetry, which delivered fascinating insights into the structural features influencing the thermodynamics of this phenomenon in aqueous solution.

    14. Solvent Effects

      Understanding the Solvent Effect on the Catalytic Oxidation of 1,4-Butanediol in Methanol over Au/TiO2 Catalyst: NMR Diffusion and Relaxation Studies (pages 14426–14433)

      Dr. Carmine D'Agostino, Dr. Gemma L. Brett, Dr. Peter J. Miedziak, Prof. David W. Knight, Prof. Graham J. Hutchings, Prof. Lynn F. Gladden and Dr. Mick D. Mantle

      Article first published online: 24 SEP 2012 | DOI: 10.1002/chem.201201922

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      The solvent effect on the catalytic oxidation of 1,4-butanediol over gold nanoparticles supported on titania (Au/TiO2) has been assessed and a detrimental effect on the reaction rate upon water addition to the initial methanol solvent was observed (see figure). NMR diffusion and relaxation studies revealed that water addition leads to a significant decrease of the diffusion coefficient and adsorption strength of the reactant over the catalyst surface, which in turn affects the reaction rate of the process.

    15. Non-Innocent Ligands

      Experimental and DFT Evidence for the Fractional Non-Innocence of a β-Diketonate Ligand (pages 14434–14443)

      Amit Das, Dipl.-Chem. Thomas Michael Scherer, Prasenjit Mondal, Dr. Shaikh M. Mobin, Prof. Dr. Wolfgang Kaim and Prof. Dr. Goutam Kumar Lahiri

      Article first published online: 23 SEP 2012 | DOI: 10.1002/chem.201201785

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      Mixed ligation: The π-acceptor effect of 2-phenylazopyridine (pap) on ruthenium is indirectly responsible for the partial oxidation of 9-oxidophenalenone (L[RIGHTWARDS ARROW]L.) in mixed-ligand complexes [Ru(pap)3−n(L)n]x (n=1, 2; see scheme).

    16. Acyl Substitution

      Direct Acyl Substitution of Carboxylic Acids: A Chemoselective O- to N-Acyl Migration in the Traceless Staudinger Ligation (pages 14444–14453)

      Andrew D. Kosal, Erin E. Wilson and Prof. Dr. Brandon L. Ashfeld

      Article first published online: 23 SEP 2012 | DOI: 10.1002/chem.201201773

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      Turning the peptide with azides: A modified Staudinger-like acylation of azides involving a highly chemoselective, direct acyl substitution of carboxylic acids is described. Structurally diverse amides are obtained after a simple aqueous workup (see scheme). The use of chlorophosphites as dual carboxylic acid–azide activating agents enables the formation of acyl C[BOND]N bonds in the presence of a wide range of nucleophilic and electrophilic functional groups.

    17. Lanthanide Complexes

      Chiral Benzamidinate Ligands in Rare-Earth-Metal Coordination Chemistry (pages 14454–14463)

      Dr. Paul Benndorf, Dipl.-Chem. Jochen Kratsch, Larissa Hartenstein, Dipl.-Chem. Corinna M. Preuss and Prof. Dr. Peter W. Roesky

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201202457

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      Enantiomerically pure lanthanide complexes were synthesized as the first rare-earth-metal complexes containing a chiral amidinate ligand (see scheme). The catalytic activities and enantioselectivities of these complexes were studied in hydroamination reactions.

    18. Anticancer Activity

      Ruthenium(II/III)-Based Compounds with Encouraging Antiproliferative Activity against Non-small-Cell Lung Cancer (pages 14464–14472)

      Dr. Eszter M. Nagy, Andrea Pettenuzzo, Giulia Boscutti, Prof. Dr. Luciano Marchiò, Prof. Dr. Lisa Dalla Via and Prof. Dr. Dolores Fregona

      Article first published online: 25 SEP 2012 | DOI: 10.1002/chem.201202171

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      006 Licence to kill: Mono- and dinuclear dithiocarbamato complexes of RuII/III have been synthesised and fully characterised by 1H NMR and IR spectroscopy (L=dimethyl-, pyrrolidinedithiocarbamate; see figure). The in vitro cytotoxicity has been evaluated on non-small-cell lung cancer NCI-H1975 cells. All the RuIII complexes show promising antiproliferative activity that is much greater than cisplatin.

    19. Nanocrystals

      Fast Synthesis of PbS Nanocrystals in Aqueous Solution with Shape Evolution from Cubic to Octahedral Structures and Their Assembled Structures (pages 14473–14478)

      Jian-Kuan Wu, Lian-Ming Lyu, Ching-Wen Liao, Yu-Ning Wang and Prof. Michael H. Huang

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201201687

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      Shape shifters: A fast and energy-efficient method for the synthesis of PbS nanocrystals with systematic shape evolution from cubic to truncated cubic, cuboctahedral, truncated octahedral, and octahedral structures has been developed (see figure). By varying the amount of thioacetamide added to the growth solution, PbS nanocrystals with different morphologies were generated in 2 h at 90 °C.

    20. Synthetic Methods

      Highly Selective Barbier-Type Propargylations and Allenylations Catalyzed by Titanocene(III) (pages 14479–14486)

      Juan Muñoz-Bascón, Iris Sancho-Sanz, Prof. Enrique Álvarez-Manzaneda, Dr. Antonio Rosales and Prof. J. Enrique Oltra

      Article first published online: 20 SEP 2012 | DOI: 10.1002/chem.201201720

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      Effectiveness, selectivity, and sustainability are key properties of this novel method for Ti-catalyzed Barbier-type propargylation/allenylation. The reaction proceeds at RT under mild conditions compatible with numerous functional groups and affords homopropargylic alcohols from aldehydes and ketones and α-hydroxy-allenes from aldehydes (see scheme).

    21. DNA Recognition

      Cationic Pentaheteroaryls as Selective G-Quadruplex Ligands by Solvent-Free Microwave-Assisted Synthesis (pages 14487–14496)

      Michele Petenzi, Dr. Daniela Verga, Dr. Eric Largy, Dr. Florian Hamon, Dr. Filippo Doria, Dr. Marie-Paule Teulade-Fichou, Aurore Guédin, Dr. Jean-Louis Mergny, Prof. Mariella Mella and Prof. Mauro Freccero

      Article first published online: 20 SEP 2012 | DOI: 10.1002/chem.201202097

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      Oxadiazoles improve binding: Microwave-assisted synthesis of water soluble acyclic pentaheteroaryls containing 1,2,4-oxadiazoles (17; see scheme) was achieved. The binding with DNA quadruplex structures was investigated by FRET melting, G4-FID and CD spectroscopy. The oxadiazole containing ligands 1, 2, and 5 were better binders than the structurally related oxazoles (810).

    22. Mixed-Valent Compounds

      Electronic Coupling between Two Amine Redox Sites through the 5,5′-Positions of Metal-Chelating 2,2′-Bipyridines (pages 14497–14509)

      Hai-Jing Nie, Xialing Chen, Chang-Jiang Yao, Prof. Dr. Yu-Wu Zhong, Prof. Dr. Geoffrey R. Hutchison and Prof. Dr. Jiannian Yao

      Article first published online: 25 SEP 2012 | DOI: 10.1002/chem.201201813

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      Amine–amine electronic coupling through the 5,5′-positions of metalchelated 2,2′-bipyridines has been studied by electrochemistry, near-infrared transition analysis, and DFT/TDDFT computations (see figure). These studies suggest that the coupling is enhanced by metal chelation and that the iridium complex has the strongest coupling.

    23. Catalysis

      You have full text access to this OnlineOpen article
      A Highly Active Bifunctional Iridium Complex with an Alcohol/Alkoxide-Tethered N-Heterocyclic Carbene for Alkylation of Amines with Alcohols (pages 14510–14519)

      Agnieszka Bartoszewicz, Dr. Rocío Marcos, Dr. Suman Sahoo, Dr. A. Ken Inge, Prof. Xiaodong Zou and Dr. Belén Martín-Matute

      Article first published online: 24 SEP 2012 | DOI: 10.1002/chem.201201845

      Thumbnail image of graphical abstract

      Working together: A series of novel iridium(III) complexes containing bidentate N-heterocyclic carbene (NHC) ligands functionalized with an alcohol were prepared. The complexes are highly active for the alkylation of anilines using alcohols as latent electrophiles at temperatures as low as 50°C (see scheme). The reactivity of structurally related iridium(III) complexes was also compared to obtain insights into the mechanism.

    24. Fluorescent Probes

      A Native-Chemical-Ligation-Mechanism-Based Ratiometric Fluorescent Probe for Aminothiols (pages 14520–14526)

      Lin Yuan, Prof. Weiying Lin, Yinan Xie, Sasa Zhu and Sheng Zhao

      Article first published online: 24 SEP 2012 | DOI: 10.1002/chem.201201606

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      Going native: A ratiometric fluorescent probe for aminothiols has been designed based on the native chemical ligation (NCL) reaction mechanism (see scheme). The probe is highly selective toward aminothiols over other thiols and exhibits a very large variation (up to 160-fold) in the fluorescence ratio (I458/I603).

    25. Decarboxylation Reactions

      Mechanism of the Pd-catalyzed Decarboxylative Allylation of α-Imino Esters: Decarboxylation via Free Carboxylate Ion (pages 14527–14538)

      Dr. Zhe Li, Yuan-Ye Jiang, Dr. Andrew A. Yeagley, James P. Bour, Prof. Lei Liu, Prof. Jason J. Chruma and Prof. Yao Fu

      Article first published online: 23 SEP 2012 | DOI: 10.1002/chem.201201425

      Thumbnail image of graphical abstract

      Decarboxylation via carboxylate ions: The Pd-catalyzed decarboxylative allylation of α-imino esters has been studied using theoretical calculations and experimental investigations. The catalytic cycle consists of three steps: oxidative addition, decarboxylation, and reductive allylation. The decarboxylation step is rate-determining, occurring via a solvent-exposed α-imino carboxylate anion (see scheme).

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