Chemistry - A European Journal

Cover image for Vol. 17 Issue 1

January 3, 2011

Volume 17, Issue 1

Pages 1–395

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
    1. Cover Picture: Silver Baits for The “Miraculous Draught” of Amphiphilic Lanthanide Helicates / A Multistate Switchable [3]Rotacatenane / Heuristic Chemistry—Addition Reactions / Steric, Electronic, and Secondary Effects on the Coordination Chemistry of Ionic Phosphine Ligands and the Catalytic Behavior of Their Metal Complexes / 4,5-Disubstituted N,N′-Di-tert-alkyl Imidazolium Salts: New Synthesis and Structural Features / Luminescent Cyclometalated Dialkynylgold(III) Complexes of 2-Phenylpyridine-Type Derivatives with Readily Tunable Emission Properties / Recent Developments in Methodology for the Direct Oxyamination of Olefins / Configurational and Constitutional Information Storage: Multiple Dynamics in Systems Based on Pyridyl and Acyl Hydrazones (Chem. Eur. J. 1/2011) (page 1)

      Dr. Emmanuel Terazzi, Dr. Laure Guénée, Johan Varin, Bernard Bocquet, Dr. Jean-François Lemonnier, Daniel Emery, Dr. Jiri Mareda, Prof. Dr. Claude Piguet, Gokhan Barin, Dr. Ali Coskun, Douglas C. Friedman, Mark A. Olson, Michael T. Colvin, Dr. Raanan Carmielli, Dr. Sanjeev K. Dey, Dr. O. Altan Bozdemir, Prof. Michael R. Wasielewski, Prof. J. Fraser Stoddart, Nicole Graulich, Prof. Dr. Henning Hopf, Prof. Dr. Peter R. Schreiner, Dr. Dennis J. M. Snelders, Prof. Dr. Gerard van Koten, Prof. Dr. Robertus J. M. Klein Gebbink, Anastasia A. Grishina, Dr. Svetlana M. Polyakova, Roman A. Kunetskiy, Dr. Ivana Císařová, Dr. Ilya M. Lyapkalo, Vonika Ka-Man Au, Dr. Keith Man-Chung Wong, Dr. Nianyong Zhu, Prof. Dr. Vivian Wing-Wah Yam, Prof. Timothy J. Donohoe, Cedric K. A. Callens, Dr. Aida Flores, Adam R. Lacy, Akshat H. Rathi, Dr. Manuel N. Chaur, Dr. Daniel Collado and Prof. Dr. Jean-Marie Lehn

      Version of Record online: 5 JAN 2011 | DOI: 10.1002/chem.201090247

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      The International Year of Chemistry 2011… …is an initiative of the International Union of Pure and Applied Chemistry (IUPAC) and the United Nations Educational, Scientific, and Cultural Organization (UNESCO). Under the motto “Chemistry—our life, our future”, it is a worldwide celebration of the achievements of chemistry and its contributions to the well-being of humankind. As part of our own contribution to the International Year of Chemistry, the cover of this special issue features a collage of chemistry from around the world. Going clockwise from the top left-hand corner, the work featured is on amphiphilic lanthanide helicates by Claude Piguet, Emmanuel Terazzi, Jiri Mareda et al. (p. 184); on a multistate switchable [3]rotacatenane by J. Fraser Stoddart et al. (p. 213); on heuristic chemistry—addition reactions by Peter Schreiner et al. (p. 30); on steric, electronic, and secondary effects on the coordination chemistry of ionic phosphine ligands and the catalytic behavior of their metal complexes by Robertus J. M. Klein Gebbink et al. (p. 42); on the synthesis and structural features of 4,5-disubstituted N,N′-di-tert-alkyl imidazolium by Svetlana Polyakova, Ilya M. Lyapkalo et al. (p. 96); on luminescent cyclometalated dialkynylgold(III) complexes of 2-phenylpyridine-type derivatives with readily tunable emission properties by Vivian Wing-Wah Yam et al. (p. 130); on recent developments in methodology for the direct oxyamination of olefins by Timothy J. Donohoe et al. (p. 58); and last but by no means least, on configurational and constitutional information storage by Nobel Prize winner, and co-founder of the journal, Jean-Marie Lehn et al. (p. 248).

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
    1. Inside Cover: Development of Fluorescent Glucose Bioprobes and Their Application on Real-Time and Quantitative Monitoring of Glucose Uptake in Living Cells (Chem. Eur. J. 1/2011) (page 2)

      Hyang Yeon Lee, Jae Jeong Lee, Jongmin Park and Prof. Seung Bum Park

      Version of Record online: 5 JAN 2011 | DOI: 10.1002/chem.201090249

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      The perturbation… … of glucose uptake in organisms is an essential barometer in various metabolic diseases. In their Full Paper on page 143 ff. S. B. Park et al. report on a novel fluorescent glucose bioprobe that can translocate into cytoplasm by glucose-specific transport systems through the competition with D-glucose. Unlike reported glucose bioprobes, such as NBDGs and 2-deoxyglucoses, this fluorescent glucose bioprobe allows the real-time and quantitative measurement of glucose uptake in living cells.

  3. Editorials

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
    1. International Year of Chemistry

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      International Year of Chemistry— A European Journal (pages 4–7)

      Neville Compton

      Version of Record online: 5 JAN 2011 | DOI: 10.1002/chem.201003569

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      Significance of the International Year of Chemistry 2011 (pages 9–11)

      Prof. Dr. Jung-Il Jin

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/chem.201003326

  4. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
  6. Concept

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
    1. Organic Chemistry

      Heuristic Chemistry—Addition Reactions (pages 30–40)

      Nicole Graulich, Prof. Dr. Henning Hopf and Prof. Dr. Peter R. Schreiner

      Version of Record online: 5 JAN 2011 | DOI: 10.1002/chem.201002370

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      A heuristic model for addition reactions has been developed to enhance the conceptual thinking in understanding and teaching organic chemistry (see picture). This approach concentrates on the basic concept of addition reactions and departs from the traditional functional group viewpoint. The use of recurrent reaction motifs provides the basis for recognizing, predicting, and planning addition reactions.

  7. Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
    1. Coordination Chemistry

      Steric, Electronic, and Secondary Effects on the Coordination Chemistry of Ionic Phosphine Ligands and the Catalytic Behavior of Their Metal Complexes (pages 42–57)

      Dr. Dennis J. M. Snelders, Prof. Dr. Gerard van Koten and Prof. Dr. Robertus J. M. Klein Gebbink

      Version of Record online: 15 DEC 2010 | DOI: 10.1002/chem.201002508

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      More than sterics and electronics: The introduction of charged groups in phosphine ligands (see scheme) not only alters their solubility and their steric and electronic properties, but often also leads to supramolecular interactions. These effects can significantly alter the coordination chemistry of the phosphine ligand with respect to a transition metal. Here, the different types of interactions that play a role, as well as their consequences with respect to catalysis, are reviewed.

    2. Synthetic Methods

      Recent Developments in Methodology for the Direct Oxyamination of Olefins (pages 58–76)

      Prof. Timothy J. Donohoe, Cedric K. A. Callens, Dr. Aida Flores, Adam R. Lacy and Akshat H. Rathi

      Version of Record online: 16 DEC 2010 | DOI: 10.1002/chem.201002323

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      Spoilt for choice: The direct conversion of an alkene to a vicinal amino alcohol derivative (oxyamination, see scheme) is one of the most important approaches to this versatile functional group, which is found in scores of biologically active molecules and other interesting synthetic targets such as ligands and auxiliaries. This review provides the reader with a tour of the methods that have emerged in the last few years so one can appreciate the myriad of different metals and reagents that can accomplish the oxyamination of alkenes.

  8. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
    1. Microporous Materials

      Ultrafine Gold Clusters Incorporated into a Metal–Organic Framework (pages 78–81)

      Dr. Hai-Long Jiang, Qi-Pu Lin, Dr. Tomoki Akita, Bo Liu, Dr. Hironori Ohashi, Dr. Hiroshi Oji, Dr. Tetsuo Honma, Prof. Dr. Takashi Takei, Prof. Dr. Masatake Haruta and Prof. Dr. Qiang Xu

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/chem.201002088

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      Trapping gold! A novel porous metal–organic framework (MOF) with an unprecedented hexagonal (4,8)-connected topology has been assembled and characterized. By employing the resultant MOF as a host, for the first time, ultrafine Au clusters with an average atom number of 2.5 were successfully prepared and incorporated into the pores of the MOF through a simple surfactant-free method (see graphic).

    2. Amine Cross-Coupling

      Microwave-Promoted Selective Mono-N-Alkylation of Anilines with Tertiary Amines by Heterogeneous Catalysis (pages 82–85)

      Dr. M. Caterina Lubinu, Dr. Lidia De Luca, Prof. Giampaolo Giacomelli and Dr. Andrea Porcheddu

      Version of Record online: 24 NOV 2010 | DOI: 10.1002/chem.201002704

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      A palladium-catalyzed N-alkylation of anilines with tertiary amines that occurs under heterogeneous transfer-hydrogenation conditions has been developed (see scheme). This protocol of transamination, which uses a relatively cheap and easily recyclable heterogeneous catalyst, can be efficiently applied to different substrates and is suitable for large-scale preparations.

    3. Gold Catalysis

      Chemoselective C[BOND]C Bond Cleavage of Epoxide Motifs: Gold(I)-Catalyzed Diastereoselective [4+3] Cycloadditions of 1-(1-Alkynyl)oxiranyl Ketones and Nitrones (pages 86–90)

      Tao Wang and Prof. Dr. Junliang Zhang

      Version of Record online: 1 DEC 2010 | DOI: 10.1002/chem.201002395

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      Cutting carbon! A novel facile strategy for the C[BOND]C bond cleavage of oxiranyl ketones has been developed. Carbophilic gold(I) activation of the alkyne side chain mediates a heterocyclization and subsequent C[BOND]C bond cleavage (see scheme).

    4. Homogeneous Catalysis

      Rhodium(III)-Catalyzed Dimerization of Aldehydes to Esters (pages 91–95)

      Dr. Cristina Tejel, Prof. Dr. Miguel A. Ciriano and Dr. Vincenzo Passarelli

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/chem.201002921

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      No sooner said than done: A rhodi- um(III) hydride complex is an outstandingly effective and selective catalyst for the dimerization of aldehydes to the corresponding esters (see scheme). Evidence for an unusual mechanism in catalysis by rhodium is given.

    5. Carbene Chemistry

      4,5-Disubstituted N,N′-Di-tert-alkyl Imidazolium Salts: New Synthesis and Structural Features (pages 96–100)

      Anastasia A. Grishina, Dr. Svetlana M. Polyakova, Roman A. Kunetskiy, Dr. Ivana Císařová and Dr. Ilya M. Lyapkalo

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/chem.201002805

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      It's getting crowded! The synthesis of a new subfamily of imidazolium cations with exceptionally spatially demanding substitution patterns (see scheme) paved the way to reconcile two antagonising effects: steric hindrance and innately high donating ability/basicity in the peralkylated imidazol-2-ylidene ligands/uncharged bases.

    6. Asymmetric Hydrogenation

      Copper-Catalyzed Enantioselective Hydrogenation of Ketones (pages 101–105)

      Dr. Kathrin Junge, Bianca Wendt, Daniele Addis, Shaolin Zhou, Shoubhik Das, Steffen Fleischer and Prof. Dr. Matthias Beller

      Version of Record online: 30 NOV 2010 | DOI: 10.1002/chem.201002311

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      Not so precious! The combination of copper acetate and chiral monodentate ligands allows the enantioselective hydrogenation of carbonyl compounds to take place in good to high yields with moderate to good enantioselectivities (see scheme).

    7. Alkynone Synthesis

      A General Palladium-Catalyzed Carbonylative Sonogashira Coupling of Aryl Triflates (pages 106–110)

      Xiao-Feng Wu, Basker Sundararaju, Dr. Helfried Neumann, Prof. Dr. Pierre H. Dixneuf and Prof. Dr. Matthias Beller

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/chem.201002653

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      Trifling with triflates: A new protocol for the carbonylative Sonogashira reactions of aryl triflates (see scheme) that provides a significant extension of this interesting methodology is described.

    8. Hydrogen Bonding

      Direct Evidence of a Liquid-Crystalline Phase Induced by Intermolecular C[BOND]H⋅⋅⋅Cl Interactions on the Basis of IR Spectroscopy and Theoretical Simulations (pages 111–116)

      Prof. Long-Li Lai, Chun-Ming Yang, Chia-Chun Liu, Dr. Kung-Lung Cheng, Dr. Yu-Shen Wen, Prof. Chen-Hsiung Hung, Dr. Tzuoo-Tsair Luo and Prof. Ming-Yu Kuo

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/chem.201002177

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      Cl-ued together: Two chloroazodyes that only differ in the length of the flexible alkyl chains demonstrate different mesogenic behavior during thermal processes. The one with the C7H15 (1 a; see picture) alkyl chain shows an SmA phase, whereas the one with the C5H11 alkyl chain does not. The corresponding SmA phase of 1 a is attributed to intermolecular Cl⋅⋅⋅H interactions.

    9. Single-Molecule Magnets

      Magnetic Relaxation of Single-Molecule Magnets in an External Magnetic Field: An Ising Dimer of a Terbium(III)–Phthalocyaninate Triple-Decker Complex (pages 117–122)

      Dr. Keiichi Katoh, Prof. Takashi Kajiwara, Prof. Motohiro Nakano, Prof. Yasuhiro Nakazawa, Prof. Wolfgang Wernsdorfer, Prof. Naoto Ishikawa, Prof. Brian K. Breedlove and Prof. Masahiro Yamashita

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/chem.201002026

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      A single magnet in a triple decker! TbIII–phthalocyaninate triple-decker 1, which has a center of symmetry, showed two magnetic relaxation processes in the low-temperature region in the presence of a direct current (dc) magnetic field. These results suggest that the single-molecule magnet/magnetic properties of 1 undergo a significant transition in a dc magnetic field.

    10. Mössbauer Spectroscopy

      Antiferromagnetically Coupled Iron Ions in a Polynuclear FeIII–Dy Complex: Confirmation by Variable-Field 57Fe Mössbauer Spectroscopy (pages 123–128)

      Dr. Valeriu Mereacre, Dr. Denis Prodius, Dr. Yanhua Lan, Prof. Dr. Constantin Turta, Dr. Christopher E. Anson and Prof. Dr. Annie K. Powell

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/chem.201002060

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      Check out the magnetism: The antiferromagnetic interactions in the Fe7 core (see picture, left) in a {Fe7Dy4} complex were confirmed by variable-field 57Fe Mössbauer spectroscopy (picture, right).

  9. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorials
    5. Graphical Abstract
    6. News
    7. Concept
    8. Reviews
    9. Communications
    10. Full Papers
    11. Preview
    1. Gold(III) Luminescence

      Luminescent Cyclometalated Dialkynylgold(III) Complexes of 2-Phenylpyridine-Type Derivatives with Readily Tunable Emission Properties (pages 130–142)

      Vonika Ka-Man Au, Dr. Keith Man-Chung Wong, Dr. Nianyong Zhu and Prof. Dr. Vivian Wing-Wah Yam

      Version of Record online: 22 OCT 2010 | DOI: 10.1002/chem.201001965

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      Luminescence enhancement: A novel class of luminescent dialkynylgold(III) complexes containing various phenylpyridine- and phenylisoquinoline-type bidentate ligands has been successfully synthesized and characterized. This class of complexes has been shown to demonstrate rich and tunable photoluminescence properties (see picture).

    2. Glucose Bioprobes

      Development of Fluorescent Glucose Bioprobes and Their Application on Real-Time and Quantitative Monitoring of Glucose Uptake in Living Cells (pages 143–150)

      Hyang Yeon Lee, Jae Jeong Lee, Jongmin Park and Prof. Seung Bum Park

      Version of Record online: 5 JAN 2011 | DOI: 10.1002/chem.201002560

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      Sugar it up: Fluorescent glucose bioprobes (GB-Cy3) have been developed and applied to the real-time and quantitative visualization of glucose uptake in living cells by using confocal laser scanning microscopy, fluorescence microscopy, and flow cytometry analysis (see graphic). Moreover, GB2-Cy3 can be utilized in high-content screening for the discovery of novel therapeutic agents in metabolic diseases.

    3. Amyloid Formation

      Amyloid Formation from an α-Helix Peptide Bundle Is Seeded by 310-Helix Aggregates (pages 151–160)

      Dr. Yogendra Singh, Dr. Philip C. Sharpe, Dr. Huy N. Hoang, Dr. Andrew J. Lucke, Dr. Alasdair W. McDowall, Prof. Stephen P. Bottomley and Prof. David P. Fairlie

      Version of Record online: 15 DEC 2010 | DOI: 10.1002/chem.201002500

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      α-Helix bundles to amyloid fibrils: A scaffold containing a 4α-helix bundle undergoes a concentration- and pH-dependent transformation to β-strand/sheet aggregates and amyloid fibrils through 310-helical intermediate structures stabilised by aggregation (see figure).

    4. Molecular Dynamics

      Modeling of Heavy-Atom–Ligand NMR Spin–Spin Coupling in Solution: Molecular Dynamics Study and Natural Bond Orbital Analysis of Hg[BOND]C Coupling Constants (pages 161–173)

      Shaohui Zheng and Jochen Autschbach

      Version of Record online: 12 NOV 2010 | DOI: 10.1002/chem.201001343

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      Dunking the doughnut: Ab initio molecular dynamics and relativistic density functional NMR methods were combined to calculate the one-bond Hg[BOND]C NMR J coupling constants of [Hg(CN)2] and [CH3HgCl] in solution. The degree of delocalization of the Hg 5dσ nonbonding orbital and the Hg[BOND]C bonding orbital between the two coupled atoms, the nature of the trans Hg[BOND]C/Cl bonding orbital, and the s character of these orbitals exhibit trends upon solvation of the complexes that, when combined, lead to a strong increase of J(Hg[BOND]C).

    5. Fluorescence Sensing

      Differentiating a Diverse Range of Volatile Organic Compounds with Polyfluorophore Sensors Built on a DNA Scaffold (pages 174–183)

      Dr. Florent Samain, Dr. Nan Dai and Prof. Dr. Eric T. Kool

      Version of Record online: 10 DEC 2010 | DOI: 10.1002/chem.201002836

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      Colorful screening: Short DNA-like molecules with fluorophores replacing the DNA bases are used as sensors of ten different volatile organic compounds. Fluorescence responses are strong and diverse, and only four sensors are needed to distinguish among all ten analytes (see scheme for an example).

    6. Heterometallic Complexes

      Silver Baits for The “Miraculous Draught” of Amphiphilic Lanthanide Helicates (pages 184–195)

      Dr. Emmanuel Terazzi, Dr. Laure Guénée, Johan Varin, Bernard Bocquet, Dr. Jean-François Lemonnier, Daniel Emery, Dr. Jiri Mareda and Prof. Dr. Claude Piguet

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/chem.201002771

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      Soft and sulfur: The introduction of soft sulfur atoms into axial terminal lipophilic alkyl chains produces specific interactions with AgI leading to the extraction of discrete dimetallic tetranuclear triple-stranded helicates from intricate mixtures of exchanging polymers (see figure).

    7. Single-Molecule Magnets

      Structural Design of Easy-Axis Magnetic Anisotropy and Determination of Anisotropic Parameters of LnIII[BOND]CuII Single-Molecule Magnets (pages 196–205)

      Prof. Dr. Takashi Kajiwara, Prof. Dr. Motohiro Nakano, Kohei Takahashi, Dr. Shinya Takaishi and Prof. Dr. Masahiro Yamashita

      Version of Record online: 10 DEC 2010 | DOI: 10.1002/chem.201002434

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      Let's stick together: Four dinuclear LnIII[BOND]CuII complexes (Ln=Tb, Dy, Ho, Er) were synthesized to investigate the relationship between their respective magnetic and ligand-field anisotropies. A uni-axial ligand field (see figure) was achieved by using three phenoxo oxygen atoms in these complexes, of which detailed single-molecule magnet behaviors and the determination of magnetic anisotropy parameters were discussed.

    8. DNA Repair

      Investigation of Excess-Electron Transfer in DNA Double-Duplex Systems Allows Estimation of Absolute Excess-Electron Transfer and CPD Cleavage Rates (pages 206–212)

      M. Pharm. Chem. Danila Fazio, Dr. Christian Trindler, Dipl.-Chem. Korbinian Heil, Dr. Chryssostomos Chatgilialoglu and Prof. Dr. Thomas Carell

      Version of Record online: 16 NOV 2010 | DOI: 10.1002/chem.201001978

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      Caught in a trap: A DNA double-duplex system was established to calculate rates of reactions triggered by single-electron reduction. The structure consists of two electron acceptors present concurrently in the 3′ and 5′ directions (see scheme). By keeping the electron trap in the 5′ direction constant, measurement of the relative cleavage rates was achieved. Cleavage of the T[DOUBLE BOND]T dimer is slower by a factor of eight than debromination of BrdU.

    9. Molecular Switches

      A Multistate Switchable [3]Rotacatenane (pages 213–222)

      Gokhan Barin, Dr. Ali Coskun, Douglas C. Friedman, Mark A. Olson, Michael T. Colvin, Dr. Raanan Carmielli, Dr. Sanjeev K. Dey, Dr. O. Altan Bozdemir, Prof. Michael R. Wasielewski and Prof. J. Fraser Stoddart

      Version of Record online: 5 JAN 2011 | DOI: 10.1002/chem.201002152

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      Happy marriage of a rotaxane and a catenane: A strategy for the synthesis of a new switchable [3]rotacatenane (see figure) and the investigation of its switching properties, which rely on the formation of tetrathiafulvalene radical π-dimer interactions—namely, the mixed-valence state and the radical-cation dimer state—under ambient conditions is described.

    10. Sensors

      A Pyrophosphate-Responsive Gadolinium(III) MRI Contrast Agent (pages 223–230)

      Dr. Andrew J. Surman, Dr. Célia S. Bonnet, Dr. Mark P. Lowe, Gavin D. Kenny, Prof. Jimmy D. Bell, Dr. Éva Tóth and Dr. Ramon Vilar

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/chem.201001397

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      Pick an anion: The anion-binding properties of functionalised Ln-DTPA-bis-amide complexes (Ln=Gd3+, Eu3+, DTPA=diethylene triamine pentaacetic acid) were investigated by using indicator displacement assays (IDAs) (see picture). A remarkable selectivity for polyphosphorylated species was observed. This has been successfully used to modulate the relaxivity of the Gd3+ complex with pyrophosphate.

    11. Chiral Linear Polyenes

      Preparation of Highly Hindered Polyenes with tert-Butyl Groups in Internal Positions (pages 231–247)

      Dr. Markus Betz, Prof. Dr. Henning Hopf, Prof. Dr. Ludger Ernst, Prof. Dr. Peter G. Jones and Prof. Dr. Yoshio Okamoto

      Version of Record online: 1 DEC 2010 | DOI: 10.1002/chem.201001250

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      Interior decoration! Although terminally tert-butylated tetraenes prefer a planar structure, the introduction of tert-butyl groups in the “interior” of a tetraene produces an orthogonal and, therefore, chiral conformation (see scheme).

    12. Dynamic Processes

      Configurational and Constitutional Information Storage: Multiple Dynamics in Systems Based on Pyridyl and Acyl Hydrazones (pages 248–258)

      Dr. Manuel N. Chaur, Dr. Daniel Collado and Prof. Dr. Jean-Marie Lehn

      Version of Record online: 13 DEC 2010 | DOI: 10.1002/chem.201002308

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      Systems multiplicity in operation: Specific pyridyl- and acyl hydrazones present chemically and physically driven triple dynamics with different time dependences: configurational (short term), constitutional (long term), and metal-ion coordination (locked) (see picture). These processes are reversible and operated through orthogonal triggers. They thus allow the implementation of three independent levels of control and give access to multiple state molecular devices of interest for the design of systems displaying a high level of functional complexity.

    13. Isotope Labeling

      Synthesis and Application of Isocyanates Radiolabeled with Carbon-11 (pages 259–264)

      Dr. Alan A. Wilson, Armando Garcia, Dr. Sylvain Houle, Dr. Oleg Sadovski and Dr. Neil Vasdev

      Version of Record online: 12 NOV 2010 | DOI: 10.1002/chem.201002345

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      Who needs phosgene anyway? Carbon-11 labeled isocyanates can be efficiently prepared by dehydration of [11C]carbamate salts, which in turn are easily formed from [11C]CO2 and amines in the presence of a CO2 fixation agent. The [11C]isocyanates are useful radiosynthons for the synthesis of a variety of [carbonyl-11C]-labeled asymmetrical ureas and carbamate esters (see scheme).

    14. Density Functional Calculations

      Reaction Site Diversity in the Reactions of Titanium Hydrazides with Organic Nitriles, Isonitriles and Isocyanates: Ti[DOUBLE BOND]Nα Cycloaddition, Ti[DOUBLE BOND]Nα Insertion and Nα[BOND]Nβ Bond Cleavage (pages 265–285)

      A. Daniel Schofield, Dr. Ainara Nova, Dr. Jonathan D. Selby, Dr. Andrew D. Schwarz, Dr. Eric Clot and Prof. Dr. Philip Mountford

      Version of Record online: 15 DEC 2010 | DOI: 10.1002/chem.201002776

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      Ti-hydrazide transformations: A range of transformations of the Ti[DOUBLE BOND]NNPh2 functional group with unsaturated organic substrates leading to Ti[DOUBLE BOND]Nα [2+2] cycloaddition, Ti[DOUBLE BOND]Nα insertion or Nα[BOND]Nβ bond cleavage products (see scheme) is reported. A DFT study of the mechanisms of the last two reaction types is described.

    15. Aziridines

      Solvent- and Temperature-Dependent Functionalisation of Enantioenriched Aziridines (pages 286–296)

      Dr. Maria Carolina de Ceglie, Dr. Biagia Musio, Dr. Francesco Affortunato, Dr. Anna Moliterni, Dr. Angela Altomare, Prof. Saverio Florio and Prof. Dr. Renzo Luisi

      Version of Record online: 12 NOV 2010 | DOI: 10.1002/chem.201002172

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      Choose the right conditions! When starting from enantioenriched parent aziridines, it is possible to address the regio- and stereoselectivity of the lithiation/electrophile trapping sequence by finely tuning the reaction conditions. Highly enantioenriched functionalised aziridines could be obtained (see graphic) and their usefulness has been demonstrated.

    16. Total Synthesis

      Stereoselective Total Synthesis of (−)-Spirofungin A by Utilising Hydrogen-Bond Controlled Spiroketalisation (pages 297–304)

      John E. Lynch, Dr. Shannon D. Zanatta, Prof. Dr. Jonathan M. White and Prof. Dr. Mark A. Rizzacasa

      Version of Record online: 10 DEC 2010 | DOI: 10.1002/chem.201002501

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      Spiro key: The stereoselective total synthesis of the spiroketal-containing Streptomyces metabolite (−)-spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular hydrogen bond, which favoured the desired spiroketal 2 (13:1 ratio). Other key steps include an efficient cross-metathesis to form the spiroketal precursor and a Stille cross-coupling reaction. A final Wittig extension followed by deprotection gave 1.

    17. Tandem Reactions

      Brønsted Acid Catalyzed Cyclization of Hydroxylated Enynes: A Concise Synthesis of Five-Membered Heterocycles (pages 305–311)

      Dr. Ke-Gong Ji, Jin Chen, Hai-Tao Zhu, Fang Yang, Ali Shaukat and Prof. Dr. Yong-Min Liang

      Version of Record online: 24 NOV 2010 | DOI: 10.1002/chem.201002222

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      Falling into place: A mild and direct pathway for the formation of five-membered heterocyclic compounds from hydroxylated enynes has been developed (see scheme; Z=N,O, Ts=tosyl). This Brønsted acid catalyzed domino process involves the formation of an allene carbocation intermediate, which can be readily trapped by olefins to give various novel five-membered heterocyclic skeletons.

    18. Anion Binding

      Aromatic and Aliphatic CH Hydrogen Bonds Fight for Chloride while Competing Alongside Ion Pairing within Triazolophanes (pages 312–321)

      Yuran Hua, Raghunath O. Ramabhadran, Esther O. Uduehi, Jonathan A. Karty, Prof. Krishnan Raghavachari and Prof. Amar H. Flood

      Version of Record online: 24 NOV 2010 | DOI: 10.1002/chem.201002340

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      Tug of war! Competition experiments were used to show that aromatic phenylene donors are stronger than aliphatic propylene C[BOND]H groups for binding chloride ions (Cl) (see figure). The analysis was aided by the use of a self-consistent model of all the binding equilibria occurring in solution, which included ion pairing for the first time. While the triazolophane separated the Cl from the cation, later in the titration the cation was found to pair with the complex.

    19. Helical Structures

      Reversible Mutarotation in a Macrocyclic Ytterbium Complex (pages 322–328)

      Prof. Francesco P. Ballistreri, Dr. Salvatore Gentile, Dr. Andrea Pappalardo, Prof. Gaetano A. Tomaselli, Sanghamitra Pradhan and Prof. Lorenzo Di Bari

      Version of Record online: 13 DEC 2010 | DOI: 10.1002/chem.201002447

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      Helices are a-changing: In a macrocyclic complex of late lanthanides, a slow ligand conformational rearrangement in solution leads to helicity inversion that can be reverted by slow solvent evaporation and provides a circular dichroism time-marker (see graphic).

    20. Natural Synthesis

      Total Synthesis of Iso- and Bongkrekic Acids: Natural Antibiotics Displaying Potent Antiapoptotic Properties (pages 329–343)

      Dr. Antoine Français, Dr. Antonio Leyva-Pérez, Dr. Gorka Etxebarria-Jardi, Javier Peña and Prof. Dr. Steven V. Ley

      Version of Record online: 13 DEC 2010 | DOI: 10.1002/chem.201002380

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      Iso-bong: A versatile first synthesis of isobongkrekic acid (IBA) has been developed. Key steps include three different palladium cross-couplings and an asymmetric homopropargylation. In-depth synthetic studies reveal the challenges faced in generating the right geometry of each diene.

    21. Biaryl Synthesis

      Synthesis of Biaryl Compounds Using Tandem Ruthenium-Catalyzed Ring-Closing Metathesis (pages 344–349)

      Prof. Dr. Kazuhiro Yoshida, Hiroaki Shida, Dr. Hidetoshi Takahashi and Prof. Dr. Akira Yanagisawa

      Version of Record online: 30 NOV 2010 | DOI: 10.1002/chem.201002074

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      A ringing endorsement: Tandem ring-closing enyne metathesis (RCEM)/ring-closing olefin metathesis (RCM) of tetraenynes with the Grubbs second-generation catalyst followed by elimination, was found to be a new and efficient synthetic approach to biaryl compounds (see scheme). A preliminary asymmetric version of this approach is also presented.

    22. Asbestos

      The Iron-Related Molecular Toxicity Mechanism of Synthetic Asbestos Nanofibres: A Model Study for High-Aspect-Ratio Nanoparticles (pages 350–358)

      Dr. Francesco Turci, Dr. Maura Tomatis, Dr. Isidoro G. Lesci, Prof. Norberto Roveri and Prof. Bice Fubini

      Version of Record online: 24 NOV 2010 | DOI: 10.1002/chem.201001893

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      The role of iron unveiled: An inert synthetic iron-free asbestos nanofibre has been used to clarify at the atomic level the role of iron in fibre-induced toxicity. Upon progressive iron loading, production of reactive oxygen species was inversely related to iron clustering, with low-iron fibres being more reactive than highly loaded ones (see picture).

    23. Symmetry

      Concurrent Symmetries: The Interplay Between Local and Global Molecular Symmetries (pages 359–367)

      Dr. Jorge Echeverría, Abel Carreras, Dr. David Casanova, Dr. Pere Alemany and Prof. Dr. Santiago Alvarez

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/chem.201002128

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      Locals only: Local symmetry is calibrated in molecular fragments of, for example, piano-stool complexes, the valence electron density distribution of which showcases three regions of different rotational symmetries (artistic rendering by Oscar Rosanes).

    24. Aurophilicity

      Aurophilicity: The Effect of the Neutral Ligand L on [{ClAuL}2] Systems (pages 368–377)

      Jesús Muñiz, Cong Wang and Prof. Pekka Pyykkö

      Version of Record online: 5 JAN 2011 | DOI: 10.1002/chem.201001765

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      The aurophilic attraction in perpendicular [{ClAuL}2] model dimers is strongly influenced by the neutral ligand L. The N-heterocyclic carbenes yield stronger interactions than PH3. The spatial orientation of certain ligands in a “paddle” configuration plays an important role on the strength of the interaction.

    25. Biocatalysis

      Enzymatic Racemization of Amines Catalyzed by Enantiocomplementary ω-Transaminases (pages 378–383)

      Dr. Dominik Koszelewski, Barbara Grischek, Dr. Silvia M. Glueck, Prof. Wolfgang Kroutil and Prof. Kurt Faber

      Version of Record online: 30 NOV 2010 | DOI: 10.1002/chem.201001602

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      ω-Transaminases play ping-pong: A biocatalytic protocol for the ‘clean’ racemization of α-chiral prim-amines was developed by an equilibrium-controlled deamination/amination sequence catalyzed by a pair of (R)- and (S)-ω-transaminases (see scheme).

    26. Nanostructures

      New-Phased Metastable V2O3 Porous Urchinlike Micronanostructures: Facile Synthesis and Application in Aqueous Lithium Ion Batteries (pages 384–391)

      Dr. Yang Xu, Dr. Lei Zheng, Prof. Changzheng Wu, Prof. Fei Qi and Prof. Yi Xie

      Version of Record online: 29 OCT 2010 | DOI: 10.1002/chem.201000691

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      A new phase in chemistry! New-phased metastable V2O3 porous urchinlike micronanostructures (see figure) have been successfully synthesized by a simple top-down approach and exhibit improved electrochemical performances with relatively high first discharge capacity and better cycle retention as anode materials in aqueous lithium ion batteries.

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      Version of Record online: 5 JAN 2011 | DOI: 10.1002/chem.201090251

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