Chemistry - A European Journal

Cover image for Vol. 13 Issue 3

January 12, 2007

Volume 13, Issue 3

Pages 723–1007

  1. Cover Picture

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    3. Graphical Abstract
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    1. Cover Picture: The Formation of Byproducts in the Autoxidation of Cyclohexane (Chem. Eur. J. 3/2007) (page 723)

      Ive Hermans, Pierre Jacobs and Jozef Peeters

      Version of Record online: 4 JAN 2007 | DOI: 10.1002/chem.200790008

      The liquid-phase autoxidation of cyclohexane is an important process in the chemical industry, producing cyclohexanone and cyclohexanol. The overlooked propagation of the hydroperoxide gives rise to cyclohexoxy radicals, able to form ring-opened ω-formyl radicals. In their Full Paper on page 754 ff., I. Hermans et al. describe new and straightforward chemistry for the conversion of these radicals into the first major byproduct, 6-hydroxyhexanoic acid, and its subsequent conversion into all other observed byproducts.

  2. Graphical Abstract

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  3. Corrigendum

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    1. You have free access to this content
      Design, Synthesis, and Delivery Properties of Novel Guanidine-Containing Molecular Transporters Built on Dimeric Inositol Scaffolds (page 732)

      Kaustabh K. Maiti, Ock-Youm Jeon, Woo Sirl Lee and Sung-Kee Chung

      Version of Record online: 4 JAN 2007 | DOI: 10.1002/chem.200790010

  4. Concept

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    4. Corrigendum
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    1. Fischer Carbene Complexes: Beautiful Playgrounds To Study Single Electron Transfer (SET) Reactions (pages 736–744)

      Miguel A. Sierra, Mar Gómez-Gallego and Roberto Martínez-Álvarez

      Version of Record online: 15 DEC 2006 | DOI: 10.1002/chem.200601470

      Thumbnail image of graphical abstract

      The reactivity of Fischer carbene complexes towards chemical electron-transfer (ET) reagents (C8K or SmI2), as well as the use of nonconventional sources of electrons, is discussed making special emphasis on the reaction mechanisms.

  5. Full Papers

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    1. 3D Architectures of Iron Molybdate: Phase Selective Synthesis, Growth Mechanism, and Magnetic Properties (pages 746–753)

      Yi Ding, Shu-Hong Yu, Chen Liu and Zheng-An Zang

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/chem.200601426

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      Monoclinic and orthorhombic Fe2(MoO4)3 microsized particles with complex 3D architectures have been selectively prepared by a template-free hydrothermal process. The magnetic properties of monoclinic and orthorhombic Fe2(MoO4)3 complex spheres (see figure) reveal ferromagnetic and antiferromagnetic behavior, respectively.

    2. The Formation of Byproducts in the Autoxidation of Cyclohexane (pages 754–761)

      Ive Hermans, Pierre Jacobs and Jozef Peeters

      Version of Record online: 11 DEC 2006 | DOI: 10.1002/chem.200601242

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      Radicals misbehaving in the liquid phase: In the autoxidation of cyclohexane, cyclohexyl hydroperoxide has now been identified as a key precursor of byproducts. Its fast α-hydrogen abstraction produces large amounts of oxy radicals that are rapidly converted into undesired products (see scheme).

    3. Design, Synthesis, and Delivery Properties of Novel Guanidine-Containing Molecular Transporters Built on Dimeric Inositol Scaffolds (pages 762–775)

      Kaustabh K. Maiti, Ock-Youm Jeon, Woo Sirl Lee and Sung-Kee Chung

      Version of Record online: 6 NOV 2006 | DOI: 10.1002/chem.200600898

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      Beat the barriers: Synthetic molecular transporters built on dimeric inositol scaffolds with octaguanidine head groups (see picture) show significant cellular uptake with different types of cell lines and organs, and with the blood–brain barrier. Doxorubicin was covalently attached to one of the transporter molecules and showed excellent uptake to mouse brain.

    4. Protonated Heme (pages 776–785)

      Barbara Chiavarino, Maria Elisa Crestoni, Simonetta Fornarini and Carme Rovira

      Version of Record online: 16 OCT 2006 | DOI: 10.1002/chem.200600748

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      Iron(II/III) character of protonated heme: Two formal descriptions ([FeII–hemeH]+ and [FeIII–hemeH.]+) concur in characterizing the structural and electronic features of the most stable isomer of protonated heme (see figure) according to density functional theory calculations. Its reactivity with NO and other ligands, and towards H/D-exchange reagents is compared with that of [FeIII–heme]+ in FTICR mass spectrometry.

    5. Unsymmetrical NiII–Imidoylamidine Complexes Derived from a Novel Oxime-Mediated Single-Pot Reaction of Nitriles (pages 786–791)

      Maximilian N. Kopylovich, Matti Haukka, Alexander M. Kirillov, Vadim Yu. Kukushkin and Armando J. L. Pombeiro

      Version of Record online: 18 OCT 2006 | DOI: 10.1002/chem.200600765

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      A new oxime-mediated transformation of nitriles provides a rather easy and convenient method to synthesise unsymmetrical genuine imidoylamidine complexes (see scheme) related to isoindolinone and phthalocyanine species, the first ones to be generated from nitriles in a single-pot reaction. The simplicity, availability and low cost of the reagents, and the relatively mild reaction conditions are further advantages of this method.

    6. Palladium-Catalyzed Intramolecular C(sp3)[BOND]H Functionalization: Catalyst Development and Synthetic Applications (pages 792–799)

      Julien Hitce, Pascal Retailleau and Olivier Baudoin

      Version of Record online: 17 OCT 2006 | DOI: 10.1002/chem.200600811

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      Activating alkyls: A combination of Pd(OAc)2 and a fluoro analogue of P(o-tol)3 shows high activity for the intramolecular C[BOND]H functionalization of alkyl groups (o-tol=2-methylphenyl). This reaction gives rise either to olefins adjacent to a quaternary carbon atom or to polycyclic molecules, depending on the nature of the alkyl group (see scheme). The method has been applied to the synthesis of the antihypertensive drug verapamil.

    7. The Water-Exchange Mechanism of the [UO2(OH2)5]2+ Ion Revisited: The Importance of a Proper Treatment of Electron Correlation (pages 800–811)

      François P. Rotzinger

      Version of Record online: 18 OCT 2006 | DOI: 10.1002/chem.200501472

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      Associative or dissociative mechanisms? For the water-exchange reaction shown in the figure, the importance of a thorough treatment of electron correlation in determining the preferred mechanism is demonstrated. Here the associative mechanism is preferred, but if the water ligands are replaced by stronger electron donors, the dissociative pathway becomes more favorable.

      Corrected by:

      Corrigendum: The Water-Exchange Mechanism of the [UO2(OH2)5]2+ Ion Revisited: The Importance of a Proper Treatment of Electron Correlation

      Vol. 14, Issue 31, 9463, Version of Record online: 21 OCT 2008

    8. Receiver–Amplifier, Self-Immolative Dendritic Device (pages 812–821)

      Roey J. Amir, Eyal Danieli and Doron Shabat

      Version of Record online: 31 OCT 2006 | DOI: 10.1002/chem.200601263

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      A self-immolative dendritic molecule was designed to resemble dendritic architectures present in nature. The synthetic molecule has bond-cleavage, signal-conducting activity that is related to that of neurons. A cleavage signal received from a multiple trigger is transferred convergently to a focal point. The signal is divergently amplified through to the other side of the dendrimer, reporter units are released, and fluorescence is emitted (see representation).

    9. Synthesis, Manipulation and Conductivity of Supramolecular Polymer Nanowires (pages 822–828)

      Liqin Dong, Tom Hollis, Steven Fishwick, Bernard A. Connolly, Nicholas G. Wright, Benjamin R. Horrocks and Andrew Houlton

      Version of Record online: 11 DEC 2006 | DOI: 10.1002/chem.200601320

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      Templating polymer nanowire growth with DNA: Supramolecular conducting polymer nanowires were synthesised by oxidising pyrrole in the presence of DNA, which acts as a template. The AFM image shows immobilised DNA on mica after in situ polymerisation of pyrrole. Non-specific absorption of polymer particulates is evident as bright spots (scale bar=200 nm).

    10. A New Copper(I)–Tetrahydrosalen-Catalyzed Asymmetric Henry Reaction and Its Extension to the Synthesis of (S)-Norphenylephrine (pages 829–833)

      Yan Xiong, Fei Wang, Xiao Huang, Yuehong Wen and Xiaoming Feng

      Version of Record online: 27 OCT 2006 | DOI: 10.1002/chem.200601262

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      A variety of aromatic, heteroaromatic, enal, and aliphatic aldehydes have been found to be suitable substrates for a novel asymmetric Henry reaction, which employs a new chiral CuI–[H4]salen catalyst. Products from this reaction are obtained in moderate to high yields with excellent enantioselectivities (see scheme). This protocol is air-tolerant and has been successfully extended to the synthesis of (S)-norphenylephrine.

    11. Synthesis and Reactivity of Rare Earth Metal Alkyl Complexes Stabilized by Anilido Phosphinimine and Amino Phosphine Ligands (pages 834–845)

      Bo Liu, Dongmei Cui, Jia Ma, Xuesi Chen and Xiabin Jing

      Version of Record online: 18 OCT 2006 | DOI: 10.1002/chem.200601125

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      A dianionic C,N,N supporting ligand is formed when rare earth metal alkyls react with anilido phosphinimines by protolysis and intramolecular C[BOND]H activation (see scheme). The resulting rare earth metal monoalkyl complexes react swiftly with aniline and water. The corresponding reaction with amido phosphines generates N,P ligand-stabilized rare earth bis-alkyl complexes, which can also be protonated by aniline. Both types of complex initiate ring-opening polymerization of lactide.

    12. Carbon Nanotube/Poly(methyl methacrylate) (CNT/PMMA) Composite Electrode Fabricated by In Situ Polymerization for Microchip Capillary Electrophoresis (pages 846–853)

      Xiao Yao, Huixia Wu, Joseph Wang, Song Qu and Gang Chen

      Version of Record online: 18 OCT 2006 | DOI: 10.1002/chem.200600469

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      Efficient detector: A novel carbon nanotube/poly(methyl methacrylate) (CNT/PMMA) composite electrode was developed as a sensitive amperometric detector of microchip capillary electrophoresis. The performance of this system was demonstrated by the separation and detection of phenolic pollutants and purines. A cross section of the CNT/PMMA composites is shown in the SEM image.

    13. Characterization of Peptide–Pyrazole Interactions in Solution by Low-Temperature NMR Studies (pages 854–861)

      Wei Wang and Klaus Weisz

      Version of Record online: 6 NOV 2006 | DOI: 10.1002/chem.200600591

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      Binding a peptide dimer: Pyrazoles recognize and cap a preformed dimeric β-sheet tripeptide through hydrogen bonding at additional outer peptide donor and acceptor sites (see scheme).

    14. Silica Gel Triggered Transformations of 3-Methylenecyclopropylmethyl Sulfonates to 3-Methylenecyclobutyl Analogues: Experimental and Computational Studies (pages 862–869)

      Li-Xiong Shao, Yu-Xue Li and Min Shi

      Version of Record online: 16 OCT 2006 | DOI: 10.1002/chem.200600722

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      In silico veritas: Methylenecyclopropylcarbinols 1 treated with sulfonyl chloride and Et3N yield the sulfonated products 3 in almost quantitative yields, which can be transformed to the corresponding 3-methylenecyclobutyl sulfonates 4 by silica gel chromatography work-up. The rational explanation was proposed on the basis of computational studies.

    15. Memory Effect of Activated Mg–Al Hydrotalcite: In Situ XRD Studies during Decomposition and Gas-Phase Reconstruction (pages 870–878)

      Javier Pérez-Ramírez, Sònia Abelló and Niek M. van der Pers

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/chem.200600767

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      Insights into the mechanism and kinetics of the thermal activation and reconstruction (memory effect) of Mg–Al hydrotalcite (see figure) have been obtained by means of in situ XRD. These are of prime importance for optimal activation of this type of material as a catalyst.

    16. Asymmetric Synthesis of Rubiginones A2 and C2 and Their 11-Methoxy Regioisomers (pages 879–890)

      M. Carmen Carreño, Álvaro Somoza, María Ribagorda and Antonio Urbano

      Version of Record online: 6 NOV 2006 | DOI: 10.1002/chem.200600809

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      Two in a row: Two domino processes allowed a short access to the angucyclinone-type antibiotic rubiginone C2 (4) and its regioisomer 5. In the first, a complete opposite regiocontrol was achieved in the convergent construction of the tetracyclic skeleton by Diels–Alder reaction of 2- or 3-(p-tolylsulfinyl) methyl juglones 2 or 3 with enantiopure vinyl cyclohexene 1, followed by sulfoxide elimination. The second domino sequence, mediated by oxygen and sunlight, led to the final targets.

    17. Synthesis, Structures, and Properties of meso-Phosphorylporphyrins: Self-Organization through P–Oxo–Zinc Coordination (pages 891–901)

      Yoshihiro Matano, Kazuaki Matsumoto, Yukiko Terasaka, Hiroki Hotta, Yasuyuki Araki, Osamu Ito, Motoo Shiro, Takahiro Sasamori, Norihiro Tokitoh and Hiroshi Imahori

      Version of Record online: 16 OCT 2006 | DOI: 10.1002/chem.200600835

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      Get organized! Copper-catalyzed C[BOND]P cross-coupling reactions are efficient and general methods for introducing phosphoryl groups at the meso position of a porphyrin ring. Zinc phosphorylporphyrins readily undergo self-organization through P–oxo–Zn coordination to form noncovalently linked, cofacial porphyrin dimers (see scheme).

    18. Glycosidation–Anomerisation Reactions of 6,1-Anhydroglucopyranuronic Acid and Anomerisation of β-D-Glucopyranosiduronic Acids Promoted by SnCl4 (pages 902–909)

      Colin O'Brien, Monika Poláková, Nigel Pitt, Manuela Tosin and Paul V. Murphy

      Version of Record online: 6 NOV 2006 | DOI: 10.1002/chem.200601111

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      The importance of anomerisation: The reaction of silylated acceptors with 2,3,4-tri-O-acetyl-6,1-anhydroglucopyranosiduronic acids catalysed by tin(IV) chloride provides 1,2-cis-glycosides; this result is accounted for by the anomerisation of initially formed 1,2-trans-glycosides.

    19. Strategies To Stabilize New Oxides in the Srn+1(CoTa)nO3n+1 Ruddlesden–Popper Homologous Series (pages 910–915)

      Khalid Boulahya, Marina Parras and José María González-Calbet

      Version of Record online: 18 OCT 2006 | DOI: 10.1002/chem.200600882

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      Results of a microstructural study, obtained by means of high-resolution electron microscopy, show a crystal that is composed of the intergrowth of n=2, 3, and 5 members (shown here) of the Ruddlesden–Popper homologous series of chemical composition Srn+1(Co0.5Ta0.5)nO3n+1.

    20. Photosynthetic Reaction Center Mimicry of a “Special Pair” Dimer Linked to Electron Acceptors by a Supramolecular Approach: Self-Assembled Cofacial Zinc Porphyrin Dimer Complexed with Fullerene(s) (pages 916–922)

      Francis D'Souza, Raghu Chitta, Suresh Gadde, Lisa M. Rogers, Paul A. Karr, Melvin E. Zandler, Atula S. D. Sandanayaka, Yasuyaki Araki and Osamu Ito

      Version of Record online: 25 OCT 2006 | DOI: 10.1002/chem.200600885

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      Mimics for the photosynthetic reaction center functionalities have been developed. Here, we have accomplished building a “special-pair” porphyrin donor self-assembled to fullerene without any covalent links to connect different entities. Efficient forward electron transfer and relatively slow reverse electron transfer from the singlet excited zinc porphyrin dimer to the fullerene entity, an important step in the photosynthetic light energy conversion, has been achieved in these novel biomimetic model systems.

    21. Chiral Fluorous Dialkoxy-Diamino Zirconium Complexes: Synthesis and Use in Stereospecific Polymerization of 1-Hexene (pages 923–935)

      Evgueni Kirillov, Laurent Lavanant, Christophe Thomas, Thierry Roisnel, Yun Chi and Jean-François Carpentier

      Version of Record online: 25 OCT 2006 | DOI: 10.1002/chem.200600895

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      Better than parents: New zirconium complexes bearing a chiral dialkoxy-diamino fluorous ligand have been prepared and found to be efficient catalyst precursors for the polymerization of 1-hexene (Mw=4800–47 200, Mw/Mn=1.17–1.79) (see picture), showing enhanced activity (up to 4500 kg PH mol Zr−1 h−1) and selectivity (up to 74 % mmmm) compared with nonchiral parent complexes.

    22. A Novel Strategy for the Design of 8-Hydroxyquinolinate-Based Lanthanide Bioprobes That Emit in the Near Infrared Range (pages 936–944)

      Steve Comby, Daniel Imbert, Caroline Vandevyver and Jean-Claude G. Bünzli

      Version of Record online: 31 OCT 2006 | DOI: 10.1002/chem.200600964

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      Efficient sensitization of the near-infrared luminescence of NdIII, ErIII, and particularly YbIII, by using a nonadentate podand based on tridentate 8-hydroxyquinolinate building blocks has been achieved (see graphic).

    23. Formation and Stability of G-Quadruplexes Self-Assembled from Guanine-Rich Strands (pages 945–949)

      Jiang Zhou, Gu Yuan, Junjun Liu and Chang-Guo Zhan

      Version of Record online: 11 OCT 2006 | DOI: 10.1002/chem.200600424

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      The formation and stability of G-quadruplexes was investigated by using ESI-MS. The G-rich strands prefer to employ “self-association” in the formation of the G-quadruplex rather than hybridized integration (see graphic), and the thermodynamic-stability order of these three G-quadruplexes is Q(2)>Q(1)>Q(3).

    24. Polyisocyanides Derived from Tripeptides of Alanine (pages 950–960)

      Gerald A. Metselaar, P. J. Hans M. Adams, Roeland J. M. Nolte, Jeroen J. L. M. Cornelissen and Alan E. Rowan

      Version of Record online: 18 OCT 2006 | DOI: 10.1002/chem.200600928

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      Helical structures: Helical polymers of isocyanotripeptides derived from alanine are stabilized by an extensive hydrogen-bonding network between the peptide side chains (see scheme). The peptide stereochemistry is a decisive influence on the strength and definition of these β-sheetlike rigidifying arrays.

    25. Palladium-Catalyzed Enantioselective Domino Heck–Cyanation Sequence: Development and Application to the Total Synthesis of Esermethole and Physostigmine (pages 961–967)

      Artur Pinto, Yanxing Jia, Luc Neuville and Jieping Zhu

      Version of Record online: 29 SEP 2006 | DOI: 10.1002/chem.200601016

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      Nontoxic cyanide! A versatile synthesis of functionalized 3-substituted-3-cyanomethyl-2-oxindole by a palladium-catalyzed domino Heck–cyanation reaction has been developed by using nontoxic potassium ferro(II)cyanide as a trapping agent for a σ-alkylpalladium complex. An enantioselective version using (S)-DIFLUORPHOS is reported and a concise synthesis of physostigmine is documented (see scheme).

    26. Inorganic–Organic Hybrid Structures: Open-Framework Iron Phosphite–Oxalates of Varying Dimensionality (pages 968–977)

      Sukhendu Mandal and Srinivasan Natarajan

      Version of Record online: 25 OCT 2006 | DOI: 10.1002/chem.200601026

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      Structural differences: Unusual bridging modes for phosphite and oxalate units have been observed in iron phosphite–oxalate frameworks. The structures show phosphite units connecting two iron centers in a honeycomb lattice (right) and oxalate units bridging two iron centers, primarily to satisfy the coordination requirements of iron (left).

    27. Aromaticity of Tri- and Tetranuclear Metal–Carbonyl Clusters Based on Magnetic Criteria (pages 978–984)

      Clémence Corminboeuf, Paul von Ragué Schleyer and R. Bruce King

      Version of Record online: 10 OCT 2006 | DOI: 10.1002/chem.200601037

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      The concept of σ-(anti)aromaticity helps to rationalize the unusual properties of cyclopropane and cyclobutane. Can this concept account for the different thermal stabilities of metal–carbonyl compounds? An example of such a compound is shown here.

    28. Reactivity of Dehydrometallophthalocyanines and -porphyrazines (pages 985–991)

      Sergei I. Vagin, Antje Frickenschmidt, Bernd Kammerer and Michael Hanack

      Version of Record online: 18 OCT 2006 | DOI: 10.1002/chem.200601056

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      A noticeable increase in reactivity (electrophilicity) of zinc dehydrobenzoporphyrazine (dehydrobenzo-Pz) and zinc dehydrophthalocyanine (dehydro-Pc) towards common solvents is observed relative to that of the unsubstituted dehydrobenzene. Thus, both diethyl ether and benzene as solvents react at room temperature with these macrocyclic intermediates (see scheme).

    29. Reusable Catalysts for the Asymmetric Diels–Alder Reaction (pages 992–1000)

      Guillaume Chollet, Marie-George Guillerez and Emmanuelle Schulz

      Version of Record online: 17 OCT 2006 | DOI: 10.1002/chem.200601081

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      Recycling by charge transfer: A new procedure based on the formation of charge-transfer complexes is described for the efficient recycling of tert-leucinol-based bis(oxazoline)–copper complexes (see figure) for the asymmetric Diels–Alder reaction.

  6. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. Concept
    6. Full Papers
    7. Preview
    1. You have free access to this content
      Preview: Chem. Eur. J. 4/2007 (page 1007)

      Version of Record online: 4 JAN 2007 | DOI: 10.1002/chem.200790007

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