Chemistry - A European Journal

Cover image for Vol. 16 Issue 28

July 26, 2010

Volume 16, Issue 28

Pages 8217–8563

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
    1. Cover Picture: Modification of Luminescent Iridium(III) Polypyridine Complexes with Discrete Poly(ethylene glycol) (PEG) Pendants: Synthesis, Emissive Behavior, Intracellular Uptake, and PEGylation Properties (Chem. Eur. J. 28/2010) (page 8217)

      Steve Po-Yam Li, Hua-Wei Liu, Kenneth Yin Zhang and Kenneth Kam-Wing Lo

      Version of Record online: 19 JUL 2010 | DOI: 10.1002/chem.201090135

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      PEGylation can significantly reduce the toxicity of biomolecules and drug molecules without sacrificing their specific biological or therapeutic properties. In their Full Paper on page 8329 ff., K. K.-W. Lo and co-workers report new luminescent iridium–PEG complexes with high biocompatibility. Hua Tuo (depicted here) was a distinguished Chinese physician during the Eastern Han Dynasty and Three Kingdoms Period. The lantern and pigeon symbolize the luminescence and gene-delivery properties, respectively, of a poly(ethyleneimine)[BOND]iridium[BOND]PEG conjugate. Ching-Sing Chan is acknowledged for the cover picture design.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
    1. Inside Cover: Preactivation-Based, One-Pot Combinatorial Synthesis of Heparin-like Hexasaccharides for the Analysis of Heparin–Protein Interactions (Chem. Eur. J. 28/2010) (page 8218)

      Zhen Wang, Yongmei Xu, Bo Yang, Gopinath Tiruchinapally, Bin Sun, Renpeng Liu, Steven Dulaney, Jian Liu and Xuefei Huang

      Version of Record online: 19 JUL 2010 | DOI: 10.1002/chem.201090136

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      Heparin-like hexasaccharides have been synthesized by using a preactivation-based, one-pot glycosylation approach for the analysis of heparin–protein interactions. In their Full Paper on page 8365 ff., X. Huang et al. describe this new strategy, which facilitates the understanding of the structure–activity relationship of fibroblast growth factor-2.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
  4. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
  5. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
    1. Coordination Chemistry

      Recent Mechanistic and Synthetic Developments in the Chemistry of Transition-Metal Vinylidene Complexes (pages 8238–8247)

      Jason M. Lynam

      Version of Record online: 6 JUL 2010 | DOI: 10.1002/chem.201000695

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      How to tautomerise alkynes: Transition-metal vinylidene complexes are important synthetic intermediates for a range of transformations involving terminal alkynes. This article reviews a number of recent developments focused on understanding the alkyne/vinylidene tautomerisation mediated by transition-metal complexes. The coupling of experimental and theoretical methods has allowed for detailed insight into this process and the factors which control it.

  6. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
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    1. Homogeneous Catalysis

      Rhodium-Catalyzed Synthesis of γ-Pyrones by Three Consecutive Redox–Aldol Reactions of Allylic Alcohols with α,β-Unsaturated Aldehydes (pages 8248–8250)

      Akio Mizuno, Hiroyuki Kusama and Nobuharu Iwasawa

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201001068

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      All together now! A unique RhI-catalyzed reaction was developed to produce γ-pyrones, which are 1,3,5-triketone equivalents. This reaction was thought to proceed by three redox reactions of allylic alcohols, two intermolecular aldol reactions of α,β-unsaturated aldehydes, and one intramolecular aldol reaction to afford 1,3-cyclohexanediones, which were then converted into γ-pyrones (see scheme; TMSOTf=trimethylsilyl trifluoromethanesulfonate).

    2. Hypervalent Arylation

      α-Arylation by Rearrangement: On the Reaction of Enolates with Diaryliodonium Salts (pages 8251–8254)

      Per-Ola Norrby, Tue B. Petersen, Marcin Bielawski and Berit Olofsson

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.201001110

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      Surprising equilibration: A new mechanism for the title reaction is supported by DFT calculations and experimental observations. The C[BOND]I and O[BOND]I intermediates are isoenergetic and equilibrate quickly. Thus, any chiral information induced in the initial complex will be destroyed. In the final C[BOND]C bond-forming step, a [2,3]-rearrangement from the O[BOND]I bonded intermediate is slightly preferred over the [1,2]-elimination from the C[BOND]I bonded isomer (see scheme).

    3. Silicon Compounds

      Nucleophilic Silylenoid Character of Stable Phosphonium Sila–ylides (pages 8255–8258)

      David Gau, Ricardo Rodriguez, Tsuyoshi Kato, Nathalie Saffon-Merceron, Fernando P. Cossío and Antoine Baceiredo

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201001054

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      Stabilising the core: Contrary to the case of non-stabilised transient silylenes, which react with carbonyl compounds to form donor–acceptor adducts, the reaction of a phosphine-coordinated silylene with an aldehyde proceeds by a concerted [2+1] cycloaddition with a very low energy barrier to afford a pentacoordinate oxasilirane (see scheme). This result clearly demonstrates the behaviour of phosphonium sila–ylides as nucleophilic silylenoids.

    4. Asymmetric Catalysis

      A Highly Effective Bis(sulfonamide)–Diamine Ligand: A Unique Chiral Skeleton for the Enantioselective Cu-Catalyzed Henry Reaction (pages 8259–8261)

      Wei Jin, Xincheng Li, Yongbo Huang, Fan Wu and Boshun Wan

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.201000964

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      A skeleton in the closet! As a unique chiral skeleton, the newly developed bis(sulfonamide)–diamine, which contains both diamine and bis(sulfonamide) moieties, was a highly effective ligand for the asymmetric Cu(OAc)2-catalyzed Henry reaction between nitromethane and aldehydes with a low catalyst loading at room temperature (see scheme). Both aliphatic and aromatic aldehydes gave excellent enantioselectivities of up to 99 % ee.

    5. Reaction Mechanisms

      Isolation of a Zwitterionic Dienegold(III) Complex Intermediate in the Direct Conversion of Enyne–Amines to Cyclopentadienes (pages 8262–8267)

      Michele Melchionna, Martin Nieger and Juho Helaja

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/chem.201000988

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      Golden ring: A route for the direct AuCl3-catalyzed conversion of an enyne–amine into cyclopentadiene is reported. The mechanism for the catalysis is proposed and supported by a resting-state zwitterionic gold(III)-cyclopentadiene structure (see figure).

    6. Nanoparticles

      Durability Improvement of a Pt Catalyst with the Use of a Graphitic Carbon Support (pages 8268–8274)

      Bao Yu Xia, Jian Nong Wang, Shang Jun Teng and Xiao Xia Wang

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.201000758

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      Graphitic carbon is the key: A Pt catalyst that is supported on carbon nanocages with a graphitic structure is found to exhibit not only a high catalytic activity, but also a superior thermal stability and electrochemical durability in harsh operating conditions when compared with a counterpart that is supported on conventional carbon black (see graphic).

    7. Liquid Crystals

      Biaxial Nematic Mesophases from Shape-Persistent Mesogens with a Fluorenone Bending Unit (pages 8275–8279)

      Matthias Lehmann, Christiane Köhn, João L. Figueirinhas, Gabriel Feio, Carlos Cruz and Ronald Y. Dong

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201001214

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      Line up! Two optical axes in nematic phases make high demands on the mesogen design. V-shaped, shape-persistent fluorenone nematogens have been shown to assemble in low-temperature nematic liquid-crystal phases with biaxial order (see figure).

    8. Cycloaddition Reactions

      Experimental and Computational Studies into an ATPH-Promoted exo-Selective IMDA Reaction: A Short Total Synthesis of Δ9-THC (pages 8280–8284)

      Emma L. Pearson, Nicholas Kanizaj, Anthony C. Willis, Michael N. Paddon-Row and Michael S. Sherburn

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/chem.201001176

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      Reversal of fortune: The inherent cis stereoselectivity of an intramolecular Diels–Alder reaction is reversed through promotion with aluminum tris(2,6-diphenylphenoxide) (ATPH), allowing a total synthesis of the natural product Δ9-tetrahydrocannabinol (see scheme). Computational studies predict the experimental findings and shed light on the stereocontrolling influences at play in these Diels–Alder reactions.

    9. Molecular Machinery

      A Bevel-Gear-Shaped Rotor Bearing a Double-Decker Porphyrin Complex (pages 8285–8290)

      Soichiro Ogi, Tomohiro Ikeda, Rie Wakabayashi, Seiji Shinkai and Masayuki Takeuchi

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000276

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      Supramolecular rotor: The interlocking of two porphyrin-based molecular rotors into a bevel-gear-shaped structure is demonstrated (see figure). The mechanical interactions between the teeth of the two porphyrin rotors enabled them to mesh and rotate with almost identical activation energies. Switching the rotational activities of one rotor by using chemical stimulation induced a change in the cooperative rotational motions of both rotors.

    10. Chemosensors

      A Micelle-Based Chemosensing Ensemble for the Fluorimetric Detection of Chloride in Water (pages 8291–8295)

      Thomas Riis-Johannessen and Kay Severin

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201001287

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      Caught in a trap! Fluorimetric chloride sensing in water is achieved by exploiting the changes in partition constant of a receptor complex in its bound and unbound states. In the presence of chloride, the complex preferentially resides in the micelle pseudo phase, where its contact with a fluorescent dye results in pronounced quenching effects (see figure).

    11. Photochromism

      Anthraquinone Sulfonate Modified, Layered Double Hydroxide Nanosheets for Dye-Sensitized Solar Cells (pages 8296–8299)

      Jong Hyeon Lee, Juyeon Chang, Ji-Hyun Cha, Duk-Young Jung, Sung Soo Kim and Ji Man Kim

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000703

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      Hybrid light sensitizer: The exfoliated, layered, double hydroxide nanosheets induced a strong photochromic function in the anthraquinone sulfonate anions that were chemically immobilized on the nanosheets. This hybrid nanosheet was applied to the dye-sensitized solar cell as a new light sensitizer that was self-organized on TiO2 spheres, resulting in a higher solar-to-electric conversion efficiency than the single-dye cell, owing to the intense photochromic function of the hybrid nanosheets.

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
    1. Host–Guest Interactions

      Molecular Recognition of Vesicles: Host–Guest Interactions Combined with Specific Dimerization of Zwitterions (pages 8300–8306)

      Jens Voskuhl, Tassilo Fenske, Marc C. A. Stuart, Birgit Wibbeling, Carsten Schmuck and Bart Jan Ravoo

      Version of Record online: 30 JUN 2010 | DOI: 10.1002/chem.201000623

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      Vesicles in close contact: Cyclodextrin vesicles stick together due to a combination of two supramolecular interactions, that is, host–guest inclusion and dimerization of zwitterions (see figure).

    2. Magnesium Amidoboranes

      Thermal Decomposition of Mono- and Bimetallic Magnesium Amidoborane Complexes (pages 8307–8318)

      Jan Spielmann, Dirk F.-J. Piesik and Sjoerd Harder

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.201000028

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      Valuable insight into the mechanism and role of the metal in the thermal decomposition of various metal amidoborane complexes has been gained by comparing the chemistry of the Mg amidoboranes with that of the Ca and Zn analogues. Bimetallic Mg amidoborane complexes (see figure) decompose differently and should be considered as more realistic models for a multi-metallic solid-state situation.

    3. Self-Assembled Monolayers

      Self-Assembled Monolayers of Alkoxy-Substituted Octadehydrodibenzo[12]annulenes on a Graphite Surface: Attempts at peri-Benzopolyacene Formation by On-Surface Polymerization (pages 8319–8328)

      Kazukuni Tahara, Koji Inukai, Noritaka Hara, Charles A. Johnson II, Michael M. Haley and Yoshito Tobe

      Version of Record online: 30 JUN 2010 | DOI: 10.1002/chem.201000711

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      Pull yourself together: Monolayers of tetraalkoxy-substituted octadehydrobenzo[12]annulene (DBA) derivatives (see picture), which have butadiyne linkages, were studied by STM at the liquid/solid interface. The reactivity of DBA in the monolayer toward external stimuli was also investigated to assess the possibility for peri-benzopolyacene formation by two-dimensionally controlled polymerization on a surface.

    4. Luminescence

      Modification of Luminescent Iridium(III) Polypyridine Complexes with Discrete Poly(ethylene glycol) (PEG) Pendants: Synthesis, Emissive Behavior, Intracellular Uptake, and PEGylation Properties (pages 8329–8339)

      Steve Po-Yam Li, Hua-Wei Liu, Kenneth Yin Zhang and Kenneth Kam-Wing Lo

      Version of Record online: 2 JUL 2010 | DOI: 10.1002/chem.201000474

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      Luminescent cyclometalated iridium(III) PEG complexes have been developed as new biological probes. The PEG pendants not only perturb the photophysical properties of the complexes, but also render them to be highly water-soluble and biocompatible with extremely low cytotoxicity. One of the complexes has been functionalized with reactive aldehyde groups (see cartoon in figure), which allow the complex to serve as the first luminescent PEGylation reagent for proteins and amine-containing polymers.

    5. Pauson–Khand Reactions

      Phosphine–Alkene Ligands as Mechanistic Probes in the Pauson–Khand Reaction (pages 8340–8346)

      Catalina Ferrer, Jordi Benet-Buchholz, Antoni Riera and Xavier Verdaguer

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201000357

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      The alkene factor: A new alkyne tetracarbonyl dicobalt complex (1 a, see scheme) of a chelated phosphine–alkene ligand has been prepared, isolated, and characterized by X-ray crystallography. Complex 1 a serves as a structural model for an intermediate in the Pauson–Khand (PK) reaction. Despite the appropriately positioned alkene fragment for 1,2-insertion, neither thermal nor NMO activation provided the PK product. In contrast, complex 3, featuring a terminal alkene, did provide the corresponding PK product.

    6. Conductivity Mechanisms

      Atomistic Characterisation of Li+ Mobility and Conductivity in Li7−xPS6−xIx Argyrodites from Molecular Dynamics Simulations, Solid-State NMR, and Impedance Spectroscopy (pages 8347–8354)

      Oliver Pecher, Shiao-Tong Kong, Thorsten Goebel, Vera Nickel, Katja Weichert, Christof Reiner, Hans-Jörg Deiseroth, Joachim Maier, Frank Haarmann and Dirk Zahn

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201000501

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      Interstitial importance: The atomistic mechanisms of Li+ ion mobility/conductivity in Li7−xPS6−xIx argyrodites are revealed from molecular dynamics simulations, solid-state NMR, and impedance spectroscopy (see figure).

    7. Ligand Effects

      Near-IR Core-Substituted Naphthalenediimide Fluorescent Chemosensors for Zinc Ions: Ligand Effects on PET and ICT Channels (pages 8355–8364)

      Xinyu Lu, Weihong Zhu, Yongshu Xie, Xin Li, Yuan Gao, Fuyou Li and He Tian

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201000461

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      Heighten your senses! Two near-IR chemosensors for Zn2+, PND and PNT, containing a novel naphthalenediimide fluorophore are conveniently synthesized and successfully applied to the imaging of living cells (see picture). The Zn2+-binding behavior and the selectivity difference between PND and PNT are investigated by absorption, fluorescence, and 1H NMR spectroscopy.

    8. Carbohydrates

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      Preactivation-Based, One-Pot Combinatorial Synthesis of Heparin-like Hexasaccharides for the Analysis of Heparin–Protein Interactions (pages 8365–8375)

      Zhen Wang, Yongmei Xu, Bo Yang, Gopinath Tiruchinapally, Bin Sun, Renpeng Liu, Steven Dulaney, Jian Liu and Xuefei Huang

      Version of Record online: 7 JUL 2010 | DOI: 10.1002/chem.201000987

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      Going fast: A preactivation-based, one-pot approach allowed chemoselective glycosylation to occur without the need to fine-tune anomeric reactivities. This enabled the repeated use of the same building block set in the rapid assembly of twelve heparin-like hexasaccharides with systematically varied and precisely controlled backbone structures in a combinatorial fashion, which facilitated the understanding of the structure–activity relationship of fibroblast growth factor-2 (see scheme).

    9. C[BOND]H Activation

      Reactivity of the Latent 12-Electron Fragment [Rh(PiBu3)2]+ with Aryl Bromides: Aryl[BOND]Br and Phosphine Ligand C[BOND]H Activation (pages 8376–8389)

      Nell S. Townsend, Adrian B. Chaplin, M. Abu Naser, Amber L. Thompson, Nicholas H. Rees, Stuart A. Macgregor and Andrew S. Weller

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000554

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      Agostic interactions: Oxidative addition of a variety of aryl bromides to the formally 12-electron RhI complex [Rh(PiBu3)2][BArF4] forms a number of products depending on the substrate, some of which proceed to give species that have undergone C[BOND]H activation and aryl elimination (see scheme), suggesting that they are isolated intermediates in a σ-bond metathesis reaction.

    10. Conducting Materials

      Electroactive Benzothiazole Hydrazones and Their [Mo6O19]2− Derivatives: Promising Building Blocks for Conducting Molecular Materials (pages 8390–8399)

      Sylvain Gatard, Sébastien Blanchard, Bernd Schollhorn, Pierre Gouzerh, Anna Proust and Kamal Boubekeur

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000427

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      Polyoxometalate functionalization: Synthesis of electroactive benzothiazole hydrazones has been achieved and they have been successfully coupled to [Mo6O19]2− to give rare examples of diazoalkane–hexamolybdates (see picture). These molecules exhibit electronic features that make these compounds very promising building blocks for the synthesis of conducting molecular materials.

    11. Organometallic Chemistry

      Reactions of Alkynes with [RuCl(cyclopentadienyl)] Complexes: The Important First Steps (pages 8400–8409)

      Barnali Dutta, Basile F. E. Curchod, Pablo Campomanes, Euro Solari, Rosario Scopelliti, Ursula Rothlisberger and Kay Severin

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000855

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      Complex chemistry: Experimental and computational studies were performed to examine the reaction of [RuCl(cyclopentadienyl)] complexes with alkynes (see figure). It is shown that η2-alkyne complexes can be isolated and that subsequent reactions are strongly dependent on steric effects.

    12. Cyclization

      Synthesis of Fused and Linked Bicyclic Nitrogen Heterocycles by Palladium-Catalyzed Domino Cyclization of Propargyl Bromides (pages 8410–8418)

      Akinori Okano, Koji Tsukamoto, Shohei Kosaka, Hatsuo Maeda, Shinya Oishi, Tetsuaki Tanaka, Nobutaka Fujii and Hiroaki Ohno

      Version of Record online: 14 JUN 2010 | DOI: 10.1002/chem.201000653

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      Palladium-catalyzed bis-cyclization: Propargyl bromides that have nucleophilic functional groups, such as 5-bromohept-3-yne-1,7-diamine derivatives, react with [Pd(PPh3)4] and NaH/MeOH to selectively give fused nitrogen heterocycles that can be readily converted into the fused pyrroles in good yields (see scheme). The reaction of a 2-alkynylazetidine derivative with a catalytic amount of [Pd(PPh3)4] proceeds under base-free conditions to give the same fused heterocycle.

    13. Multicomponent Reactions

      Efficient One-Pot Synthesis of N-Containing Heterocycles by Multicomponent Coupling of Silicon-Tethered Diynes, Nitriles, and Isocyanides through Intramolecular Cyclization of Iminoacyl[BOND]Zr Intermediates (pages 8419–8426)

      Shaoguang Zhang, Wen-Xiong Zhang and Zhenfeng Xi

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201000708

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      Iminoacyl[BOND]Zr intermediates: The synthesis, structures, and intramolecular cyclization of mono- and bis(iminoacyl)[BOND]Zr intermediates formed in zirconocene-mediated multicomponent coupling of silicon-tethered diynes, nitriles, and isocyanides have been investigated and directed to the efficient one-pot synthesis of 5-azaindoles and dihydropyrrolo[3,2-c]azepines (see scheme).

    14. Ring Contraction.

      Stereocontrolled Synthesis of Spiro[n.2]alkenes by Ring Contraction of Fused-Cyclobutanols (pages 8427–8432)

      Kiyosei Takasu, Yuuki Nagamoto and Yoshiji Takemoto

      Version of Record online: 14 JUN 2010 | DOI: 10.1002/chem.201000930

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      Spiro strain: An unusual ring-contraction rearrangement that gives spirocyclopropanes from fused cyclobutanols has been developed. It was found that the strain energy of the substrates derived from an additional fused ring and the stereoelectronic effect of the migrating σ bond were important factors. It is noteworthy that the rearrangement proceeds in a stereospecific manner.

    15. Biosensors

      Simple Biosensor with High Selectivity and Sensitivity: Thiol-Specific Biomolecular Probing and Intracellular Imaging by AIE Fluorogen on a TLC Plate through a Thiol–Ene Click Mechanism (pages 8433–8438)

      Yang Liu, Yong Yu, Jacky W. Y. Lam, Yuning Hong, Mahtab Faisal, Wang Zhang Yuan and Ben Zhong Tang

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.200902505

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      Bright SHparks! A spot of tetraphenylethene–maleimide adduct on a TLC plate is only lit up by thiol-containing biomolecules (e.g., cysteine; see figure), even in trace amounts as low as approximately 1 ppb, thus affording a convenient bioprobe with very high selectivity and sensitivity.

    16. Peptidomimetics

      Synthesis of the Phenylpyridal Scaffold as a Helical Peptide Mimetic (pages 8439–8445)

      Gregory T. Bourne, Daniel J. Kuster and Garland R. Marshall

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.201000315

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      Small is beautiful: A phenylpyridal scaffold has been designed and synthesized as a helical peptide mimetic. The synthesis is concise and high yielding, allowing flexibility at the designated attachment points on the scaffold. A small library was synthesized to show the versatility of the method.

    17. Lanthanides

      Lanthanide(III) Complexes of 4,10-Bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans-H6do2a2p) in Solution and in the Solid State: Structural Studies Along the Series (pages 8446–8465)

      M. Paula C. Campello, Sara Lacerda, Isabel C. Santos, Giovannia A. Pereira, Carlos F. G. C. Geraldes, Jan Kotek, Petr Hermann, Jakub Vaněk, Přemysl Lubal, Vojtěch Kubíček , Éva Tóth and Isabel Santos

      Version of Record online: 10 JUN 2010 | DOI: 10.1002/chem.201000320

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      Arm twisting: An abrupt change was observed between the structural parameters of the hydrated/non-hydrated LnIII complexes of trans-H6do2a2p in the solid state. The coordinated water strongly changes the OP-Ln-OP angle and twist angle of the phosphonic/acetic pendant arms (see figure).

    18. Compound Labeling

      Simple Synthesis of Ruthenium π Complexes of Aromatic Amino Acids and Small Peptides (pages 8466–8470)

      Dmitry S. Perekalin, Eduard E. Karslyan, Pavel V. Petrovskii, Yulia V. Nelyubina, Konstantin A. Lyssenko, Alexey S. Kononikhin, Eugene N. Nikolaev and Alexander R. Kudinov

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201000520

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      Simple labeling of amino acids and peptides: Ruthenium π complexes with aromatic amino acids and small peptides have been synthesized in water at room temperature (see scheme) in the presence of oxygen and concomitant biological substances (non-aromatic amino acids, sugars, and nucleotides).

    19. Organic Semiconductors

      2,3,7,8,12,13-Hexaaryltruxenes: An ortho-Substituted Multiarm Design and Microwave-Accelerated Synthesis toward Starburst Macromolecular Materials with Well-Defined π Delocalization (pages 8471–8479)

      Wen-Yong Lai, Ruidong Xia, Donal D. C. Bradley and Wei Huang

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.201000168

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      Starburst macromolecules: A “homogeneous” starburst fluorene system based on a 2,3,7,8,12,13-hexaaryltruxene scaffold is presented (see scheme). Microwave heating proved to be a powerful tool throughout the synthetic procedure. The electronic properties were compared with those of corresponding linear and three-armed counterparts. The novel ortho-substituted, multiarm design provides materials with a nonplanar geometry that helps to define π delocalization.

    20. Supramolecular Catalysis

      Supramolecular Catalysis with Extended Aggregates and Gels: Inversion of Stereoselectivity Caused by Self-Assembly (pages 8480–8486)

      Francisco Rodríguez-Llansola, Juan F. Miravet and Beatriu Escuder

      Version of Record online: 10 JUN 2010 | DOI: 10.1002/chem.201000654

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      Upside down: The stereoselectivity of 1,4-conjugate addition of cyclohexanone to nitrostyrene is dramatically affected by self-assembly of the catalyst. Ultimately, self-assembly of the catalyst into a supramolecular gel yields a self-supported heterogeneous catalyst with reliable activity and stereoselectivty (see scheme).

    21. Mesophases

      Cubic Mesoporous Titanium Phosphonates with Multifunctionality (pages 8487–8494)

      Tian-Yi Ma, Xiu-Zhen Lin and Zhong-Yong Yuan

      Version of Record online: 10 JUN 2010 | DOI: 10.1002/chem.201000364

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      Gleaning the cube: Periodic cubic mesoporous titanium phosphonate materials with bridged organic groups inside the framework were synthesized and were further applied in the photodegradation of rhodamine B (RhB) and adsorption of heavy metal ions and CO2 (see graphic).

    22. Ligand Effects

      Effect of the Nature of the Substituent in N-Alkylimidazole Ligands on the Outcome of Deprotonation: Ring Opening versus the Formation of N-Heterocyclic Carbene Complexes (pages 8495–8507)

      Miguel A. Huertos, Julio Pérez, Lucía Riera, Jesús Díaz and Ramón López

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000459

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      Competing families: Two different families of compounds can be obtained by the deprotonation of [Re(CO)3(N-RIm)3]+ (N-RIm=N-alkylimidazole), depending on the nature of the alkyl substituent. Ring-opened products are obtained if there is at least one aryl group, whereas imidazol-2-yl and, after reaction with electrophiles, N-heterocyclic carbene complexes are produced otherwise (see scheme).

    23. Amine–Boranes

      Group 2 Promoted Hydrogen Release from NMe2H⋅BH3: Intermediates and Catalysis (pages 8508–8515)

      David J. Liptrot, Michael S. Hill, Mary F. Mahon and Dugald J. MacDougall

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201000127

      Thumbnail image of graphical abstract

      Alkaline release: Stoichiometric and catalytic reactions of alkaline earth (Mg and Ca) alkyls and amides with Me2NHBH3 result in the formation of the corresponding amidoborane derivatives and dehydrogenative coupling of two amine–borane fragments under mild conditions (see graphic).

    24. Vinylation Reactions

      Base-Catalyzed Stereoselective Vinylation of Ketones with Arylacetylenes: A New C(sp3)[BOND]C(sp2) Bond-Forming Reaction (pages 8516–8521)

      Boris A. Trofimov, Elena Yu. Schmidt, Igor' A. Ushakov, Nadezhda V. Zorina, Elena V. Skital'tseva, Nadezhda I. Protsuk and Al'bina I. Mikhaleva

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.201000227

      Thumbnail image of graphical abstract

      A valuable vinylation! Previously unknown C-vinylation of ketones occurs with high E stereoselectivity and excellent yields when alkylaryl- and alkylheteroarylketones are treated with arylacetylenes in the presence of KOH/DMSO at 100 °C. This represents a new C(sp3)[BOND]C(sp2) bond-forming reaction of wide scope (see scheme).

    25. High-Density Energetic Salts

      Nitroguanidine-Fused Bicyclic Guanidinium Salts: A Family of High-Density Energetic Materials (pages 8522–8529)

      Ruihu Wang, Yong Guo, Rongjian Sa and Jean'ne M. Shreeve

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.200903286

      Thumbnail image of graphical abstract

      Be explosive! The nitroguanidine-fused bicyclic guanidinium energetic salts (see figure) exhibit excellent thermal stabilities, positive calculated heats of formation, high density, and promising energetic performance.

    26. Green Chemistry

      Metal–Organic Frameworks as Efficient Heterogeneous Catalysts for the Regioselective Ring Opening of Epoxides (pages 8530–8536)

      Amarajothi Dhakshinamoorthy, Mercedes Alvaro and Hermenegildo Garcia

      Version of Record online: 14 JUN 2010 | DOI: 10.1002/chem.201000588

      Thumbnail image of graphical abstract

      Pop goes the epoxide! An iron-based metal–organic framework has been found to efficiently catalyse the ring opening of styrene oxide with alcohols and aniline under mild reaction conditions. Methanol was found to be the most reactive alcohol (see scheme).

    27. Self-Assembly

      Isomeric Squaraine-Based [2]Pseudorotaxanes and [2]Rotaxanes: Synthesis, Optical Properties, and Their Tubular Structures in the Solid State (pages 8537–8544)

      Min Xue, Yong-Sheng Su and Chuan-Feng Chen

      Version of Record online: 10 JUN 2010 | DOI: 10.1002/chem.201000773

      Thumbnail image of graphical abstract

      Rotate your chemistry! A series of squaraine-based isomeric [2]pseudorotaxanes and [2]rotaxanes were synthesized with triptycene-derived tetralactam macrocycles as wheels. Based on different linking modes of triptycene derivatives and different directions of nonsymmetrical squaraine insertion, three isomers of [2]rotaxanes were formed (see scheme).

    28. Diversity-Oriented Synthesis

      Application of an Enyne Metathesis/Diels–Alder Cycloaddition Sequence: A New Versatile Approach to the Syntheses of C-Aryl Glycosides and Spiro-C-Aryl Glycosides (pages 8545–8556)

      Ayyagari V. Subrahmanyam, Kalanidhi Palanichamy and Krishna P. Kaliappan

      Version of Record online: 14 JUN 2010 | DOI: 10.1002/chem.201000482

      Thumbnail image of graphical abstract

      Simple sequence for a difficult task! A sequential enyne metathesis/Diels–Alder reaction/aromatization strategy has been developed to access the synthesis of a library of C-aryl and spiro-C-aryl glycosides (see scheme). This strategy has also been extended to the synthesis of a set of hybrids of C-aryl and spiro-C-aryl glycosides.

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      Preview: Chem. Eur. J. 29/2010 (page 8563)

      Version of Record online: 19 JUL 2010 | DOI: 10.1002/chem.201090139

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