Chemistry - A European Journal

Cover image for Vol. 14 Issue 7

February 27, 2008

Volume 14, Issue 7

Pages 1991–2291

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    1. Cover Picture: Tailor-Made Poly(amidoamine)s for Controlled Complexation and Condensation of DNA (Chem. Eur. J. 7/2008) (page 1991)

      Laura Hartmann, Stefanie Häfele, Regine Peschka-Süss, Markus Antonietti and Hans G. Börner

      Version of Record online: 21 FEB 2008 | DOI: 10.1002/chem.200890019

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      Tailor-Made Complexation is described by H. G. Börner et al. in their Full paper on page 2025 ff. They developed a platform of monodisperse poly(amidoamine)s (PAA)s to mimic natural packing tools for DNA. A set of tailor-made PEO–PAA conjugates was synthesized and complexation properties with DNA were studied.

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  3. News

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  4. Concept

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    1. Superelectrophiles: Charge–Charge Repulsive Effects (pages 2004–2015)

      Douglas A. Klumpp

      Version of Record online: 28 DEC 2007 | DOI: 10.1002/chem.200701470

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      Coulombic interactions: Superelectrophilies are small-sized, highly charged ions. Charge–charge repulsive effects profoundly influence their chemistry. The effects of Coulombic interactions and their role in the chemistry of superelectrophiles are described herein (see scheme).

  5. Full Papers

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    1. Glycerol Etherification over Highly Active CaO-Based Materials: New Mechanistic Aspects and Related Colloidal Particle Formation (pages 2016–2024)

      Agnieszka M. Ruppert, Johannes D. Meeldijk, Bonny W. M. Kuipers, Ben H. Erné and Bert M. Weckhuysen

      Version of Record online: 29 JAN 2008 | DOI: 10.1002/chem.200701757

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      Calcium oxide and colloids in the act: Different basic oxides, such as MgO, CaO, SrO, and BaO, were investigated for the etherification of glycerol to di- and triglycerol. In particular, CaO turned out to be an interesting material and both basicity and Lewis acidity play an active role in glycerol etherification (see figure).

    2. Tailor-Made Poly(amidoamine)s for Controlled Complexation and Condensation of DNA (pages 2025–2033)

      Laura Hartmann, Stefanie Häfele, Regine Peschka-Süss, Markus Antonietti and Hans G. Börner

      Version of Record online: 7 FEB 2008 | DOI: 10.1002/chem.200701223

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      Controlled DNA complexation with new carrier systems that are based on monodisperse, sequence-defined poly(amidoamines) (PAA) are reported. A set of polymer carriers for DNA delivery is synthesized by combining monodisperse, sequence-defined, poly(amidoamine) segments with poly(ethylene oxide) blocks; this enables a controlled compression of double-strand plasmid DNA and a direct correlation of the chemical PAA-structure (monomer sequence) with the resulting biological properties of the carrier.

    3. Delicate Crystal Structure Changes Govern the Magnetic Properties of 1D Coordination Polymers Based on 3d Metal Carboxylates (pages 2034–2043)

      Konstantin S. Gavrilenko, Olivier Cador, Kevin Bernot, Patrick Rosa, Roberta Sessoli, Stéphane Golhen, Vitaly V. Pavlishchuk and Lahcène Ouahab

      Version of Record online: 28 DEC 2007 | DOI: 10.1002/chem.200701316

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      Single-chain magnet behavior found at low temperatures in homometallic 1D coordination polymers of transition metals, and exemplified here in the graph, is explained by a combination of ferromagnetic interactions with high magnetic anisotropy. Both homo- and heterometallic title compounds have been synthesized by an in-situ ligand generation route.

    4. Anchoring of Histidine-Tagged Proteins to Molecular Printboards: Self-assembly, Thermodynamic Modeling, and Patterning (pages 2044–2051)

      Manon J. W. Ludden, Alart Mulder, Katrin Schulze, Vinod Subramaniam, Robert Tampé and Jurriaan Huskens

      Version of Record online: 11 JAN 2008 | DOI: 10.1002/chem.200701478

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      Protein prints: Proteins can be reversibly immobilized through nitrilotriacetate–His tag interactions with a molecular printboard. The multivalent binding of hexahistidine (His6)-tagged proteins to β-cyclodextrin self-assembled monolayers is described. The use of the nickel(II) complex of a hetero-divalent orthogonal adamantyl nitrilotriacetate linker for this purpose enabled proper assessment of the thermodynamics as well as stable surface patterning (see figure).

    5. A Library of Chiral Imidazoline–Aminophenol Ligands: Discovery of an Efficient Reaction Sphere (pages 2052–2059)

      Takayoshi Arai, Naota Yokoyama and Akira Yanagisawa

      Version of Record online: 9 JAN 2008 | DOI: 10.1002/chem.200701439

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      Sphere of influence: Analysis by solid-phase catalysis/circular dichroism high-throughput screening revealed that a copper-catalyzed Henry reaction was highly efficient (<95 % ee) when novel imidazoline–aminophenol ligands were employed (see scheme). This unique reaction sphere was also efficient for the Friedel–Crafts alkylation of indole and nitroalkenes (<83 % ee).

    6. Highly Enantio- and s-trans C[DOUBLE BOND]C Bond Selective Catalytic Hydrogenation of Cyclic Enones: Alternative Synthesis of (−)-Menthol (pages 2060–2066)

      Takashi Ohshima, Hiroshi Tadaoka, Kiyoto Hori, Noboru Sayo and Kazushi Mashima

      Version of Record online: 13 DEC 2007 | DOI: 10.1002/chem.200701505

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      Fresh mint: A highly enantioselective catalytic hydrogenation of cyclic enones was achieved by using the combination of a cationic RhI complex, (S)-5,5′-bis{di(3,5-di-tert-butyl-4-methoxyphenylphosphino)}-4,4′-bi-1,3-benzodioxole (DTBM-SEGPHOS), and (CH2CH2PPh3Br)2 (see graphic). The catalysis was successfully applied to a new synthetic method for optically pure (−)-menthol to obtain high enantio- and s-trans selectivities and the addition of a halogen source to a cationic Rh complex was essential.

    7. Antiaromaticity and Reactivity of a Planar Cyclooctatetraene Fully Annelated with Bicyclo[2.1.1]hexane Units (pages 2067–2074)

      Tohru Nishinaga, Takayuki Uto, Ryota Inoue, Akira Matsuura, Noach Treitel, Mordecai Rabinovitz and Koichi Komatsu

      Version of Record online: 14 DEC 2007 | DOI: 10.1002/chem.200701405

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      Higher reactivity: A planar cyclooctatetraene (COT) annelated with bicyclo[2.1.1]hexane units (see picture) has a weakened antiaromatic nature. This COT showed higher reactivity in [4+2] cycloaddition, epoxidation, and cyclopropanation reactions relative to the tub-shaped parent COT. In addition to cancellation of the unfavorable antiaromaticity of the planarized 8π-electron system, theoretical studies revealed that the release of strain is also an important factor in the enhanced reactivity.

    8. Two-Photon Fluorescent Probes for Long-Term Imaging of Calcium Waves in Live Tissue (pages 2075–2083)

      Hwan Myung Kim, Bo Ra Kim, Myoung Jin An, Jin Hee Hong, Kyoung J. Lee and Bong Rae Cho

      Version of Record online: 3 JAN 2008 | DOI: 10.1002/chem.200701453

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      Creating a good image: 2-Acetyl-6-(dimethylamino)naphthalene-derived two-photon fluorescent probes for Ca2+ can visualize the calcium waves in live cells and living tissue for a long period of time without mistargeting and photobleaching problems (see picture).

    9. The Isomers of Gadolinium Scandium Nitride Clusterfullerenes GdxSc3−xN@C80 (x=1, 2) and Their Influence on Cluster Structure (pages 2084–2092)

      Shangfeng Yang, Alexey Popov, Martin Kalbac and Lothar Dunsch

      Version of Record online: 9 JAN 2008 | DOI: 10.1002/chem.200701598

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      Mixed-metal nitride clusterfullerenes GdxSc3−xN@C80 [x=2 (1, 4); x=1 (2, 5)] have been synthesized by the “reactive gas atmosphere” method and isolated by recycling HPLC. Their isomeric cage structures exhibit Ih (1, 2; picture, top) and D5h symmetry (4, 5; bottom). Scalar-relativistic DFT calculations have shown that the Gd2ScN and GdSc2N clusters are planar, as opposed to the pyramidal Gd3N cluster (Gd green, N blue, Sc violet).

    10. Linear Uranium Complexes X2UL5 with L=Cyanide, Isocyanate: DFT Evidence for Similarities between Uranyl (X=O) and Uranocene (X=Cp) Derivatives (pages 2093–2099)

      Nathalie Iché-Tarrat, Noémi Barros, Colin J. Marsden and Laurent Maron

      Version of Record online: 7 JAN 2008 | DOI: 10.1002/chem.200701511

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      Kindred ligands: Isolobality between linear Cp2U and UO2 fragments is demonstrated (see figure) and allows us to propose possible new uranium(VI, V, IV) stable structures.

    11. Folding Control in Cyclic Peptides through N-Methylation Pattern Selection: Formation of Antiparallel β-Sheet Dimers, Double Reverse Turns and Supramolecular Helices by 3α,γ Cyclic Peptides (pages 2100–2111)

      Manuel Amorín, Luis Castedo and Juan R. Granja

      Version of Record online: 28 DEC 2007 | DOI: 10.1002/chem.200701059

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      Self-assembly of cyclic peptides: Foldameric cyclic peptides (3α,γ-CPs) are described. Depending on their backbone N-methylation patterns and the medium, they can either remain as flat rings that dimerize through arrays of hydrogen bonds of antiparallel β-sheet types, or can fold into twisted double reverse turns that, in the case of double γ-turns, associate in nonpolar solvents to form helical supramolecular structures (see scheme).

    12. Concise Enantioselective Total Syntheses of (+)-Homochelidonine, (+)-Chelamidine, (+)-Chelidonine, (+)-Chelamine and (+)-Norchelidonine by a PdII-Catalyzed Ring-Opening Strategy (pages 2112–2124)

      Matthew J. Fleming, Helen A. McManus, Alena Rudolph, Walter H. Chan, Jérémy Ruiz, Chris Dockendorff and Mark Lautens

      Version of Record online: 17 JAN 2008 | DOI: 10.1002/chem.200701775

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      Five for the price of one: five natural products with one ring-opening reaction. An efficient and highly convergent enantioselective synthesis of B/C hexahydrobenzo[c]phenanthridine alkaloids has been achieved. The approach relied on the development of a new and powerful desymmetrizing ring-opening reaction of a meso-azabicyclic alkene with an aryl boronic acid (MOM=methoxymethyl, Cbz=carbobenzyloxy).

    13. Dissecting the Differences between the α and β Anomers of the Oxidative DNA Lesion FaPydG (pages 2125–2132)

      Florian Büsch, J. Carsten Pieck, Matthias Ober, Johannes Gierlich, Gerald W. Hsu, Lorena S. Beese and Thomas Carell

      Version of Record online: 14 JAN 2008 | DOI: 10.1002/chem.200701373

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      Mutagenesis: The synthesis of a stabilised version of the α-configured main oxidative DNA lesion FaPydG (see graphic) was achieved. After incorporation into DNA, its mutagenic potential could be evaluated.

    14. Supramolecular Gels Formed by Amphiphilic Low-Molecular-Weight Gelators of Nα,Nε-Diacyl-L-Lysine Derivatives (pages 2133–2144)

      M. Suzuki, M. Yumoto, H. Shirai and K. Hanabusa

      Version of Record online: 27 DEC 2007 | DOI: 10.1002/chem.200701111

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      Cool gels! A water-soluble L-lysine carboxylate compound undergoes acid-triggered hydrogelation, and two-component gelators (see figure) that consist of carboxylate and carboxylic acid compounds function as amphiphilic gelators that can gel not only aqueous solutions, but also organic solvents and oils.

    15. Enantioselective C[BOND]C Bond Formation to Sulfonylimines through Use of the 2-Pyridinesulfonyl Group as a Novel Stereocontroller (pages 2145–2152)

      Shuichi Nakamura, Hiroki Nakashima, Hideki Sugimoto, Hideaki Sano, Masataka Hattori, Norio Shibata and Takeshi Toru

      Version of Record online: 14 DEC 2007 | DOI: 10.1002/chem.200701425

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      Enantioselective synthesis: Enantioselective C[BOND]C bond formation with imines possessing a 2-pyridinesulfonyl substituent (see scheme) afforded products with good enantioselectivity. Since the 2-pyridinesulfonyl group can easily be removed after the reactions, it acts not only as an activating group but also as an efficient stereocontroller.

    16. Exploring the Relation between Amplification and Binding in Dynamic Combinatorial Libraries of Macrocyclic Synthetic Receptors in Water (pages 2153–2166)

      Peter T. Corbett, Jeremy K. M. Sanders and Sijbren Otto

      Version of Record online: 14 DEC 2007 | DOI: 10.1002/chem.200701413

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      Amplification of the fittest? Exposing dynamic combinatorial libraries of host molecules to a template (see graphic) should give amplification of strong binders. But is amplification by a given guest selective for the best receptor? And does the best guest induce the largest amplification of a given receptor?

    17. Half-Sandwich o-N,N-Dimethylaminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine P[BOND]H Bond Addition to Carbodiimides (pages 2167–2179)

      Wen-Xiong Zhang, Masayoshi Nishiura, Tomohiro Mashiko and Zhaomin Hou

      Version of Record online: 14 DEC 2007 | DOI: 10.1002/chem.200701300

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      The rarer the better: Rare-earth metal o-N,N-Dimethylaminobenzyl complexes bearing silylene-linked cyclopentadienyl-amido ligands have been synthesized and structurally characterized for the first time over the full size range of the rare-earth metal series. These complexes can serve as efficient catalyst precursors for the eventual formation of a series of phosphaguanidine derivatives (see figure).

    18. Gas-Phase Study on the C[BOND]C Coupling of Naphthol Catalyzed by CuII⋅TMEDA: Evidence for the Key Role of Binuclear Clusters (pages 2180–2188)

      Jana Roithová and Detlef Schröder

      Version of Record online: 7 JAN 2008 | DOI: 10.1002/chem.200701277

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      Cluster with two copper ions needed! Binuclear copper(II) clusters are crucial for promoting oxidative C[BOND]C coupling of naphthols in the gas phase with a CuII/TMEDA catalyst to give binaphthols (BINOLs). The diamine ligand TMEDA supports cluster formation and enhances the reactivity of the naphthoxo ligands towards C[BOND]C coupling. The proposed catalytic cycle for BINOL formation via a Cu2 complex with two TMEDA ligands is depicted (X=counteranions, TMEDA=N,N,N′,N′-tetramethylethylenediamine).

    19. New Chiral Lanthanide Amide Ate Complexes for the Catalysed Synthesis of Scalemic Nitrogen-Containing Heterocycles (pages 2189–2200)

      Isabelle Aillaud, Jacqueline Collin, Carine Duhayon, Régis Guillot, Dmitrii Lyubov, Emmanuelle Schulz and Alexander Trifonov

      Version of Record online: 14 DEC 2007 | DOI: 10.1002/chem.200701090

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      Lanthanide catalysts: New chiral binaphthylamido yttrium and ytterbium ate complexes with lithium and potassium counterions are efficient catalysts for the cyclisation of a variety of aminoalkenes, including internal double bonds, with enantiomeric excesses up to 87 % (see scheme). An influence of the counter cation on activity and enantioselectivity is evidenced.

    20. Strong Dissimilarities Between the Gas-Phase Acidities of Saturated and α,β-Unsaturated Boranes and the Corresponding Alanes and Gallanes (pages 2201–2208)

      José A. Gámez, Jean-Claude Guillemin, Otilia Mó and Manuel Yáñez

      Version of Record online: 9 JAN 2008 | DOI: 10.1002/chem.200701254

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      Where do they deprotonate? Saturated and α,β-unsaturated boranes, alanes, and gallanes have very different behavior as acids in the gas phase. Boranes are CαH acids, much stronger than the corresponding hydrocarbons and stronger than the corresponding alanes and gallanes. Alanes are CβH acids yielding three-membered cycles, whereas gallanes deprotonate at the GaH2 group and are the weakest acids of the group (see scheme).

    21. RhIII- and IrIII-Catalyzed Asymmetric Transfer Hydrogenation of Ketones in Water (pages 2209–2222)

      Xiaofeng Wu, Xiaohong Li, Antonio Zanotti-Gerosa, Allan Pettman, Jianke Liu, Allan James Mills and Jianliang Xiao

      Version of Record online: 19 DEC 2007 | DOI: 10.1002/chem.200701258

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      Fast and enantioselective asymmetric transfer hydrogenation of various ketones by formate in neat water enabled by Rh- and Ir-TsDPEN catalysts is described. The reaction afforded ee values of up to 99 % even under air. The reaction is highly pH-dependent, operating favourably in the pH windows of 5.5–10.0 for RhIII and 6.5–8.5 for IrIII.

    22. A New Strategy for Designing Non-C2-Symmetric Monometallic Bifunctional Catalysts and Their Application in Enantioselective Cyanation of Aldehydes (pages 2223–2231)

      Fei Yang, Siping Wei, Chien-An Chen, Peihua Xi, Li Yang, Jingbo Lan, Han-Mou Gau and Jingsong You

      Version of Record online: 9 JAN 2008 | DOI: 10.1002/chem.200701660

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      Only one! A monometallic bifunctional catalyst, in which only one imidazolyl moiety is directly attached at the 3-position of a binaphthol moiety, has been developed. The ligand lacks C2 symmetry and flexible linkers and, in combination with Ti(OiPr)4, has been demonstrated to promote the general and highly enantioselective cyanation of aldehydes with trimethylsilylcyanide.

    23. The Total Synthesis of (+)-Tedanolide—A Macrocyclic Polyketide from Marine Sponge Tedania ignis (pages 2232–2247)

      Gunnar Ehrlich, Jorma Hassfeld, Ulrike Eggert and Markus Kalesse

      Version of Record online: 28 DEC 2007 | DOI: 10.1002/chem.200701529

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      Tedanolide represents a group of natural products which exhibit a primary hydroxyl group incorporated in the lactone moiety. We describe the synthesis and characterization of the unusual natural product and provide clues on the biosynthetic origin of the macrolactone.

    24. Cooperative AND Ion-Pair Recognition by Heteroditopic Calix[4]diquinone Receptors (pages 2248–2263)

      Michael D. Lankshear, Ian M. Dudley, Kar-Man Chan, Andrew R. Cowley, Sérgio M. Santos, Vitor Felix and Paul D. Beer

      Version of Record online: 7 JAN 2008 | DOI: 10.1002/chem.200701347

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      Working in tandem: An unprecedented AND ion-pair contact binding phenomenon operates in a new family of heteroditopic calix[4]diquinone receptors (see picture). This peculiar binding mechanism has been elucidated from extensive solution, X-ray crystallographic, and computational investigations.

    25. Reaction Mechanism of Apocarotenoid Oxygenase (ACO): A DFT Study (pages 2264–2276)

      Tomasz Borowski, Margareta R. A. Blomberg and Per E. M. Siegbahn

      Version of Record online: 7 JAN 2008 | DOI: 10.1002/chem.200701344

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      The mechanism of oxidative cleavage catalyzed by apocarotenoid oxygenase (ACO) was studied by using a quantum chemical (DFT: B3LYP) method. A reactive peroxo species evolves into either a dioxetane or an epoxide intermediate. The former easily decays into the final aldehyde products, whereas the oxidation of the epoxide to the proper products of the reaction requires involvement of a water molecule. The calculated activation barriers favor the dioxetane mechanism (shown in scheme), yet the mechanism involving the epoxide intermediate cannot be ruled out.

    26. Towards a Tunable Tautomeric Switch in Azobenzene Biomimetics: Implications for the Binding Affinity of 2-(4′-Hydroxyphenylazo)benzoic Acid to Streptavidin (pages 2277–2285)

      Joan-Antoni Farrera, Ivan Canal, Pedro Hidalgo-Fernández, M. Lluïsa Pérez-García, Oscar Huertas and F. Javier Luque

      Version of Record online: 27 DEC 2007 | DOI: 10.1002/chem.200701407

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      Switchable biomimetics: Modulation of the binding affinity of 2-(4′-hydroxyphenylazo)benzoic acid (HABA) and related compounds towards streptavidin can be achieved by triggering azo–hydrazone tautomerism (see scheme) through simple chemical effectors such as (de)protonation, (de)protection, chemical substitution, and change in the polarity of the environment.

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      Preview: Chem. Eur. J. 8/2008 (page 2291)

      Version of Record online: 21 FEB 2008 | DOI: 10.1002/chem.200890022

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