Chemistry - A European Journal

Cover image for Vol. 11 Issue 23

November 18, 2005

Volume 11, Issue 23

Pages 6775–7131

    1. Cover Picture: Lipase Active-Site-Directed Anchoring of Organometallics: Metallopincer/Protein Hybrids (Chem. Eur. J. 23/2005) (page 6775)

      Cornelis A. Kruithof, Miguel A. Casado, Gabriela Guillena, Maarten R. Egmond, Anca van der Kerk-van Hoof, Albert J. R. Heck, Robertus J. M. Klein Gebbink and Gerard van Koten

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/chem.200590072

      Site-directed attachment… of organometallic complexes to enzymes is described by means of irreversible enzyme inhibitors as anchoring moieties by G. van Koten et al. on page 6869 ff. The cover picture was generated using PyMol software: W. L. DeLano, The PyMOL Molecular Graphics System 2002, DeLano Scientific, San Carlos, CA (USA);

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      200 Not Out! (pages 6776–6777)

      Neville Compton

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/chem.200501278

    3. PNA Encoding (PNA=peptide nucleic acid): From Solution-Based Libraries to Organized Microarrays (pages 6792–6801)

      Jennifer L. Harris and Nicolas Winssinger

      Version of Record online: 22 JUL 2005 | DOI: 10.1002/chem.200500305

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      Microarrays have become an indispensable technology in post-genomic research and a number of strategies have been developed to immobilize analytes in the microarray format. This concept article describes a supramolecular preparation based on sequence specific hybridization of PNA. This approach allows the use of the libraries as mixtures in solution which can be converted to an organized microarray in one step by a self-sorting process.

    4. Structure and IR Spectrum of Phenylalanyl–Glycyl–Glycine Tripetide in the Gas-Phase: IR/UV Experiments, Ab Initio Quantum Chemical Calculations, and Molecular Dynamic Simulations (pages 6803–6817)

      D. Řeha, H. Valdés, J. Vondrášek, P. Hobza, Ali Abu-Riziq, Bridgit Crews and Mattanjah S. de Vries

      Version of Record online: 10 AUG 2005 | DOI: 10.1002/chem.200500465

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      The tripeptide phenylalanyl–glycyl–glycine was studied in the gas phase by means of IR/UV double-resonance spectroscopy and quantum chemical and statistical thermodynamic calculations (see figure). Theoretical results, when performed at a high correlated level, fully reproduce the experimental findings. Lower-level methods like DFT fail to localize the most stable structures.

    5. Ion-Triggered Multistate Molecular Switching Device Based on Regioselective Coordination-Controlled Ion Binding (pages 6818–6828)

      Anne Petitjean, Nathalie Kyritsakas and Jean-Marie Lehn

      Version of Record online: 17 AUG 2005 | DOI: 10.1002/chem.200500625

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      Iono-mechanical devices are versatile building blocks for nanotechnology. The design and study of a new molecular switch that accesses up to four optical and conformational states and relates to both areas of molecular mechanical devices and logic gates is illustrated. It is based on the regioselective complexation of metal ions to a heterocyclic ligand triad, which is dictated by the accessible coordination geometry and electrostatic properties of two distinct binding subunits.

    6. 2-Bromophospholide Ions: Synthesis and Theoretical Study (pages 6829–6832)

      Eliane Deschamps and François Mathey

      Version of Record online: 22 JUL 2005 | DOI: 10.1002/chem.200500459

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      Stable toward self-arylation as a result of the lowered nucleophilicity of the in-plane phosphorus lone pair, a 2-bromophospholide ion has been synthesized by based-induced dealkylation of a 1-(2-ethoxycarbonylethyl)-2-bromophosphole (see scheme). Reaction of this ion with FeCl2 provides a route to the corresponding diphosphaferrocene derivative.

    7. Monodisperse Oligofluorenes with Keto Defect as Models to Investigate the Origin of Green Emission From Polyfluorenes: Synthesis, Self-Assembly, and Photophysical Properties (pages 6833–6845)

      Chunyan Chi, Chan Im, Volker Enkelmann, Andreas Ziegler, Günter Lieser and Gerhard Wegner

      Version of Record online: 31 AUG 2005 | DOI: 10.1002/chem.200500275

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      Getting all photoexcited: Oligofluorenes with one fluorenone group in the center exhibit liquid crystal phases of the smectic type (an example of the single-crystal structure is shown here). Spectral and electrochemical data reveal rapid energy transfer from the photoexcited fluorene segments to the fluorenone group.

    8. A Photoactive Molecular Triad as a Nanoscale Power Supply for a Supramolecular Machine (pages 6846–6858)

      Sourav Saha, Erik Johansson, Amar H. Flood, Hsian-Rong Tseng, Jeffrey I. Zink and J. Fraser Stoddart

      Version of Record online: 5 AUG 2005 | DOI: 10.1002/chem.200500371

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      Nanoscale machines require power supplies that are attuned in dimensions and abilities to power molecular movement. A light-harvesting molecular triad has been employed as a power supply to photochemically drive the dethreading process of a supramolecular machine in the form of a [2]pseudorotaxane (see scheme).

    9. Mechanistic Insights into Iridium-Catalyzed Asymmetric Hydrogenation of Dienes (pages 6859–6868)

      Xiuhua Cui, Yubo Fan, Michael B. Hall and Kevin Burgess

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500762

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      Mechanistic mystery: Mechanistic aspects of homogeneous hydrogenation of unfunctionalized alkenes with iridium catalysts are somewhat mysterious, and more mysterious still when the substrates are dienes. Attempts to clarify the situation are reported. The observed products and some calculated intermediates are shown here.

    10. Lipase Active-Site-Directed Anchoring of Organometallics: Metallopincer/Protein Hybrids (pages 6869–6877)

      Cornelis A. Kruithof, Miguel A. Casado, Gabriela Guillena, Maarten R. Egmond, Anca van der Kerk-van Hoof, Albert J. R. Heck, Robertus J. M. Klein Gebbink and Gerard van Koten

      Version of Record online: 13 OCT 2005 | DOI: 10.1002/chem.200500671

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      An organometallic-complex/lipase hybridization method: p-Nitrophenol phosphonate esters have been used as anchoring units to incorporate organometallic pincer complexes into the active site of the lipase cutinase. Hybridization of cutinase with the organometallic phosphonates 13 results in organometallic pincer cutinase hybrids that contain exactly one transition-metal pincer complex at a predetermined position.

    11. Total Synthesis of (+)-Batzelladine A and (−)-Batzelladine D, and Identification of Their Target Protein (pages 6878–6888)

      Jun Shimokawa, Takanori Ishiwata, Koji Shirai, Hiroyuki Koshino, Aya Tanatani, Tadashi Nakata, Yuichi Hashimoto and Kazuo Nagasawa

      Version of Record online: 14 SEP 2005 | DOI: 10.1002/chem.200500852

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      Enantioselective total synthesis of (+)-batzelladine A (illustrated here) and (−)-batzelladine D has been achieved. The target protein of these natural products was also identified to be CD4.

    12. Cyclic Enolates of Ni and Pd: Equilibrium between C- and O-Bound Tautomers and Reactivity Studies (pages 6889–6904)

      Juan Cámpora, Celia M. Maya, Pilar Palma, Ernesto Carmona, Enrique Gutiérrez, Caridad Ruiz, Claudia Graiff and Antonio Tiripicchio

      Version of Record online: 21 SEP 2005 | DOI: 10.1002/chem.200500622

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      Slow equilibration between O- and C-enolate tautomers is observed for a cyclic nickel complex (see scheme). While the C-enolate tautomer is unreactive towards aldehydes, the corresponding O-enolate adds to MeCHO and PhCHO. The carbonylation of these products cleanly leads to the formation of enol lactones in a highly selective manner.

    13. A Multisite Molecular Mechanism for Baeyer–Villiger Oxidations on Solid Catalysts Using Environmentally Friendly H2O2 as Oxidant (pages 6905–6915)

      Mercedes Boronat, Avelino Corma, Michael Renz, Germán Sastre and Pedro M. Viruela

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500184

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      A multidisciplinary approach combining catalyst synthesis methods, in situ characterization techniques, quantum-chemical calculations, and kinetic experiments has been carried out to investigate the mechanism of the Baeyer–Villiger oxidation of ketones in Sn-beta zeolite. The figure shows examples of the structures involved (ε-caprolactone=orange, O=red, Sn=yellow, Si=purple).

    14. Recognition-Induced Polymersomes: Structure and Mechanism of Formation (pages 6916–6920)

      Oktay Uzun, Hao Xu, Eunhee Jeoung, Raymond J. Thibault and Vincent M. Rotello

      Version of Record online: 27 SEP 2005 | DOI: 10.1002/chem.200500809

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      Random yet organized! Random polystyrene copolymers grafted with complementary recognition elements produce vesicular aggregates when combined in chloroform (see scheme). These systems are unique in recognition-induced polymersomes (RIPs). These RIPs have been characterized.

    15. Induced Axial Chirality in the Biphenyl Core of the Proatropoisomeric, Cα-Tetrasubstituted α-Amino Acid Residue Bip in Peptides (pages 6921–6929)

      Jean-Paul Mazaleyrat, Karen Wright, Anne Gaucher, Nathalie Toulemonde, Laurence Dutot, Michel Wakselman, Quirinus B. Broxterman, Bernard Kaptein, Simona Oancea, Cristina Peggion, Marco Crisma, Fernando Formaggio and Claudio Toniolo

      Version of Record online: 15 JUL 2005 | DOI: 10.1002/chem.200500187

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      Inducing circular dichroism: Bip dipeptides (see structure) have been synthesized and their induced axial chirality has been investigated by CD and 1H NMR spectroscopic techniques and in one case by X-ray diffraction as well. The sequence Bip-Xaa* (Xaa* is any chiral, aliphatic α-amino acid) gives induced circular dichroism signals remarkably higher than those of the isomeric Xaa*-Bip sequence.

    16. Preparation and Optical Investigation of Monodisperse Oligo(9,9-dioctylfluorene)s Containing One Fluorenone Unit (pages 6930–6936)

      Jing Li, Ming Li and Zhishan Bo

      Version of Record online: 24 AUG 2005 | DOI: 10.1002/chem.200500261

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      Monodisperse oligo(9,9-dioctylfluorene)s (an example of which is shown here) containing one central fluorenone unit were synthesized by using iterative Suzuki cross-coupling and iododesilylation reactions. These oligomers emitted in the green region and have low fluorescence quantum efficient yields.

    17. Palladium(0)-Catalyzed Cycloisomerization of Enallenes (pages 6937–6943)

      Katja Närhi, Johan Franzén and Jan-E. Bäckvall

      Version of Record online: 14 SEP 2005 | DOI: 10.1002/chem.200500303

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      A novel and efficient palladium-catalyzed cycloisomerization of enallenes has been developed to give stereodefined bicyclic compounds or functionalized cyclopentene derivatives in high yield (see scheme).

    18. Novel Multichiral Diols and Diamines by Highly Stereoselective Pinacol Coupling of Planar Chiral [2.2]Paracyclophane Derivatives (pages 6944–6961)

      Elena V. Sergeeva, Valeria I. Rozenberg, Dmitrii Yu. Antonov, Evgenii V. Vorontsov, Zoya A. Starikova, Ivan V. Fedyanin and Henning Hopf

      Version of Record online: 2 SEP 2005 | DOI: 10.1002/chem.200500413

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      The planar chirality stereoselectively governs the formation of two chiral centres: The pinacol coupling of the enantiomerically pure carbonyl- or imino derivatives of [2.2]paracyclophane give rise to the single diastereomers of the respective diols (X = O) or diamines (X = NR) from three possible alternatives.

    19. Synthesis and Some First-Row Transition-Metal Complexes of the 1,2,4-Triazole-Based Bis(terdentate) Ligands TsPMAT and PMAT (pages 6962–6973)

      Marco H. Klingele, Boujemaa Moubaraki, Keith S. Murray and Sally Brooker

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500387

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      The first examples of bis(terdentate) 1,2,4-triazole-based ligands, PMAT and TsPMAT (shown in the graphic), have been prepared by a nucleophilic substitution rather than a Schiff base condensation.

    20. Molecular Design of Glycoprotein Mimetics: Glycoblotting by Engineered Proteins with an Oxylamino-Functionalized Amino Acid Residue (pages 6974–6981)

      Naoki Matsubara, Kei Oiwa, Takahiro Hohsaka, Reiko Sadamoto, Kenichi Niikura, Norio Fukuhara, Akio Takimoto, Hirosato Kondo and Shin-Ichiro Nishimura

      Version of Record online: 6 SEP 2005 | DOI: 10.1002/chem.200500531

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      A novel method for site-directed glycosylation of proteins based on chemoselective blotting of common reducing sugars by genetically encoded proteins is described. The oxylamino-functionalized L-homoserine residues, 2-amino-4-O-(N-methylaminooxy) butanoic acid and 2-amino-4-aminooxy butanoic acid, were efficiently incorporated into proteins by using the four-base codon/anticodon pair strategy in Escherichia coli in vitro translation (see scheme).

    21. Linear and Branched Phospha[n]triangulanes (pages 6982–6993)

      J. Chris Slootweg, Frans J. J. de Kanter, Marius Schakel, Martin Lutz, Anthony L. Spek, Sergei I. Kozhushkov, Armin de Meijere and Koop Lammertsma

      Version of Record online: 3 AUG 2005 | DOI: 10.1002/chem.200500538

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      Linear and branched mono- and diphospha[n]triangulanes (see picture) have been prepared in high yields by the CuCl-catalyzed phosphinidene addition to spirocyclopropanated methylenecyclopropanes and bicyclopropylidenes. These esthetically attractive phosphacycles are remarkably stable in spite of their high ring strain.

    22. Lanthanide(III)/Actinide(III) Differentiation in the Cerium and Uranium Complexes [M(C5Me5)2(L)]0,+ (L=2,2′-Bipyridine, 2,2′:6′,2′′-Terpyridine): Structural, Magnetic, and Reactivity Studies (pages 6994–7006)

      Thouraya Mehdoui, Jean-Claude Berthet, Pierre Thuéry, Lionel Salmon, Eric Rivière and Michel Ephritikhine

      Version of Record online: 2 SEP 2005 | DOI: 10.1002/chem.200500479

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      Distinct structures and reactions of the analogous low-valent cerium and uranium compounds [M(Cp*)2(terpy)]I and [M(Cp*)2(terpy)] (M=Ce, U; terpy=2,2′:6′,2′′-terpyridine) reveal more extensive electron transfer from the metal to the terpyridine ligand in the actinide complexes (see scheme).

    23. Diastereoselective Reactions at Enantiomerically Pure, Sterically Congested Cyclohexanes as an Entry to Wailupemycins A and B: Total Synthesis of (+)-Wailupemycin B (pages 7007–7023)

      Stefan F. Kirsch and Thorsten Bach

      Version of Record online: 6 SEP 2005 | DOI: 10.1002/chem.200500640

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      The structurally unique antibiotic (+)-wailupemycin B was synthesized in 23 steps and 6 % overall yield from (S)-(+)-carvone. Diastereoselective carbonyl addition reactions allowed for the formation of the C-6/C-7 and C-12/C-13 bonds. Other strategies towards a synthesis of wailupemycin B and its epimer wailupemycin A are presented and comprehensively analyzed.

    24. Acyclic Chiral Amines and Amino Acids as Inexpensive and Readily Tunable Catalysts for the Direct Asymmetric Three-Component Mannich Reaction (pages 7024–7029)

      Ismail Ibrahem, Weibiao Zou, Magnus Engqvist, Yongmei Xu and Armando Córdova

      Version of Record online: 28 SEP 2005 | DOI: 10.1002/chem.200500746

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      Cheap and tunable! Simple acyclic chiral amines and amino acids catalyzed the direct, three-component, asymmetric Mannich reactions between unmodified ketones, p-anisidine, and aldehydes with high chemo- and stereoselectivity (see scheme). The corresponding Mannich bases were produced with up to >99 % ee.

    25. Synthesis of Nitrogen- and Oxygen-Containing Macrocycles—Derivatives of Lithocholic Acid (pages 7030–7039)

      Alexei D. Averin, Elena R. Ranyuk, Nikolai V. Lukashev and Irina P. Beletskaya

      Version of Record online: 27 SEP 2005 | DOI: 10.1002/chem.200500784

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      A convenient method for the synthesis of nitrogen- and oxygen-containing macrocycles (an example of which is shown here) incorporating steroidal moieties has been elaborated. The method is based on intramolecular catalytic diamination of 3,24-bis(3-bromophenoxy)cholane.

    26. Hydrocarbon Oxidation by β-Halogenated Dioxoruthenium(VI) Porphyrin Complexes: Effect of Reduction Potential (RuVI/V) and C[BOND]H Bond-Dissociation Energy on Rate Constants (pages 7040–7053)

      Chi-Ming Che, Jun-Long Zhang, Rui Zhang, Jie-Sheng Huang, Tat-Shing Lai, Wai-Man Tsui, Xiang-Ge Zhou, Zhong-Yuan Zhou, Nianyong Zhu and Chi Kwong Chang

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500814

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      Fluorine can make a difference! β-Halogenated oxometalloporphyrin complexes have been isolated and spectroscopically characterized. The dioxoruthenium(VI) complex of perfluorinated porphyrin (1, see scheme) oxidizes alkenes and C[BOND]H bonds with second-order rate constants up to 28-fold larger than 2. The log of the rate constants of hydrocarbon oxidations by dioxoruthenium(VI) porphyrin complexes linearly correlates with the reduction potentials of RuVI to RuV and the dissociation energies of C[BOND]H bonds (BDE).

    27. Supramolecular Assembly of 2,7-Dimethyldiazapyrenium and Cucurbit[8]uril: A New Fluorescent Host for Detection of Catechol and Dopamine (pages 7054–7059)

      Vladimir Sindelar, Mabel A. Cejas, Françisco M. Raymo, Weizhong Chen, Samantha E. Parker and Angel E. Kaifer

      Version of Record online: 21 SEP 2005 | DOI: 10.1002/chem.200500917

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      Fluorescent sensors: The inclusion complex formed by 2,7-dimethyldiazapyrenium and cucurbit[8]uril acts as a fluorescent-sensitive host for catechol and dopamine (see scheme).

    28. On the Importance of Carbohydrate–Aromatic Interactions for the Molecular Recognition of Oligosaccharides by Proteins: NMR Studies of the Structure and Binding Affinity of AcAMP2-like Peptides with Non-Natural Naphthyl and Fluoroaromatic Residues (pages 7060–7074)

      M. Isabel Chávez, Cecilia Andreu, Paloma Vidal, Nuria Aboitiz, Felix Freire, Patrick Groves, Juan Luis Asensio, Gregorio Asensio, Michiro Muraki, Francisco Javier Cañada and Jesús Jiménez-Barbero

      Version of Record online: 12 OCT 2005 | DOI: 10.1002/chem.200500367

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      Recognition of sugars by non-natural proteins: NMR structural and binding studies on mutant hevein-like domains (see figure) demonstrate that the chemical nature of the aromatic rings in the recognition sites of carbohydrate-binding proteins strongly influences the thermodynamics of sugar recognition.

    29. Enantioselective Palladium-Catalyzed Addition of 1,3-Dicarbonyl Compounds to an Allene Derivative (pages 7075–7082)

      Barry M. Trost, Alessandro B. C. Simas, Bernd Plietker, Christoph Jäkel and Jia Xie

      Version of Record online: 30 SEP 2005 | DOI: 10.1002/chem.200500826

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      Atom economy: A highly atom-economic addition of Meldrum's acids and 1,3-diketones (pronucleophiles 1) to alkoxyallene 2 using a chiral Pd complex based on ligand (R,R)-3 as catalyst provides the branched adducts exclusively in excellent enantioselectivity.

    30. Mechanistic Investigation of the 2,5-Diphenylpyrrolidine-Catalyzed Enantioselective α-Chlorination of Aldehydes (pages 7083–7090)

      Nis Halland, Mette Alstrup Lie, Anne Kjærsgaard, Mauro Marigo, Birgit Schiøtt and Karl Anker Jørgensen

      Version of Record online: 12 OCT 2005 | DOI: 10.1002/chem.200500776

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      The sigmatropic shift might be the key! The mechanism for the 2,5-diphenylpyrrolidine-catalyzed enantioselective α-chlorination of aldehydes has been investigated by both experimental and computational methods. This has led to a proposed mechanism that proceeds through an initial N-chlorination followed by an enantioselective sigmatropic 1,3-shift of the chlorine atom to the enamine carbon (see scheme).

    31. Functionalized Nanodiamonds Part I. An Experimental Assessment of Diamantane and Computational Predictions for Higher Diamondoids (pages 7091–7101)

      Andrey A. Fokin, Boryslav A. Tkachenko, Pavel A. Gunchenko, Dmitriy V. Gusev and Peter R. Schreiner

      Version of Record online: 30 SEP 2005 | DOI: 10.1002/chem.200500031

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      Crude oil provides diamondoids that have the potential to be spectacular nanomolecular organic building blocks. Yet, methods for selective functionalizations of such (chemical) gems are scarce. We present a wide array of methods to probe C[BOND]H substitution selectivities involving radicals, cations, and radical cations (schematized above).

    32. Metal Aminocarboxylate Coordination Polymers with Chain and Layered Structures (pages 7102–7109)

      Meenakshi Dan and C. N. R. Rao

      Version of Record online: 12 OCT 2005 | DOI: 10.1002/chem.200500922

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      Acidity matters: Linear-chain and layered (see figure) metal aminocarboxylates have been prepared under hydro- or solvothermal conditions. The nature of the metal coordination depends on the acidity of the medium, which determines whether the aminocarboxylic acid is in a zwitterionic form.

    33. Multiple Component Approaches to C-Glycosyl β-Amino Acids by Complementary One-Pot Mannich-Type and Reformatsky-Type Reactions (pages 7110–7125)

      Alessandro Dondoni, Alessandro Massi and Simona Sabbatini

      Version of Record online: 14 OCT 2005 | DOI: 10.1002/chem.200500823

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      Genuine C-glycosyl β-amino acids are synthesized for the first time via complementary one-pot three-component Mannich and Reformatsky approaches exploiting C-glycosyl formaldehydes (galacto, gluco, manno, ribo and arabino series) as key components. Both routes occur with complete internal asymmetric induction furnishing the target β-amino acids with R configuration at β carbon. The synthesis of α,α-difluoro C-glycosyl β-amino acids by the use of the traditional two-step Reformatsky methodology is also reported.

    34. Preview: Chem. Eur. J. 23/2005 (page 7131)

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/chem.200590074