Chemistry - A European Journal

Cover image for Vol. 14 Issue 22

July 28, 2008

Volume 14, Issue 22

Pages 6563–6819

  1. Cover Picture

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    3. Graphical Abstract
    4. News
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    1. Cover Picture: Laves Phases, γ-Brass, and 2×2×2 Superstructures: A New Class of Quasicrystal Approximants and the Suggestion of a New Quasicrystal (Chem. Eur. J. 22/2008) (page 6563)

      Robert F. Berger, Stephen Lee, Jeffreys Johnson, Ben Nebgen and Adrian Chi-Yau So

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200890085

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      Crystals in hyperspace! The mysterious quality of many large unit-cell inorganic crystal structures reminds us that chemists do not yet have a unified understanding of what drives certain structures to exist over others. S. Lee et al. show, in their Full Paper on page 6627 ff., that several common intermetallic structure types and their more complex superstructures are rational projections of a single higher dimensional crystal lattice.

  2. Graphical Abstract

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    3. Graphical Abstract
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  3. News

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  4. Concept

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    1. Understanding Chemical Reactivity: The Case for Atom, Proton and Methyl Transfers (pages 6578–6587)

      Luis G. Arnaut and Sebastião J. Formosinho

      Version of Record online: 19 MAY 2008 | DOI: 10.1002/chem.200701986

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      Predict reactivity? For atom, proton and methyl transfers it is possible to deconstruct the reactivity of many molecular systems into its determining factors, and to reconstruct them to examine the success and failure of widely used structure–reactivity relationships.

  5. Communications

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    1. Self-Aggregation Tendency of Zirconocenium Ion Pairs Which Model Polymer-Chain-Carrying Species in Aromatic and Aliphatic Solvents with Low Polarity (pages 6589–6592)

      Luca Rocchigiani, Cristiano Zuccaccia, Daniele Zuccaccia and Alceo Macchioni

      Version of Record online: 23 JUN 2008 | DOI: 10.1002/chem.200800818

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      From pairs to double pairs: Zirconocene ion pairs bearing an aliphatic chain of variable length were synthesized and investigated by means of NOE and diffusion NMR spectroscopy experiments. The presence of long aliphatic chains allowed an unprecedented investigation of their self-aggregation tendency in cyclohexane (see figure), which has a dielectric constant similar to that of isoparaffins used in industrial plants.

    2. Highly Enantioselective Synthesis of N,N-Dialkylbenzamides with Aryl–Carbonyl Axial Chirality by Rhodium-Catalyzed [2+2+2] Cycloaddition (pages 6593–6596)

      Takeshi Suda, Keiichi Noguchi, Masao Hirano and Ken Tanaka

      Version of Record online: 20 JUN 2008 | DOI: 10.1002/chem.200800953

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      Access to new chiral reagents: The first catalytic enantioselective synthesis of axially chiral N,N-dialkylbenzamides was developed in high yields with outstanding enantiomeric excesses (>99 % ee) by aromatization through a cationic rhodium(I)/segphos or binap complex catalyzed [2+2+2] cycloaddition of 1,6-diynes with N,N-dialkylalkynylamides (see scheme).

    3. H2 Adsorption in Metal-Organic Frameworks: Dispersion or Electrostatic Interactions? (pages 6597–6600)

      Agnieszka Kuc, Thomas Heine, Gotthard Seifert and Hélio A. Duarte

      Version of Record online: 24 JUN 2008 | DOI: 10.1002/chem.200800878

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      The role of the two principal metal-organic framework (MOF) components, the inorganic connector and the organic linker (see scheme), is studied at DFT and ab initio (HF and MP2) levels. We prove that electrostatic interactions (polar MOF connector with induced dipole on H2) have a negligible contribution to the interaction energy, but many sites show appreciable London dispersion attraction to H2 (3–5 kJ mol−1).

    4. Selective Ruthenium-Catalyzed Hydration of Nitriles to Amides in Pure Aqueous Medium Under Neutral Conditions (pages 6601–6605)

      Victorio Cadierno, Javier Francos and José Gimeno

      Version of Record online: 20 JUN 2008 | DOI: 10.1002/chem.200800847

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      Simple, general, efficient, and green: Selective hydration of nitriles to amides (see scheme) can be performed in water under neutral conditions by using the novel hydrosoluble ruthenium(II) catalyst [RuCl26-C6Me6)(PTA-Bn)] (PTA-Bn=1-benzyl-3,5-diaza-1-azonia-7-phosphaadamantane chloride).

    5. Diastereoselective Total Synthesis of (±)-Codeine (pages 6606–6608)

      Marie Varin, Elvina Barré, Bogdan Iorga and Catherine Guillou

      Version of Record online: 18 JUN 2008 | DOI: 10.1002/chem.200800744

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      The value of a tricyclic spirocyclohexadienone intermediate has been illustrated again in the diastereoselective synthesis of (±)-codeine. From this useful intermediate, the formation of the B and D rings of codeine involved a Claisen–Eschenmoser rearrangement as a key step.

    6. Structure and Mechanism of an Unusual Malonate Decarboxylase and Related Racemases (pages 6609–6613)

      Krzysztof Okrasa, Colin Levy, Bernhard Hauer, Nina Baudendistel, David Leys and Jason Micklefield

      Version of Record online: 23 JUN 2008 | DOI: 10.1002/chem.200800918

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      Hole in one! The first structure of an arylmalonate decarboxylase (AMDase; see picture), which reveals the mechanism by which this unusual cofactor-independent enzyme catalyses the decarboxylation of α-arylmalonates, is presented. Notably, an active site “dioxyanion hole” motif is utilised to stabilise a putative high-energy enediolate intermediate. Other AMDases are also characterised, along with a Glu-racemase that also possesses a dioxyanion hole and promiscuous malonate decarboxylase activity.

  6. Full Papers

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    1. A Universal Model for Nanoporous Carbon Supercapacitors Applicable to Diverse Pore Regimes, Carbon Materials, and Electrolytes (pages 6614–6626)

      Jingsong Huang, Bobby G. Sumpter and Vincent Meunier

      Version of Record online: 24 JUN 2008 | DOI: 10.1002/chem.200800639

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      A universal model applicable to diverse pore regimes, carbon materials, and electrolytes is presented for nanoporous carbon supercapacitors. With pore curvature effects included, it takes the form of an electric double-cylinder capacitor (EDCC) for mesopores (2–50 nm), becomes an electric wire-in-cylinder capacitor (EWCC) for micropores (<2 nm), and can be reduced to the commonly used electric double-layer capacitor (EDLC) for macropores (>50 nm).

    2. Laves Phases, γ-Brass, and 2×2×2 Superstructures: A New Class of Quasicrystal Approximants and the Suggestion of a New Quasicrystal (pages 6627–6639)

      Robert F. Berger, Stephen Lee, Jeffreys Johnson, Ben Nebgen and Adrian Chi-Yau So

      Version of Record online: 4 JUL 2008 | DOI: 10.1002/chem.200800336

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      Parallel structure: Several complex cubic crystal structures of varying size and complexity (including Li21Si5; schematic, lower right) are shown to be rational projections of the same higher dimensional crystal lattice (schematic, upper left). This suggests the possible existence of a parent quasicrystal—one with perpendicular pseudo fivefold axes—which has never been observed.

    3. Fluorescent Hydrophobic Zippers inside Duplex DNA: Interstrand Stacking of Perylene-3,4:9,10-tetracarboxylic Acid Bisimides as Artificial DNA Base Dyes (pages 6640–6645)

      Daniela Baumstark and Hans-Achim Wagenknecht

      Version of Record online: 23 JUN 2008 | DOI: 10.1002/chem.200800514

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      A color-changing zipper: The formation of interstrand and intrastrand stacks of the perylene bisimide dye inside duplex DNA (see structure) changes the emission color from green to red, thereby allowing fluorescent readout.

    4. Highly Convenient Amine-Free Sonogashira Coupling in Air in a Polar Mixed Aqueous Medium by trans- and cis-[(NHC)2PdX2] (X=Cl, Br) Complexes of N/O-Functionalized N-Heterocyclic Carbenes (pages 6646–6655)

      Lipika Ray, Samir Barman, Mobin M. Shaikh and Prasenjit Ghosh

      Version of Record online: 18 JUN 2008 | DOI: 10.1002/chem.200800301

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      Two newtrans- andcis-[(NHC)2PdX2]-type complexes (X=Cl, Br) of N/O-functionalized N-heterocyclic carbenes have been synthesized as precatalysts for highly convenient amine-free Sonogashira cross-coupling reactions in air in a polar mixed aqueous medium (see figure).

    5. Discovery of New Biocatalysts for the Glycosylation of Terpenoid Scaffolds (pages 6656–6662)

      Lorenzo Caputi, Eng-Kiat Lim and Dianna J. Bowles

      Version of Record online: 18 JUN 2008 | DOI: 10.1002/chem.200800548

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      Glycosyltransferases for terpenoids: In this study, active biocatalysts that recognise mono-, sesqui- and diterpenoid scaffolds were identified from a unique library of plant glycosyltransferases (GTs; see scheme). These biocatalysts were used in a microbial cell system to biotransform terpenoids into glucosides, providing an alternative route to chemical synthesis.

    6. Comparison of the Acid–Base Properties of Ribose and 2′-Deoxyribose Nucleotides (pages 6663–6671)

      Ariel Mucha, Bernd Knobloch, Małgorzata Jeżowska-Bojczuk, Henryk Kozłowski and Roland K. O. Sigel

      Version of Record online: 20 JUN 2008 | DOI: 10.1002/chem.200800496

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      pKavalues of nucleotides: The 2′-deoxyribose nucleotides (dNMP2−, dNDP3−, dNTP4−) are more basic than the corresponding ribose nucleotides (NMP2−, NDP3−, NTP4−) and N7 is more strongly affected by the absence of the 2′-OH group than N1 or N1. In total, 56 acidity constants are listed and compared.

    7. Gold-Catalyzed Synthesis of Chroman, Dihydrobenzofuran, Dihydroindole, and Tetrahydroquinoline Derivatives (pages 6672–6678)

      A. Stephen K. Hashmi, Matthias Rudolph, Jan W. Bats, Wolfgang Frey, Frank Rominger and Thomas Oeser

      Version of Record online: 23 JUN 2008 | DOI: 10.1002/chem.200800210

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      Golden in minutes! The gold-catalyzed cyclization of furans containing an ynamide or alkynyl ether moiety in the side chain delivered dihydroindole, dihydrobenzofuran, chroman, and tetrahydroquinoline derivatives at room temperature (see scheme). The stabilizing effect of the heteroatom directly attached to the intermediate arene oxides led to highly selective reactions, even in the case of only monosubstituted furans.

    8. A New Catalytic Route to Boryl- and Borylsilyl-Substituted Buta-1,3-dienes (pages 6679–6686)

      Jȩdrzej Walkowiak, Magdalena Jankowska-Wajda and Bogdan Marciniec

      Version of Record online: 13 JUN 2008 | DOI: 10.1002/chem.200800518

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      New catalytic method: For the preparation of boryl- and borylsilyl-substituted dienes, a new catalytic route involving the efficient coupling of vinylboronates with terminal alkynes is reported (see scheme).

    9. An EXAFS Spectroscopic, Large-Angle X-Ray Scattering, and Crystallographic Study of Hexahydrated, Dimethyl Sulfoxide and Pyridine 1-Oxide Hexasolvated Mercury(II) Ions (pages 6687–6696)

      Ingmar Persson, Lars Eriksson, Patric Lindqvist-Reis, Per Persson and Magnus Sandström

      Version of Record online: 18 JUN 2008 | DOI: 10.1002/chem.200800225

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      Solvated structures: The mercury(II) ion is hexasolvated in the oxygen-donor solvents water and dimethyl sulfoxide (see figure) with wide asymmetric distributions of the Hg[BOND]O distances around centroid values of 2.38 Å, as determined by EXAFS spectroscopy and large-angle X-ray scattering.

    10. Palladium-Catalyzed Formation of Highly Substituted Naphthalenes from Arene and Alkyne Hydrocarbons (pages 6697–6703)

      Yao-Ting Wu, Ke-Hsin Huang, Chien-Chueh Shin and Tsun-Cheng Wu

      Version of Record online: 12 JUN 2008 | DOI: 10.1002/chem.200800538

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      Naphthalene synthesis: Highly substituted naphthalenes 3 have been simply synthesized from an arene 1 with two molecules of an alkyne 2. The naphthalene cores in 3 are twisted from the planar geometry.

    11. Fragmentation of Carbohydrate Anomeric Alkoxyl Radicals: New Synthesis of Chiral 1-Fluoro-1-halo-1-iodoalditols (pages 6704–6712)

      Cosme G. Francisco, Concepción C. González, Alan R. Kennedy, Nieves R. Paz and Ernesto Suárez

      Version of Record online: 23 JUN 2008 | DOI: 10.1002/chem.200800734

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      Chiral trihalocarbons: Synthesis of 1,1,1-trihaloalditols from glycal derivatives in which the halogens are introduced sequentially in each of the three different steps of the process (see scheme). In some cases, the trihalo diasteromers could be separated by chromatography.

      Corrected by:

      Corrigendum: Fragmentation of Carbohydrate Anomeric Alkoxyl Radicals: New Synthesis of Chiral 1-Fluoro-1-halo-1-iodoalditols

      Vol. 14, Issue 33, 10179, Version of Record online: 10 NOV 2008

      Corrected by:

      Corrigendum: Fragmentation of Carbohydrate Anomeric Alkoxyl Radicals: New Synthesis of Chiral 1-Fluoro-1-halo-1-iodoalditols

      Vol. 14, Issue 35, 10871, Version of Record online: 2 DEC 2008

    12. “Click Chemistry” in Zeolites: Copper(I) Zeolites as New Heterogeneous and Ligand-Free Catalysts for the Huisgen [3+2] Cycloaddition (pages 6713–6721)

      Stefan Chassaing, Abdelkarim Sani Souna Sido, Aurélien Alix, Mayilvasagam Kumarraja, Patrick Pale and Jean Sommer

      Version of Record online: 23 JUN 2008 | DOI: 10.1002/chem.200800479

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      Click in zeolites! Copper(I) zeolites are practical, highly versatile, and efficient catalysts for the Huisgen cycloaddition (see scheme). These cheap catalysts thus fulfill the “click chemistry” criteria. Mechanistic investigations reveal that this heterogeneous version of the Huisgen click reaction follows a pathway different from the Meldal–Sharpless version.

    13. Preparation of 2,4-Disubstituted Cyclopentenones by Enantioselective Iridium-Catalyzed Allylic Alkylation: Synthesis of 2′-Methylcarbovir and TEI-9826 (pages 6722–6733)

      Pierre Dübon, Mathias Schelwies and Günter Helmchen

      Version of Record online: 23 JUN 2008 | DOI: 10.1002/chem.200800495

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      Prostaglandin synthesis: Chiral 2- or 2,4-substituted cyclopent-2-enones with up to 98 % ee are available through asymmetric Ir-catalyzed allylic alkylation reactions and ring-closing metathesis (see figure; ee=enantiomeric excess). This new method has been applied in syntheses of the prostaglandin analogue TEI-9826 and 2′-methylcarbovir.

    14. Study of Hopping Transport in Long Oligothiophenes and Oligoselenophenes: Dependence of Reorganization Energy on Chain Length (pages 6734–6741)

      Sanjio S. Zade and Michael Bendikov

      Version of Record online: 13 JUN 2008 | DOI: 10.1002/chem.200701182

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      Internal reorganization energies for self-exchange hole-transfer processes were calculated for a series of oligothiophenes and oligoselenophenes up to the 50-mers. A linear correlation between reorganization energy (λ) and reciprocal chain length (1/n) was observed (see picture). The reorganization energy approaches zero (at the B3LYP/6-31G(d) level of theory) for infinite numbers of oligomer units, that is, for polythiophene and polyselenophene.

    15. Reactivity of Molecular Dioxygen towards a Series of Isostructural Dichloroiron(III) Complexes with Tripodal Tetraamine Ligands: General Access to μ-Oxodiiron(III) Complexes and Effect of α-Fluorination on the Reaction Kinetics (pages 6742–6753)

      Nasser K. Thallaj, Olaf Rotthaus, Leila Benhamou, Nicolas Humbert, Mourad Elhabiri, Mohammed Lachkar, Richard Welter, Anne-Marie Albrecht-Gary and Dominique Mandon

      Version of Record online: 18 JUN 2008 | DOI: 10.1002/chem.200701967

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      μ-Oxodiiron(III) compounds are systematically formed by reaction of O2 with dichloroiron(II) complexes containing tris(2-pyridylmethyl)amine (TPA) ligands. Kinetic studies revealed that the reaction proceeds in two distinct steps, of which coordination of O2 to the metal center is the crucial step. Since α-fluoro substituents on the TPA ligands increase the reaction rate (see schematic), coordination of dioxygen seems to be accelerated by higher Lewis acidity at the metal center.

    16. Copper Complexes of Mono- and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models (pages 6754–6770)

      Kai Ruth, Sandor Tüllmann, Hannes Vitze, Michael Bolte, Hans-Wolfram Lerner, Max C. Holthausen and Matthias Wagner

      Version of Record online: 20 JUN 2008 | DOI: 10.1002/chem.200800588

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      Copper scorpionates: Copper complexes of mono- and heteroditopic scorpionate ligands [PhBpz2(CH2SMe)] (pz: pyrazol-1-yl) and p-[pz3B[BOND]C6H4[BOND]Bpz2(CH2SMe)]2− (see graphic) have been prepared and evaluated as model systems for the copper enzymes peptidylglycine α-hydroxylating monooxygenase and dopamine β-monooxygenase.

    17. New Insights on the Mechanism of the Transition-Metal Stereoselective Olefin Cyclopropanation (pages 6771–6779)

      Elena Soriano and José Marco-Contelles

      Version of Record online: 23 JUN 2008 | DOI: 10.1002/chem.200800305

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      Different pathways: The intermolecular cyclopropanation of propargylic carboxylates with olefins (see scheme), which is catalyzed by late transition metals, follows a different mechanistic sequence than the intramolecular process. Our results suggest that the entropic effects could modulate the operative mechanism and account for the mechanistic discrepancy.

    18. A Materials Approach to Site-Isolation of Grubbs Catalysts from Incompatible Solvents and m-Chloroperoxybenzoic Acid (pages 6780–6788)

      Martin T. Mwangi, M. Brett Runge, Kevin M. Hoak, Michael D. Schulz and Ned B. Bowden

      Version of Record online: 18 JUN 2008 | DOI: 10.1002/chem.200800094

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      Simple site-isolation: Site-isolation of >99.5 % of the Grubbs catalyst within polydimethylsiloxane (PDMS) thimbles allowed new cascade reactions with m-chloroperoxybenzoic acid (MCPBA). The catalyst and MCPBA did not diffuse through PDMS, but small organic reagents did and reacted on both sides of the thimbles (see figure).

    19. Asymmetric Three-Component Strecker Reactions Catalyzed by trans-4-Hydroxy-L-proline-Derived N,N′-Dioxides (pages 6789–6795)

      Yuehong Wen, Bo Gao, Yingzi Fu, Shunxi Dong, Xiaohua Liu and Xiaoming Feng

      Version of Record online: 12 JUN 2008 | DOI: 10.1002/chem.200800319

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      Star Strecker! Novel trans-4-hydroxy-L-proline-derived N,N′-dioxides have been developed and used as efficient organocatalysts for the one-pot three-component Strecker reaction (see scheme; ee=enantiomeric excess, TMS=trimethylsilyl). Both aromatic and aliphatic aldehydes were found to be suitable substrates. The corresponding α-amino nitriles were obtained in high yields with up to 95 % ee under mild conditions.

    20. General Synthesis and Aggregation Behaviour of New Single-Chain Bolaphospholipids: Variations in Chain and Headgroup Structures (pages 6796–6804)

      Simon Drescher, Annette Meister, Gesche Graf, Gerd Hause, Alfred Blume and Bodo Dobner

      Version of Record online: 11 JUN 2008 | DOI: 10.1002/chem.200800033

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      Head and chain: New synthetic strategies for the preparation of single-chain bolaphospholipids with modified chain and headgroup structures are presented. Calorimetric and TEM investigations of the temperature-dependent aggregation behaviour of these bolalipids into nanofibres and spherical micelles are described.

    21. Thermal Isomerization of (+)-cis- and (−)-trans-Pinane Leading to (−)-β-Citronellene and (+)-Isocitronellene (pages 6805–6814)

      Achim Stolle, Bernd Ondruschka, Werner Bonrath, Thomas Netscher, Matthias Findeisen and Markus M. Hoffmann

      Version of Record online: 18 JUN 2008 | DOI: 10.1002/chem.200800298

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      Rearrangements in the gaseous phase: Does the ratio of products formed from fragmentations of a cyclobutane ring depend on the stereochemistry of a carbon atom that is not part of the ring? A study investigating the stereochemical influence of such a carbon atom on the selectivity of products obtained from gas-phase rearrangements (see scheme) of a rigid bridged cyclobutane ring is discussed.

  7. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Concept
    6. Communications
    7. Full Papers
    8. Preview
    1. Preview: Chem. Eur. J. 23/2008 (page 6819)

      Version of Record online: 21 JUL 2008 | DOI: 10.1002/chem.200890088

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