Chemistry - A European Journal

Cover image for Vol. 9 Issue 7

April 4, 2003

Volume 9, Issue 7

Pages 1451–1654

    1. Macrocycles from Perhalogenated Heterocycles (pages 1464–1469)

      Graham Sandford

      Version of Record online: 13 MAR 2003 | DOI: 10.1002/chem.200390165

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      Perhalogenated heteroaromatic systems, such as 1, are multifunctional building blocks that react with difunctional nucleophiles to give macrocyclic and cage-like compounds that have unusual structural and complexation characteristics, such as the recognition of anions in solution. The great number of available perhaloheterocyclic compounds and suitable nucleophiles makes the number of supramolecular systems that is available through this approach virtually limitless.

    2. High-Pressure Structural Trends of Group 15 Elements: Simple Packed Structures versus Complex Host–Guest Arrangements (pages 1471–1478)

      Ulrich Häussermann

      Version of Record online: 13 MAR 2003 | DOI: 10.1002/chem.200390166

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      The high-pressure structural sequence of the heavier elements As, Sb, and Bi is distinguished by the occurrence of a complex incommensurately modulated host–guest structure, whereas that of P displays the rare simple hexagonal (sh) structure (see picture). Ab initio density functional calculations revealed that the different high-pressure behavior of Group 15 elements can be explained by the elements' different ability to s–d mixing under pressure. In P s–d mixing becomes especially effective because of the absence of d electrons in the core.

    3. A Novel Design Method of Ratiometric Fluorescent Probes Based on Fluorescence Resonance Energy Transfer Switching by Spectral Overlap Integral (pages 1479–1485)

      Hideo Takakusa, Kazuya Kikuchi, Yasuteru Urano, Hirotatsu Kojima and Tetsuo Nagano

      Version of Record online: 13 MAR 2003 | DOI: 10.1002/chem.200390167

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      A novel design method of ratiometric fluorescent probes has been developed using fluorescence resonance energy transfer switching by spectral overlap integral. Based on this approach, we succeeded in developing novel fluorescent probes for protein tyrosine phosphatase (see scheme).

    4. DFT Study of the NMR Properties of Xenon in Covalent Compounds and van der Waals Complexes—Implications for the Use of 129Xe as a Molecular Probe (pages 1486–1495)

      Alessandro Bagno and Giacomo Saielli

      Version of Record online: 13 MAR 2003 | DOI: 10.1002/chem.200390168

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      DFT calculations allow for the accurate estimation of the 129Xe chemical shifts and couplings in covalent xenon compounds, as well as the prediction of chemical shifts and through-space couplings in van der Waals complexes modeling the environment of Xe when used as a molecular probe. The picture shows one such complex modeling a xenon–zeolite interaction. The calculated through-space J(129Xe,17O) coupling with the central oxygen is about 4 Hz.

    5. Chalcogenide-Lewis Acid Mediated Reactions of Electron-Deficient Alkynes with Aldehydes (pages 1496–1502)

      Sayaka Kinoshita, Hironori Kinoshita, Tatsunori Iwamura, Shin-ichi Watanabe and Tadashi Kataoka

      Version of Record online: 13 MAR 2003 | DOI: 10.1002/chem.200390169

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      Reactions of but-3-yn-2-one with aldehydes in the presence of a Lewis acid and dimethyl sulfide predominantly gave (E)-α-(halomethylene) aldols in high yields, while reactions of methyl propiolate mainly afforded (Z)-3-halogeno-2-(hydroxymethyl)acrylates in low to moderate yields.

    6. Theoretical Study of the [2+3] Cycloaddition of Nitrones to Nitriles—Influence of Nitrile Substituent, Solvent and Lewis Acid Coordination (pages 1503–1510)

      Gabriele Wagner

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390172

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      Lewis acids promote the cycloaddition of nitrones to nitriles by changing the reaction mechanism from a concerted pathway towards a two-step reaction (see scheme). The Lewis acid does not modify the reactivity of the nitrile, but rather stabilizes transition states, intermediates and products. This alternative concept of activation might give new inspiration for a further development in Lewis acid promoted chemistry.

    7. Palladium-Catalyzed Cascade Reaction of α,β-Unsaturated Sulfones with Aryl Iodides (pages 1511–1520)

      Pablo Mauleón, Angel A. Núñez, Inés Alonso and Juan C. Carretero

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390173

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      The reaction of α,β-unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions takes place mainly by a cascade process affording 9,10-dihydrophenanthrenes [Eq. (1)].

    8. Adjustment of Twist Angles in Pseudo-Helical Lanthanide Complexes by the Size of Metal Ions (pages 1521–1528)

      Shin Mizukami, Hirohiko Houjou, Masatoshi Kanesato and Kazuhisa Hiratani

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390174

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      Fine-tuning of helical structures: Solid-state structure analyses of a series of seven-coordinate lanthanide complexes (from La to Lu) were carried out (two examples of which are shown here). The result shows that the twist angles of tripodal pseudo-helical complexes can be finely adjusted by choosing a suitable lanthanide ion. Lanthanide complexes are promising nanomodules for building micro- or nanostructures.

    9. Large Enhancement of the Nonlinear Optical Response of Reduced Fullerene Derivatives (pages 1529–1534)

      Emmanuil Koudoumas, Maria Konstantaki, Antonis Mavromanolakis, Stelios Couris, Marianna Fanti, Francesco Zerbetto, Konstantinos Kordatos and Maurizio Prato

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390175

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      The third-order nonlinear optical properties of fulleropyrrolidine, its salt, and their reduced forms are investigated (the reduced forms of the salt are shown here). Upon reduction, the response increases by up to, and sometimes more than, three orders of magnitude, giving values comparable to the largest ever reported.

    10. Quantitative Comparison of Kinetic Stabilities of Metallomacrocycle-Based Rotaxanes (pages 1535–1541)

      Sung-Youn Chang, Hye-Young Jang and Kyu-Sung Jeong

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390176

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      The kinetic stabilities of four metallomacrocycle-based rotaxanes have been quantitatively measured and compared with one another by 1H NMR spectroscopic techniques. The rhenium-based one is found to be a novel rotaxane in which two contradictory properties, kinetic stability and reversibility (see scheme), are properly balanced.

    11. The Structure of Lipid A of the Lipopolysaccharide from Burkholderia caryophylli with a 4-Amino-4-deoxy-L-arabinopyranose 1-Phosphate Residue Exclusively in Glycosidic Linkage (pages 1542–1548)

      Antonio Molinaro, Buko Lindner, Cristina De Castro, Birte Nolting, Alba Silipo, Rosa Lanzetta, Michelangelo Parrilli and Otto Holst

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390177

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      The complete structure of lipid A from the lipopolysaccharides of the plant-pathogenic bacterium Burkholderia caryophylli was characterized. For the first time, a 4-amino-4-deoxy-L-arabinopyranose 1-phosphate residue was proven to be exclusively linked to the reducing end of lipid A from a wild-type LPS. The structure (see picture) was characterized by MALDI-TOF mass spectrometry and by 1H and 13C NMR spectroscopy.

    12. Photochemical Reaction of N,N-Dimethyl-4-chloroaniline with Dienes: New Synthetic Paths via a Phenyl Cation (pages 1549–1555)

      Benedetta Guizzardi, Mariella Mella, Maurizio Fagnoni and Angelo Albini

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390178

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      The photochemically generated 4-aminophenyl cation adds to dienes and when these are cyclic intramolecular C[BOND]C bond formation ensues (see scheme).

    13. Getting Closer to the Real Bacterial Cell Wall Target: Biomolecular Interactions of Water-Soluble Lipid II with Glycopeptide Antibiotics (pages 1556–1565)

      Pauline J. Vollmerhaus, Eefjan Breukink and Albert J. R. Heck

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390179

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      The noncovalent interactions of vancomycin-group glycopeptide antibiotics with a novel water-soluble lipid II derivative that mimics bacterial cell walls are reported for the first time.

    14. Highly Stereoselective Radical Cyclization of Haloacetals Controlled by the Acetal Center (pages 1566–1577)

      Félix Villar, Tanja Kolly-Kovac, Olivier Equey and Philippe Renaud

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390180

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      Chiral acetal centers allow to control the diastereoselectivity of Ueno–Stork radical cyclizations. This highly diastereoselctive reaction has been applied to the asymmetric synthesis of polysubstituted tetrahydrofurans and γ-lactones such as (+)-eldanolide starting from achiral allylic alcohols and chiral vinyl ethers as depicted.

    15. A Computational Study of Radical Haloacetal Cyclizations Controlled by the Acetal Center (pages 1578–1584)

      Olivier Corminboeuf, Philippe Renaud and Carl H. Schiesser

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390181

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      The stereochemical outcome of the Ueno–Stork reaction has been examined by ab initio and other molecular orbital techniques. A simplified computational procedure, which provides excellent predictive ability for the stereochemical outcome this reaction, has been developed. A novel twist transition state (see figure) has been identified for the first time in 5-exo-trig radical cyclization reactions.

    16. Driving Force Dependence of Intermolecular Electron-Transfer Reactions of Fullerenes (pages 1585–1593)

      Shunichi Fukuzumi, Kei Ohkubo, Hiroshi Imahori and Dirk M. Guldi

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390182

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      Pulse-radiolytic studies were performed to determine the rate constants (ket) of intermolecular electron transfer from fullerenes to a series of arene radical cations in dichloromethane. Electron-transfer reduction of fullerenes with anthracene radical anion was also examined by laser flash photolysis in benzonitrile. The driving force dependence of log ket shows a pronounced decrease towards the highly exothermic region, representing the first definitive confirmation of the existence of the Marcus inverted region in a truly intermolecular electron transfer (see scheme).

    17. Shape-Controlled Bridged Silsesquioxanes: Hollow Tubes and Spheres (pages 1594–1599)

      Joël J. E. Moreau, Luc Vellutini, Michel Wong Chi Man and Catherine Bied

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390183

      A new step has been overcome in the design of shape-controlled nanostructured hybrid silicas. Tubular and spherical bridged silsesquioxanes were synthesized by the hydrolysis of silylated chiral diureido derivatives of trans-(1,1)-diaminocyclohexane. This result opens a novel approach to the development of new hybrid materials with tunable shapes and functionalities.

    18. Synthesis, Structure, and Properties of Novel Open-Cage Fullerenes Having Heteroatom(s) on the Rim of the Orifice (pages 1600–1609)

      Yasujiro Murata, Michihisa Murata and Koichi Komatsu

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390184

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      A 13-membered-ring orifice was formed on the fullerene cage by the insertion of a sulfur atom into the open-cage fullerene derivative having a 12-membered-ring orifice (see diagram). The structures and properties of the related derivatives were investigated by NMR and UV/Vis studies, X-ray analysis, DFT calculations, and DPV measurements.

    19. A Quantum Chemical Study of Racemization Pathways in Substituted Chrysene Derivatives (pages 1610–1619)

      Carsten Kind, Andreas W. Götz and Bernd A. Hess

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390185

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      Complex racemisation pathways of substituted chrysene derivatives (see figure) were identified after an appropriate investigation of the potential-energy surface by means of density functional calculations. Analysis of homodesmotic reactions gave further insights into the strain energy inherent to the substituted compounds.

    20. Sequence-Selective Metalation of Double-Helical Oligodeoxyribonucleotides with PtII, MnII, and ZnII Ions (pages 1620–1630)

      J. Vinje, J. A. Parkinson, P. J. Sadler, T. Brown and E. Sletten

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390186

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      A rule for sequence-selective metalation of double-helical oligonucleotides is proposed that involves both labile and nonlabile complexes. This study represents a new approach in which N15-labeled platinum complexes are used to follow the kinetics of platination of intact double-helical oligonucleotides (see scheme).

    21. The Experimental Electron Density Distribution in the Complex of (E)-1,2-Bis(4-pyridyl)ethylene with 1,4-Diiodotetrafluorobenzene at 90 K (pages 1631–1638)

      Riccardo Bianchi, Alessandra Forni and Tullio Pilati

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390187

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      The nature of the I⋅⋅⋅N halogen bonding in the complex of (E)-1,2-bis(4-pyridyl)ethylene with 1,4-diiodotetrafluorobenzene (see picture) has been characterized by topological analysis of the electron density determined by X-ray diffraction at 90 K with the multipole model and by accurate theoretical calculations.

    22. Photochemical and Thermal Transformations of 1-Aryloxy-2- and 4-Azidoanthraquinones (pages 1639–1644)

      Lubov S. Klimenko, Elena A. Pritchina and Nina P. Gritsan

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390188

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      Photolysis of 1-aryloxy-2-azidoanthraquinones (see scheme) in benzene gave 1-hydroxy-2-arylaminoanthraquinones and two types of 5H-naphtho[2,3-c]phenoxazine-8,13-diones. A mechanism of the photolysis and thermolysis of 2-azido-1-aryloxyanthraquinones is proposed and supported by the data of semiempirical calculations.

    23. Growth of Well-Aligned γ-MnO2 Monocrystalline Nanowires through a Coordination-Polymer-Precursor Route (pages 1645–1651)

      Yujie Xiong, Yi Xie, Zhengquan Li and Changzheng Wu

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390189

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      A new coordination-polymer-precursor route has been developed to synthesize nanowires under hydrothermal conditions. In this work, well-aligned γ-MnO2 nanowires, growing along [0 0 2] axis (shown here), have been successfully prepared by selecting an appropriate coordination polymer, [{Mn(SO4)(4,4′-bpy)(H2O)2}n], as the precursor.

    24. Preview: Chem. Eur. J. 7/2003 (page 1654)

      Version of Record online: 20 MAR 2003 | DOI: 10.1002/chem.200390190