Chemistry - A European Journal

Cover image for Vol. 14 Issue 8

March 7, 2008

Volume 14, Issue 8

Pages 2295–2631

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    1. Cover Picture: Facile, One-Step Production of Niacin (Vitamin B3) and Other Nitrogen-Containing Pharmaceutical Chemicals with a Single-Site Heterogeneous Catalyst (Chem. Eur. J. 8/2008) (page 2295)

      Robert Raja, John Meurig Thomas, Michael Greenhill-Hooper, Steven V. Ley and Filipe A. Almeida Paz

      Version of Record online: 28 FEB 2008 | DOI: 10.1002/chem.200890023

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      Single-Site Catalytic green production of Niacin is reported by R. Raja, J. M. Thomas et al. on page 2340 ff. The compound, which is used for the preparation of Vitamin B3, is obtained in a single-step, solvent-free, and environmentally benign manner with a solid source of active oxygen.

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  3. News

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  4. Concept

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    1. (Me3Si)3SiH: Twenty Years After Its Discovery as a Radical-Based Reducing Agent (pages 2310–2320)

      Chryssostomos Chatgilialoglu

      Version of Record online: 28 DEC 2007 | DOI: 10.1002/chem.200701415

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      Tris(trimethylsilyl)silane: The flexibility and applicability of (Me3Si)3SiH in several synthetic transformations are described. The reactivity of (Me3Si)3SiH penetrates areas as diverse as organic synthesis and materials science.

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    1. Concise Total Synthesis of the Thiazolyl Peptide Antibiotic GE2270 A (pages 2322–2339)

      Oscar Delgado, H. Martin Müller and Thorsten Bach

      Version of Record online: 12 FEB 2008 | DOI: 10.1002/chem.200701823

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      A modular assembly of the individual thiazole fragments to the central pyridine core was achieved by regioselective cross-coupling reactions giving access to the title compound (see graphic) in an overall yield of 4.8 % over 20 steps. The successful implementation of orthogonal metallation and protecting group strategies further contributed to the brevity of the total synthesis.

    2. Facile, One-Step Production of Niacin (Vitamin B3) and Other Nitrogen-Containing Pharmaceutical Chemicals with a Single-Site Heterogeneous Catalyst (pages 2340–2348)

      Robert Raja, John Meurig Thomas, Michael Greenhill-Hooper, Steven V. Ley and Filipe A. Almeida Paz

      Version of Record online: 28 JAN 2008 | DOI: 10.1002/chem.200701679

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      It's green and selective! Single-site heterogeneous catalysts (shown here) can be judiciously combined with a solid source of active oxygen for the single-step, solvent-free, and environmentally benign production of Niacin (used in the preparation of Vitamin B3) and other fine-chemical, pharmaceutical, and agrochemical intermediates.

    3. Design of Hydrophobic Polyoxometalate Hybrid Assemblies Beyond Surfactant Encapsulation (pages 2349–2354)

      Yu-Fei Song, Nicola McMillan, De-Liang Long, Johannes Thiel, Yulong Ding, Haisheng Chen, Nikolaj Gadegaard and Leroy Cronin

      Version of Record online: 7 FEB 2008 | DOI: 10.1002/chem.200701629

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      Sea urchin architectures: The design of polyoxometalate nanoscale hybrid assemblies comprising a core–shell hydrophilic–hydrophobic structure has been achieved by covalently tethering alkyl chains (C6, C16 and C18) to a Mn-Anderson cluster core producing a surface-grafted cluster architecture. The resulting compounds give highly organized structures on silicon substrates as 1D rods with tetrabutyl ammonium (TBA+; see graphic) and 3D-spherical or sea urchin architectures with dimethyl dioctadecyl ammonium (DMDOA+).

    4. Grafting and Thermal Stripping of Organo-Bimetallic Clusters on Au Surfaces: Toward Controlled Co/Ru Aggregates (pages 2355–2362)

      Ahmed Naitabdi, Olivier Toulemonde, Jean Pierre Bucher, Jacky Rosé, Pierre Braunstein, Richard Welter and Marc Drillon

      Version of Record online: 18 JAN 2008 | DOI: 10.1002/chem.200701500

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      All self-organized: A thiol-functionalized, heterometallic carbonyl cluster [RuCo3(CO)11(H)(Ph2PCH2CH2SH)] (see picture) has been self-assembled on a Au(111) surface. Thermal annealing of this cluster in ultra-high vacuum led to the formation of a bimetallic alloy. Preliminary experiments indicate that the double cluster, with a disulfide linkage between two {RuCo3} tetrahedra, behaves similarly.

    5. Monitoring Transport Phenomena of Paramagnetic Metal-Ion Complexes Inside Catalyst Bodies with Magnetic Resonance Imaging (pages 2363–2374)

      Jaap A. Bergwerff, Anna A. Lysova, Leticia Espinosa-Alonso, Igor V. Koptyug and Bert M. Weckhuysen

      Version of Record online: 7 JAN 2008 | DOI: 10.1002/chem.200700990

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      How do you want your eggs? Magnetic resonance imaging (MRI) was used to monitor the distribution of paramagnetic metal-ion complexes inside catalyst extrudates. By addition of citric acid to the impregnation solution, the distribution of Co2+ complexes inside Al2O3 bodies could be varied from eggshell through egg white and egg yolk to uniform. In all cases, the distribution was reliably determined by MRI in a noninvasive manner (see picture).

    6. The Search for a Potentially Prebiotic Synthesis of Nucleotides via Arabinose-3-phosphate and Its Cyanamide Derivative (pages 2375–2388)

      Carole Anastasi, Fabien F. Buchet, Michael A. Crowe, Madeleine Helliwell, Jim Raftery and John D. Sutherland

      Version of Record online: 18 JAN 2008 | DOI: 10.1002/chem.200701351

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      Prebiotic nucleotide assembly—back to basics? Arabinose-3-phosphate can be converted into an activated nucleotide under potentially prebiotic conditions (see scheme), but can this ostensibly simple sugar phosphate—or its cyanamide derivative—self-assemble from simple building blocks?

    7. Structural Changes and Coordinatively Unsaturated Metal Atoms on Dehydration of Honeycomb Analogous Microporous Metal–Organic Frameworks (pages 2389–2397)

      Pascal D. C. Dietzel, Rune E. Johnsen, Richard Blom and Helmer Fjellvåg

      Version of Record online: 18 JAN 2008 | DOI: 10.1002/chem.200701370

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      Empty honeycombs: The topotactic dehydration reaction of two coordination polymers was studied by powder X-ray diffraction using synchrotron radiation. The process is smooth and continuous for the cobalt compound with the coordinatively bound water molecule leaving last as evidenced by the progression of site-occupancy factors (see figure). In contrast, the isostructural zinc compound passes through several distinct phases.

    8. Creation of Hierarchical Carbon Nanotube Assemblies through Alternative Packing of Complementary Semi-Artificial β-1,3-Glucan/Carbon Nanotube Composites (pages 2398–2404)

      Munenori Numata, Kouta Sugikawa, Kenji Kaneko and Seiji Shinkai

      Version of Record online: 17 JAN 2008 | DOI: 10.1002/chem.200701205

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      Entrapped structures: If single-walled carbon nanotubes (SWNTs) are entrapped into the helical superstructure of either cationic or anionic semi-artificial β-1,3-glucans, then these oppositely-charged SWNT composites can be easily organized into their hierarchical structures that feature the ordered SWNT structure (see graphic).

    9. Highly Effective Acyclic Carbohydrate Receptors Consisting of Aminopyridine, Imidazole, and Indole Recognition Units (pages 2405–2419)

      Monika Mazik and Matthias Kuschel

      Version of Record online: 18 JAN 2008 | DOI: 10.1002/chem.200701269

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      Very receptive: High binding affinity and selectivity of new carbohydrate receptors (depicted in figure) was achieved through the participation of different types of binding units, which included recognition units that are used in nature as well as analogues of the natural units, in the recognition process. The design of these receptors was inspired by the analysis of the binding motifs found in the crystal structures of protein–carbohydrate receptors.

    10. Remarkable Ligand Effect in Ni- and Pd-Catalyzed Bisthiolation and Bisselenation of Terminal Alkynes: Solving the Problem of Stereoselective Dialkyldichalcogenide Addition to the C[TRIPLE BOND]C Bond (pages 2420–2434)

      Valentine P. Ananikov, Konstantin A. Gayduk, Irina P. Beletskaya, Victor N. Khrustalev and Mikhail Yu. Antipin

      Version of Record online: 21 JAN 2008 | DOI: 10.1002/chem.200701278

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      Two new catalytic systems were developed to carry out stereoselective addition of dialkyldichalcogenides (Alk2E2; E=S, Se) to terminal alkynes (see scheme). A comparative study has revealed that the Ni catalyst is superior with respect to high catalytic activity and wide scope. The advantages and disadvantages of both catalytic systems (Ni and Pd) were analyzed in details in the present study.

    11. Sugar–Oligoamides: Bound-State Conformation and DNA Minor-Groove-Binding Description by TR-NOESY and Differential-Frequency Saturation-Transfer-Difference Experiments (pages 2435–2442)

      Florence Souard, Eva Muñoz, Pablo Peñalver, Concepción Badía, Rafael del Villar-Guerra, Juan Luis Asensio, Jesús Jiménez-Barbero and Cristina Vicent

      Version of Record online: 18 JAN 2008 | DOI: 10.1002/chem.200701103

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      In the groove: Selective-frequency saturation-transfer-difference spectra allow the description of complexes established between minor-groove binders (such as 1 and 2; β-L-Fuc: β-L-fucose; Py: N-methylpyrrole; γ: γ-aminobutyric linker; Ind: indole) and long tracts of calf thymus DNA.

    12. Pd-Catalyzed Aryl Amination Mediated by Well Defined, N-Heterocyclic Carbene (NHC)–Pd Precatalysts, PEPPSI (pages 2443–2452)

      Michael G. Organ, Mirvat Abdel-Hadi, Stephanie Avola, Igor Dubovyk, Niloufar Hadei, Eric Assen B. Kantchev, Christopher J. O'Brien, Mahmoud Sayah and Cory Valente

      Version of Record online: 25 JAN 2008 | DOI: 10.1002/chem.200701621

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      A practical protocol for the amination of aryl chlorides and bromides catalyzed by Pd-PEPPSI precatalysts affords a range of sterically hindered and functionalized, drug-like aryl amines in good to excellent yield under strongly (tBuOK) or weakly basic (Cs2CO3) conditions.

    13. Studies on Thermal Reactivity of β-(1,2-Allenyl)butenolides and 2-Allyl-3-allenylcyclohex-2-enones (pages 2453–2464)

      Zhenhua Gu and Shengming Ma

      Version of Record online: 21 JAN 2008 | DOI: 10.1002/chem.200701171

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      A series of thermal pericyclic reactions of β-allenylfuranones have been studied. It was observed that β-allenylfuranones would undergo 1,5-hydrogen shifts to afford new types of trienes upon heating. Due to their high reactivity, these trienes would undergo subsequent pericyclic reactions based on the nature of the substituent group R (see scheme).

    14. Synthesis and In Vitro Biological Properties of Novel Cationic Derivatives of Amphotericin B (pages 2465–2481)

      Valérie Paquet, Astrid A. Volmer and Erick M. Carreira

      Version of Record online: 14 JAN 2008 | DOI: 10.1002/chem.200701237

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      The modular approach: The introduction of an amide function at C-16 and a polyamine moiety on the mycosamine of amphotericin B (see graphic) lead to a significant improvement in antifungal activity and reduced toxicity.

    15. Switchable C- and N-Bound Isomers of Transition-Metal Cyanocarbanions: Synthesis and Interconversions of Cyclopentadienyl Ruthenium Complexes of Phenylsulfonylacetonitrile Anions (pages 2482–2498)

      Takeshi Naota, Akio Tannna, Shigeaki Kamuro, Masayuki Hieda, Kazuki Ogata, Shun-Ichi Murahashi and Hikaru Takaya

      Version of Record online: 14 JAN 2008 | DOI: 10.1002/chem.200701315

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      Sliding makes it easy: The synthesis, structure, and specific linkage isomerization of bistable C- and N-bound isomers of transition-metal cyanocarbanions are described. Experimental and theoretical studies revealed that both the N-to-C and C-to-N isomerizations proceed unimolecularly through the sliding of the metal atom over the C[BOND]C[TRIPLE BOND]N surface (see graphic).

    16. Selective Mono- and 1,2-Difunctionalisation of Cyclopentene Derivatives via Mg and Cu Intermediates (pages 2499–2506)

      Christina Despotopoulou, Richard C. Bauer, Arkady Krasovskiy, Peter Mayer, Jeffrey M. Stryker and Paul Knochel

      Version of Record online: 29 JAN 2008 | DOI: 10.1002/chem.200701431

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      Cyclopentene derivatives have been mono- and difunctionalised in a one-pot reaction using Br/Mg exchange. A β-bromocyclopentenylmagnesium intermediate was prepared from 1,2-dibromocyclopentene and iPrMgCl⋅ LiCl. Treatment of this Grignard reagent with a range of electrophiles gave the corresponding substituted cyclopentenes in good yields. Substitution of the second bromo substituent permitted difunctionalisation.

    17. Direct Thermal Decomposition of Metal Nitrates in Octadecylamine to Metal Oxide Nanocrystals (pages 2507–2513)

      Ding-Sheng Wang, Ting Xie, Qing Peng, Shao-Yan Zhang, Jun Chen and Ya-Dong Li

      Version of Record online: 11 JAN 2008 | DOI: 10.1002/chem.200701668

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      Advancing nanotechnology: A method of direct thermal decomposition of metal nitrates was developed to synthesize various metal oxide nanocrystals, such as Mn3O4, NiO, ZnO, CeO2, CoO, and Co3O4, with controllable shape and size. The nanocrystals were used as building blocks to construct meso-architectures (figure right). The as-obtained mesoporous metal oxides show potential applications in catalysis and lithium-ion batteries.

    18. A Family of Enneanuclear Iron(II) Single-Molecule Magnets (pages 2514–2526)

      Athanassios K. Boudalis, Yiannis Sanakis, Juan Modesto Clemente-Juan, Bruno Donnadieu, Vassilios Nastopoulos, Alain Mari, Yanick Coppel, Jean-Pierre Tuchagues and Spyros P. Perlepes

      Version of Record online: 22 JAN 2008 | DOI: 10.1002/chem.200701487

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      Single-molecule magnets: Pseudohalide substitution in the ferrous enneanuclear complex [Fe9(OH)2(O2CMe)8{(2-py)2CO2}4] does not disrupt its structure, but leads to the analogous N3 and NCO complexes (see graphic). These exhibit stronger ferromagnetic interactions and higher ground-state spins. They are also found to behave as single-molecule magnets at low temperatures.

    19. Efficient Synthesis of the Structural Core of Tetracyclines by a Palladium-Catalyzed Domino Tsuji–Trost–Heck–Mizoroki Reaction (pages 2527–2535)

      Lutz F. Tietze, Thomas Redert, Hubertus P. Bell, Sascha Hellkamp and Laura M. Levy

      Version of Record online: 17 JAN 2008 | DOI: 10.1002/chem.200701676

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      Multiple-ring synthesis: Hexahydronaphthacenes and octahydroanthracenes can be formed by a palladium-catalyzed domino Tsuji–Trost–Heck–Mizoroki reaction with starting materials that contain an allyl acetate and a halogen aryl moiety (see scheme; dppe: 1,2-bis(diphenylphosphino)ethane). The octahydroanthracene and hexahydronaphthacene motifs are found in many natural products, such as the tetracycline antibiotics.

    20. Utilizing Reversible Copper(II) Peptide Coordination in a Sequence-Selective Luminescent Receptor (pages 2536–2541)

      Stefan Stadlbauer, Alexander Riechers, Andreas Späth and Burkhard König

      Version of Record online: 21 JAN 2008 | DOI: 10.1002/chem.200701442

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      More rational design of sequence-selective peptide receptors: Coordination chemistry and ammonium ion recognition by crown ethers join forces in a luminescent peptide receptor with selectivity for glycine–histidine sequences (see graphic). Nearly micromolar affinities for GGH and GHG are observed.

    21. First Principles Computation of Lattice Energies of Organic Solids: The Benzene Crystal (pages 2542–2547)

      Ashley L. Ringer and C. David Sherrill

      Version of Record online: 7 JAN 2008 | DOI: 10.1002/chem.200701622

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      Highly accurate: A methodology for computing lattice energies of neutral organic crystals within chemical accuracy is established and applied to crystalline benzene (see scheme). Three-body interactions are negligible for this system, but dimers beyond the first coordination sphere contribute about 10 % of the lattice energy.

    22. Covalent Tethering of Organic Functionality to the Surface of Glassy Carbon Electrodes by Using Electrochemical and Solid-Phase Synthesis Methodologies (pages 2548–2556)

      Jean-Mathieu Chrétien, Mohamed A. Ghanem, Philip N. Bartlett and Jeremy D. Kilburn

      Version of Record online: 18 JAN 2008 | DOI: 10.1002/chem.200701559

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      Covalent grafting of the anthraquinone redox system onto glassy carbon (GC) electrodes via different linkers and spacers (see picture) has been achieved by using electrochemical and solid-phase synthesis methodologies. The surface coverage, stability and electron transfer of the tethered anthraquinone redox centre through the different spacers have been investigated by cyclic voltammetry, and the effects of pH and scanning rate studied.

    23. Osmium Pyme Complexes for Fast Hydrogenation and Asymmetric Transfer Hydrogenation of Ketones (pages 2557–2563)

      Walter Baratta, Maurizio Ballico, Alessandro Del Zotto, Katia Siega, Santo Magnolia and Pierluigi Rigo

      Version of Record online: 28 DEC 2007 | DOI: 10.1002/chem.200701719

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      Thetransandciscomplexes [OsCl2P2(Pyme)] (Pyme=1-(pyridin-2-yl)methanamine) efficiently catalyze the hydrogenation (turnover frequency (TOF) up to 1.5×104 h−1) and transfer hydrogenation (TH) of several ketones in basic alcohols (TOF up to 5.7×105 h−1; see scheme). High enantioselective TH (up to 96 %) has been observed by using [OsCl2(PPh3)3] with chiral diphosphane and Pyme ligands.

    24. Molecular and Electronic Structures of One-Electron Oxidized NiII–(Dithiosalicylidenediamine) Complexes: NiIII–Thiolate versus NiII–Thiyl Radical States (pages 2564–2576)

      Philip A. Stenson, Ashley Board, Armando Marin-Becerra, Alexander J. Blake, E. Stephen Davies, Claire Wilson, Jonathan McMaster and Martin Schröder

      Version of Record online: 21 JAN 2008 | DOI: 10.1002/chem.200701108

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      Radical ping-pong: The complexes [Ni(N2S2)]+ switch between formal NiII–thiyl radical or NiIII–thiolate states that are dependent on the nature of the axial ligands; the NiII–thiyl radical centers undergo S–S coupling to form Ni-S-S-Ni bonded dimers, which are, for the first time, characterized crystallographically (see graphic).

    25. New Synthesis of 2-Heteroarylperfluoropropionic Acids Derivatives by Reaction of Azine N-Oxides with Hexafluoropropene (pages 2577–2589)

      Rafał Loska and Mieczysław Mąkosza

      Version of Record online: 11 JAN 2008 | DOI: 10.1002/chem.200701416

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      Unstable and spontaneous! One-step conversion of aromatic azine N-oxides into α-heteroaryl perfluoropropionyl fluorides. These fluorides can be used for the acylation of a wide range of nucleophiles (see scheme), whereas treatment of the fluorides in situ with water results in hydrolysis and instantaneous decarboxylation.

    26. Redox-Active p-Quinone-Based Bis(pyrazol-1-yl)methane Ligands: Synthesis and Coordination Behaviour (pages 2590–2601)

      Sebastian Scheuermann, Tonia Kretz, Hannes Vitze, Jan W. Bats, Michael Bolte, Hans-Wolfram Lerner and Matthias Wagner

      Version of Record online: 10 JAN 2008 | DOI: 10.1002/chem.200701615

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      Reverse transitions: Mono- and ditopic, redox-active p-quinone-based bis(pyrazol-1-yl)methane ligands (see figure) have been prepared. These ligands can be oxidised on a preparative scale and complexes with palladium can be prepared that are active in C[BOND]C coupling reactions.

    27. Synthesis and Electronic Properties of Monodisperse Oligophenothiazines (pages 2602–2614)

      Markus Sailer, Adam W. Franz and Thomas J. J. Müller

      Version of Record online: 22 JAN 2008 | DOI: 10.1002/chem.200701341

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      A construction kit synthesis: Oligophenothiazines, such as depicted, can be easily synthesized by Suzuki coupling. They are highly fluorescent with high fluorescence quantum yields and large Stokes shifts, and are highly electroactive with low oxidation potentials.

    28. Synthesis, Structures and DFT Calculations on Alkaline-Earth Metal Azide-Crown Ether Complexes (pages 2615–2624)

      Michael D. Brown, Martin F. Davis, John M. Dyke, Francesco Ferrante, William Levason, J. Steven Ogden and Michael Webster

      Version of Record online: 28 JAN 2008 | DOI: 10.1002/chem.200701502

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      A variety of coordination modes for the azide groups including κ1, μ-1,3 and linkages via H-bonded water molecules in addition to azide ions are displayed by a series of azide complexes of Ca, Sr and Ba with crown ethers. For example, [Ba([18]crown-6)(N3)2(MeOH)]⋅1/3 MeOH contains dinuclear cations and three μ-1,3-NNN bridges (see picture), the first of this type in main group chemistry.

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      Preview: Chem. Eur. J. 9/2008 (page 2631)

      Version of Record online: 28 FEB 2008 | DOI: 10.1002/chem.200890026

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