Chemistry - A European Journal

Cover image for Vol. 17 Issue 45

November 4, 2011

Volume 17, Issue 45

Pages 12525–12831

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
    1. Cover Picture: Catalytic Hydrofunctionalization of Alkynes through P[BOND]H Bond Addition: The Unique Role of Orientation and Properties of the Phosphorus Group in the Insertion Step (Chem. Eur. J. 45/2011) (page 12525)

      Prof. Dr. Valentine P. Ananikov, Dr. Anton V. Makarov and Prof. Dr. Irina P. Beletskaya

      Article first published online: 25 OCT 2011 | DOI: 10.1002/chem.201190226

      Thumbnail image of graphical abstract

      Alkyne insertion into metal–phosphorus and metal–hydrogen bonds is a key stage in the metal-catalyzed formation of carbon–phosphorus bonds. The present study reveals the unique influence of the lone pair on the phosphorus and the role of the oxygen atom on the outcome of the insertion reaction. Several reaction pathways have been found that depend on the geometrical arrangement of the phosphorus group and of the metal center. For more details see the Full Paper by V. P. Ananikov et al. on page 12623 ff.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
    1. You have free access to this content
      Corrigendum: Carbodicarbenes and Related Divalent Carbon(0) Compounds (page 12536)

      Susanne Klein, Ralf Tonner and Gernot Frenking

      Article first published online: 25 OCT 2011 | DOI: 10.1002/chem.201190228

      This article corrects:

      Carbodicarbenes and Related Divalent Carbon(0) Compounds

      Vol. 16, Issue 33, 10160–10170, Article first published online: 19 JUL 2010

    2. You have free access to this content
    3. You have free access to this content
      Corrigendum: Boron-Based Dipolar Multicomponent Reactions: Simple Generation of Substituted Aziridines, Oxazolidines and Pyrrolidines (page 12537)

      Nicola Kielland, Federica Catti, Davide Bello, Nicolas Isambert, Ignacio Soteras, F. Javier Luque and Rodolfo Lavilla

      Article first published online: 25 OCT 2011 | DOI: 10.1002/chem.201190229

      This article corrects:
    4. You have free access to this content
      Corrigendum: Metal–Arene Interactions in Dialkylbiarylphosphane Complexes of Copper, Silver, and Gold (page 12537)

      Patricia Pérez-Galán, Nicolas Delpont, Elena Herrero-Gómez, Feliu Maseras and Antonio M. Echavarren

      Article first published online: 25 OCT 2011 | DOI: 10.1002/chem.201190233

      This article corrects:

      Metal–Arene Interactions in Dialkylbiarylphosphane Complexes of Copper, Silver, and Gold

      Vol. 16, Issue 18, 5324–5332, Article first published online: 14 APR 2010

    5. You have free access to this content
      Corrigendum: Metal Ions Drive Thermodynamics and Photochemistry of the Bis(styryl) Macrocyclic Tweezer (page 12537)

      Elena V. Tulyakova, Gaston Vermeersch, Elena N. Gulakova, Olga A. Fedorova, Yuri V. Fedorov, Jean Claude Micheau and Stéphanie Delbaere

      Article first published online: 25 OCT 2011 | DOI: 10.1002/chem.201190234

      This article corrects:

      Metal Ions Drive Thermodynamics and Photochemistry of the Bis(styryl) Macrocyclic Tweezer

      Vol. 16, Issue 19, 5661–5671, Article first published online: 13 APR 2010

    6. You have free access to this content
      Corrigendum: trans-[Pt(BCat′)Me(PCy3)2]: An Experimental Case Study of Reductive Elimination Processes in Pt–Boryls through Associative Mechanisms (page 12537)

      Prof. Dr. Holger Braunschweig, Dr. Rüdiger Bertermann, Peter Brenner, Dr. Michael Burzler, Dr. Rian D. Dewhurst, Dr. Krzysztof Radacki and Dr. Fabian Seeler

      Article first published online: 25 OCT 2011 | DOI: 10.1002/chem.201190235

      This article corrects:
  4. News

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

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

      Developments Towards Regioselective Synthesis of 1,2-Disubstituted Benzimidazoles (pages 12544–12555)

      Luísa C. R. Carvalho, Dr. Eduarda Fernandes and Dr. M. Manuel B. Marques

      Article first published online: 11 OCT 2011 | DOI: 10.1002/chem.201101508

      Thumbnail image of graphical abstract

      From classical to modern: 1,2-Disubstituted benzimidazoles play an important role in several areas and particularly as drug-discovery targets. Several methods to assemble these structures are reviewed, from the classical approaches to the more recently developed processes.

  6. Communications

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

      Dehydrogenative Heck Reaction of Furans and Thiophenes with Styrenes under Mild Conditions and Influence of the Oxidizing Agent on the Reaction Rate (pages 12556–12560)

      Alexandre Vasseur, Dr. Jacques Muzart and Dr. Jean Le Bras

      Article first published online: 29 SEP 2011 | DOI: 10.1002/chem.201101992

      Thumbnail image of graphical abstract

      C[BOND]H vs. C[BOND]Br in Heck: The direct dehydrogenative coupling of furans and thiophenes with styrenes occurs under mild conditions (see scheme). This method allows the coupling of brominated substrates through C[BOND]H bond activation. In addition, DMSO and benzoquinone had a positive effect on the reaction rate.

    2. Synthetic Methods

      Copper(I)-Catalyzed Deacetylenative Coupling of Propargylic Amines: An Efficient Synthesis of Symmetric 1,4-Diamino-2-butynes (pages 12561–12563)

      Dr. Yongeun Kim and Prof. Dr. Hiroyuki Nakamura

      Article first published online: 29 SEP 2011 | DOI: 10.1002/chem.201102710

      Thumbnail image of graphical abstract

      Deacetylenative coupling: Propargylic amines undergo copper-catalyzed deacetylenative coupling to give the symmetric 1,4-diamino-2-butynes. In the presence of a base, the Glaser-type homocoupling takes place, whereas in the absence of a base the deacetylenative coupling takes place (see scheme).

    3. Foldamers

      Quaternary Centres as a Tool for Modulating Foldamer Conformation (pages 12564–12568)

      Dr. Roberta Galeazzi, Dr. Gianluca Martelli, Prof. Andrea Mazzanti, Prof. Mario Orena and Dr. Samuele Rinaldi

      Article first published online: 4 OCT 2011 | DOI: 10.1002/chem.201102103

      Thumbnail image of graphical abstract

      Centre refold: (3R,4S,1′S)-4-Amino-1-(1′-(4-methoxyphenyl)ethyl)-3-methyl-5-oxopyrrolidine-3-carboxylic acid (AMMOPC) gives a foldamer with an 8-helix conformation. When it was inserted in the 12-helix foldamer of (3R,4S,1′S)-4-amino-1-(1′-(4-methoxyphenyl)ethyl)-5-oxo-pyrrolidine-3-carboxylic acid (AMOPC), it locally induced formation of an 8-helix conformation (see figure).

    4. Total Synthesis

      Efficient Total Synthesis of Marine Alkaloid (−)-Nakadomarin A (pages 12569–12572)

      Dr. Bin Cheng, Fufang Wu, Dr. Xiaobao Yang, Yuedong Zhou, Xiaolong Wan and Prof. Dr. Hongbin Zhai

      Article first published online: 29 SEP 2011 | DOI: 10.1002/chem.201102101

      Thumbnail image of graphical abstract

      Z's top: For the total synthesis of the marine alkaloid (−)-nakadomarin A, (−)-camphorsulfonic acid assisted, Z-selective, olefin RCM of a monoamine (less polar) rather than a diamine (more polar) was found to be highly practical for constructing the F ring. The ABCD-tetracyclic core was assembled through a novel efficacious PtCl2-promoted cascade reaction sequence (see scheme).

    5. C[BOND]H Activation

      Ruthenium-Catalyzed Isoquinolone Synthesis through C[BOND]H Activation Using an Oxidizing Directing Group (pages 12573–12577)

      Prof. Dr. Bin Li, Huiliang Feng, Prof. Shansheng Xu and Prof. Dr. Baiquan Wang

      Article first published online: 29 SEP 2011 | DOI: 10.1002/chem.201102445

      Thumbnail image of graphical abstract

      The oxidant directs: A mild, practical, efficient, and regioselective Ru-catalyzed isoquinolone synthesis with a broad substrate scope was reported (see scheme). In this redox neutral process, the aromatic C[BOND]H bond functionalization can be performed at room temperature without using any external oxidant. The mechanism of the reaction was probed, and it was found that C[BOND]H activation is the turnover-limiting step.

    6. Synthetic Methods

      Rhodium-Catalyzed Asymmetric [2+2+2] Cyclization of 1,6-Enynes and Aldehydes (pages 12578–12581)

      Mana Ishida, Yu Shibata, Prof. Dr. Keiichi Noguchi and Prof. Dr. Ken Tanaka

      Article first published online: 5 OCT 2011 | DOI: 10.1002/chem.201102418

      Thumbnail image of graphical abstract

      Asymmetric catalysis: The rhodium-catalyzed asymmetric [2+2+2] cyclization of 1,6-enynes and aldehydes was achieved by using a cationic rhodium(I)/(R)-binap complex as a catalyst (see scheme; cod=1,5-cyclooctadiene). Coordination of the substrate heteroatom to the cationic rhodium plays an important role in this cyclization reaction.

    7. Diels–Alder Reactions

      Grignard Reagent Acceleration of the Intramolecular Diels–Alder Reaction of Furans with Unactivated Alkynes: Towards Structurally Complex Oxabicyclic Alkenes (pages 12582–12586)

      Yifeng Chen, Lu Wang, Prof. Dr. Yuanhong Liu and Prof. Dr. Yuxue Li

      Article first published online: 29 SEP 2011 | DOI: 10.1002/chem.201102028

      Thumbnail image of graphical abstract

      Chelate to accelerate: A cascade reaction of ortho-(alkynyl)phenyl furanyl ketones with Grignard reagents, involving an interesting intramolecular Diels–Alder reaction of furans with unactivated alkynes, is described (see scheme). DFT calculations and experimental results suggest that the formation of a chelated magnesium alkoxide plays an important role in accelerating the reaction rate and determining the stereoselectivity.

    8. Drug Design

      Water-Soluble Prodrug of Antimicrotubule Agent Plinabulin: Effective Strategy with Click Chemistry (pages 12587–12590)

      Dr. Fumika Yakushiji, Hironari Tanaka, Kyohei Muguruma, Takahiro Iwahashi, Yuri Yamazaki and Prof. Dr. Yoshio Hayashi

      Article first published online: 29 SEP 2011 | DOI: 10.1002/chem.201102293

      Thumbnail image of graphical abstract

      Click for improved solubility: A water-soluble prodrug of plinabulin was designed and synthesized efficiently by using click chemistry in three steps (see scheme). The product was highly water-soluble, and the parent compound could be regenerated by esterase hydrolysis.

    9. Annulation Reactions

      Rhodium-Catalyzed Annulation of N-Benzoylsulfonamide with Isocyanide through C[BOND]H Activation (pages 12591–12595)

      Dr. Chen Zhu, Dr. Weiqing Xie and Prof. Dr. John R. Falck

      Article first published online: 4 OCT 2011 | DOI: 10.1002/chem.201102475

      Thumbnail image of graphical abstract

      The first rhodium-catalyzed annulation of N-benzoylsulfonamide (1) with isocyanide (2) through C[BOND]H activation is described. The transformation is broadly compatible with N-benzoylsulfonamides as well as isocyanides with different electronic properties. From a practical point of view, this method provides the most straightforward approach to a series of 3-(imino)isoindolinones (3). Ts=4-toluenesulfonyl.

    10. Biomimetics

      Aerobic Lactonization of Diols by Biomimetic Oxidation (pages 12596–12601)

      Dr. Yoshinori Endo and Prof. Dr. Jan-E. Bäckvall

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201102168

      Thumbnail image of graphical abstract

      Coming up for air: Highly efficient aerobic lactonization can be carried out by a biomimetic oxidation system based on coupled redox catalysts (ruthenium catalyst and electron transfer mediators). This system leads to a low-energy electron transfer from diol to molecular oxygen. Various diols were aerobically oxidized to the corresponding five- to nine-membered lactones in good to high yields under mild reaction conditions (see scheme).

    11. Asymmetric Synthesis

      N-Sulfinylcarboximidates as a New Class of Chiral Bidentate Ligands: Application to Asymmetric Coordination Chemistry (pages 12602–12605)

      Zhijie Lin, Dr. Mehmet Ali Celik, Chen Fu, Dr. Klaus Harms, Prof. Dr. Gernot Frenking and Prof. Dr. Eric Meggers

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101886

      Thumbnail image of graphical abstract

      A class of its own: A new chiral bidentate ligand, N-acetyl-tert-butanesulfinamide, was applied to the asymmetric synthesis of octahedral ruthenium polypyridyl complexes. This new class of ligands coordinates in a bidentate fashion through its deprotonated N-sulfinylcarboximidate form (see scheme). This sulfinamide auxiliary should be highly valuable for the efficient asymmetric synthesis of a large variety of ruthenium complexes.

    12. Nanomaterials

      Bis(azobenzene)-Based Photoswitchable, Prochiral, Cα-Tetrasubstituted α-Amino Acids for Nanomaterials Applications (pages 12606–12611)

      Paola Fatás, Edoardo Longo, Dr. Federico Rastrelli, Dr. Marco Crisma, Prof. Claudio Toniolo, Dr. Ana I. Jiménez, Prof. Carlos Cativiela and Dr. Alessandro Moretto

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201102609

      Thumbnail image of graphical abstract

      Light-driven chirality: Sequential light-driven isomerization of prochiral, bis(azobenzene)-containing amino acids results in the formation of chiral entities that have been characterized by different techniques. Metal nanoparticles conjugated with these amino acids retain the photoswitching properties and show conformation-dependent magnetic susceptibility that can be reversibly controlled by irradiation (see figure).

  7. Full Papers

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

      Telomere Structure and Stability: Covalency in Hydrogen Bonds, Not Resonance Assistance, Causes Cooperativity in Guanine Quartets (pages 12612–12622)

      Dr. Célia Fonseca Guerra, Hester Zijlstra, Dr. Gábor Paragi and Prof. Dr. F. Matthias Bickelhaupt

      Article first published online: 13 OCT 2011 | DOI: 10.1002/chem.201102234

      Thumbnail image of graphical abstract

      Separation leads to cooperation: Quantum chemical analyses show that telomere structures receive additional stabilization from cooperativity effects in guanine quartets (see graphic). This cooperativity derives directly from the charge separation across guanine bases, induced by the unidirectional donor–acceptor orbital interactions in the hydrogen bonds.

    2. Palladium Catalysis

      Catalytic Hydrofunctionalization of Alkynes through P[BOND]H Bond Addition: The Unique Role of Orientation and Properties of the Phosphorus Group in the Insertion Step (pages 12623–12630)

      Prof. Dr. Valentine P. Ananikov, Dr. Anton V. Makarov and Prof. Dr. Irina P. Beletskaya

      Article first published online: 4 OCT 2011 | DOI: 10.1002/chem.201101898

      Thumbnail image of graphical abstract

      The unique influence of the nature of the phosphorus center in the P[DOUBLE BOND]PR2, P(O)R2, and P(O)(OR)2 groups on the outcome of alkyne insertion into metal–phosphorus and metal–hydrogen bonds has been investigated by means of density functional calculations. Several pathways for the formation of C[BOND]P bonds have been found that depend on the geometrical arrangement of the phosphorus group and of the metal center (see scheme).

    3. Electronic Structure

      Incorporation of Spiroxanthene Units in Blue-Emitting Oligophenylene Frameworks: A New Molecular Design for OLED Applications (pages 12631–12645)

      Dr. Cyril Poriel, Dr. Nicolas Cocherel, Dr. Joëlle Rault-Berthelot, Dr. Laurence Vignau and Dr. Olivier Jeannin

      Article first published online: 27 SEP 2011 | DOI: 10.1002/chem.201100790

      Thumbnail image of graphical abstract

      Energize your chemistry! New spiro-configured blue fluorophores containing an intracyclic oxygen atom, dispiroxanthene-indenofluorene (DSX-IF) and dispiroxanthene-ladder pentaphenylene (DSX-LPP), have been synthesized by different synthetic approaches (see graphic). Their properties have been investigated in detail and compared with those of their ‘all-carbon’ analogues.

    4. Liquid Crystals

      Pentadecyl Phenol- and Cardanol-Functionalized Fluorescent, Room-Temperature Liquid-Crystalline Perylene Bisimides: Effect of Pendant Chain Unsaturation on Self-Assembly (pages 12646–12658)

      Ghanashyam A. Bhavsar and Dr. S. K. Asha

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101011

      Thumbnail image of graphical abstract

      Shape shifters: The new perylene bisimide building block 1 formed a disordered columnar hexagonal mesophase at high temperature and transformed into a highly ordered plastic columnar phase around 160 °C that was retained until room temperature. The analogous derivative with pendant unsaturation formed a disordered columnar mesophase with a lower liquid-crystalline window.

    5. Drug Delivery

      Clickable Functionalization of Liposomes with the gH625 Peptide from Herpes simplex Virus Type I for Intracellular Drug Delivery (pages 12659–12668)

      Rossella Tarallo, Dr. Antonella Accardo, Dr. Annarita Falanga, Dr. Daniela Guarnieri, Dr. Giuseppe Vitiello, Prof. Paolo Netti, Dr. Gerardino D'Errico, Prof. Giancarlo Morelli and Dr. Stefania Galdiero

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101425

      Thumbnail image of graphical abstract

      Clickable liposomes for drug delivery: Liposomes, externally modified by click chemistry with the Herpes simplex virus type I derived peptide gH625 for improving cellular uptake of encapsulated drugs, are presented in this study (see picture). The results suggest that the functionalized liposomes may act as promising intracellular targeting carriers for efficient delivery of drugs, such as chemotherapeutic agents, into tumor cells.

    6. Actinide Chemistry

      A Base-Free Thorium–Terminal-Imido Metallocene: Synthesis, Structure, and Reactivity (pages 12669–12682)

      Wenshan Ren, Prof. Guofu Zi, Prof. De-Cai Fang and Dr. Marc D. Walter

      Article first published online: 4 OCT 2011 | DOI: 10.1002/chem.201101972

      Thumbnail image of graphical abstract

      Man of actinide: A base-free thorium–terminal-imido metallocene (see scheme) has been prepared and structurally characterized. It does not show nucleophilic behavior, but it exhibits activity with electron-rich or unsaturated reagents. DFT studies provide a detailed understanding of the experimentally observed reactivity patterns.

    7. Asymmetric Hydrogenation

      Unravelling the Reaction Path of Rhodium–MonoPhos-Catalysed Olefin Hydrogenation (pages 12683–12695)

      Dr. Elisabetta Alberico, Priv.-Doz. Dr. Wolfgang Baumann, Prof. Dr. Johannes G. de Vries, Dr. Hans-Joachim Drexler, Prof. Dr. Serafino Gladiali, Prof. Dr. Detlef Heller, Huub J. W. Henderickx and Dr. Laurent Lefort

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101793

      Thumbnail image of graphical abstract

      Dimers are forever: Reaction intermediates around the catalytic cycle of the asymmetric hydrogenation of methyl (Z)-2-acetamidocinnamate by [Rh(MonoPhos)2(nbd)]SbF6 (nbd=bicyclo[2.2.1]hepta-2,5-diene) catalyst (see scheme) were detected by using 1H, 31P and 103Rh NMR spectroscopy and ESI-MS. The asymmetric hydrogenation appears to follow a Halpern-like mechanism.

    8. Boron-Containing Heterocycles

      Unsymmetrically Substituted 9,10-Dihydro-9,10-diboraanthracenes as Versatile Building Blocks for Boron-Doped π-Conjugated Systems (pages 12696–12705)

      Dipl.-Chem. Estera Januszewski, Dr. Andreas Lorbach, B. Sc. Rekha Grewal, Dr. Michael Bolte, Dr. Jan W. Bats, Dr. Hans-Wolfram Lerner and Prof. Dr. Matthias Wagner

      Article first published online: 5 OCT 2011 | DOI: 10.1002/chem.201101701

      Thumbnail image of graphical abstract

      Putting boron in the ring: The unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracene MesB(C6H4)2BH, which exists as a dimeric species in the solid state and shows strong photoluminescence (see figure), is a versatile reagent that can be used to introduce a rigid, boron-doped moiety into conjugated π-electron systems through hydroboration reactions.

    9. C[BOND]H Arylation

      Palladium Nanoparticles Encapsulated in a Metal–Organic Framework as Efficient Heterogeneous Catalysts for Direct C2 Arylation of Indoles (pages 12706–12712)

      Dr. Yuanbiao Huang, Dr. Zujin Lin and Prof. Rong Cao

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101705

      Thumbnail image of graphical abstract

      MOF-encapsulated catalyst: Highly dispersed palladium nanoparticles encapsulated in the mesoporous metal–organic framework (MOF) MIL-101(Cr) exhibited high catalytic activities for the direct C2 arylation of substituted indoles with a range of substituted iodobenzenes (see figure) by only using a very low amount of the Pd catalyst (0.1 mol %). The catalyst is easily recovered and can be reused several times without leaching into solution and loss of activity.

    10. Organozinc Reagents

      Reactions of ZnR2 Compounds with Dibenzoyl: Characterisation of the Alkyl-Transfer Products and a Striking Product-Inhibition Effect (pages 12713–12721)

      Dr. Izabela Dranka, Marcin Kubisiak, Dr. Iwona Justyniak, Michał Lesiuk, Dominik Kubicki and Prof. Dr. Janusz Lewiński

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101997

      Thumbnail image of graphical abstract

      It all depends on R: The first systematic theoretical and experimental study of ZnR2 (R=Me, Et or tBu) with dibenzoyl revealed that the character of the metal-bonded alkyl group as well as the reaction conditions (e.g., ratio of the reagents, temperature) modulate the reaction outcome (see scheme). Monitoring the dibenzoyl conversion over the reaction course revealed a product-inhibition effect, which highlights possible participation of multiple equilibria of different zinc alkoxide/ZnR2 aggregates.

    11. Low-Molecular-Weight Compounds

      Holographic Investigations of Azobenzene-Containing Low-Molecular-Weight Compounds in Pure Materials and Binary Blends with Polystyrene (pages 12722–12728)

      Dr. Hubert Audorff, Roland Walker, Prof. Lothar Kador and Prof. Hans-Werner Schmidt

      Article first published online: 29 SEP 2011 | DOI: 10.1002/chem.201100941

      Thumbnail image of graphical abstract

      Fast holographic response: The formation of volume gratings in photochromic low-molecular-weight compounds is investigated. The compounds consist of a central core with azobenzene-based arms attached through esterification (see image). Films of the neat compounds and binary blends of the low-molecular-weight compounds with polystyrene are investigated in holographic experiments.

    12. P Ligands

      Assessment of the Electronic Properties of P ligands Stemming from Secondary Phosphine Oxides (pages 12729–12740)

      Dr. David Martin, Dr. Delphine Moraleda, Dr. Thierry Achard, Dr. Laurent Giordano and Prof. Gérard Buono

      Article first published online: 29 SEP 2011 | DOI: 10.1002/chem.201101663

      Thumbnail image of graphical abstract

      A generous donation: The net donating ability of monodentate and bidentate P ligands stemming from secondary phosphine oxides (SPOs) is spread on an unprecedented range: from π-accepting phosphite-like compounds, as far as extremely electron-donating ligands outclassing N-heterocyclic carbenes (NHCs; see figure).

    13. Synthetic Methods

      Synthesis, Structure, and Glutathione Peroxidase-Like Activity of Amino Acid Containing Ebselen Analogues and Diaryl Diselenides (pages 12741–12755)

      Karuthapandi Selvakumar, Poonam Shah, Prof. Harkesh B. Singh and Prof. Ray J. Butcher

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201100930

      Thumbnail image of graphical abstract

      Peroxidase-like activity: Reaction of compound 1 (see figure) with glutathione (GSH) leads to the formation of the corresponding selenenyl sulfide and diaryl diselenide intermediates. The reaction of these intermediates with H2O2 leads to the formation of 1 via arylselenenic acid. This process hampers the GPx-like activity at low GSH concentrations.

    14. Pentannulation

      Palladium-Catalyzed Pentannulation of Polycyclic Aromatic Hydrocarbons (pages 12756–12762)

      Christian Lütke Eversloh, Dr. Yuri Avlasevich, Dr. Chen Li and Prof. Dr. Klaus Müllen

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101126

      Thumbnail image of graphical abstract

      Give me five! A new and versatile one-step synthesis of a series of small molecular chromophores based on cyclopentannulated pyrene, anthracene, and perylene is presented. The pentannulation is achieved by the straightforward Pd0-catalyzed carbannulation with various substituted acetylenes and arylbromides. UV/Vis absorption as well as cyclovoltammetric measurements were performed for characterization.

    15. Cycloaddition

      Versatile Stereoselective Cycloadditions between Heterocumulenes and Phosphagermaallene Tip(tBu)Ge[DOUBLE BOND]C[DOUBLE BOND]PMes*: Experimental and Theoretical Investigations (pages 12763–12772)

      Dr. Dumitru Ghereg, Dr. Erwan André, Prof Dr. Heinz Gornitzka, Dr. Jean Escudié, Dr. Fatima Ouhsaine, Dr. Nathalie Saffon, Dr. Karinne Miqueu and Dr. Jean-Marc Sotiropoulos

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201100281

      Thumbnail image of graphical abstract

      Acting on Ge[DOUBLE BOND]C[DOUBLE BOND]P: Phosphagermaallene Tip(tBu)Ge[DOUBLE BOND]C[DOUBLE BOND]PMes* (Tip=2,4,6-triisopropylphenyl, Mes*=2,4,6-tri-tert-butylphenyl) reacts with PhNCO by a [2+2] cycloaddition that involves the Ge[DOUBLE BOND]C bond to afford germacyclobutanes; in contrast, it reacts with PhNCS by a [3+2] cycloaddition that involves the whole Ge[DOUBLE BOND]C[DOUBLE BOND]P group to give transient phosphagermacarbenes (see scheme).

    16. Nickel Chemistry

      Synthetic Applications of the Nickel-Catalyzed Cyclization of Alkynes Combined with Addition Reactions in a Domino Process (pages 12773–12783)

      Dr. Muriel Durandetti, Dr. Lucie Hardou, Rudy Lhermet, Mathieu Rouen and Dr. Jacques Maddaluno

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201100967

      Thumbnail image of graphical abstract

      Yes nickel can! Carbonickelation of alkynes and functionalization of the resulting vinylnickel moiety occurs efficiently. Overall, a domino cyclization–condensation process propagated by substoichiometric nickel catalysis takes place (see scheme). This one-pot synthesis provides substituted polyheterocyclic compounds in good yields and high stereoselectivity.

    17. Metal Oxide Methanesulfonates

      Methanesulfonates of High-Valent Metals: Syntheses and Structural Features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and Their Thermal Decomposition under N2 and O2 Atmosphere (pages 12784–12801)

      Ulf Betke, Kai Neuschulz and Mathias S. Wickleder

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101618

      Thumbnail image of graphical abstract

      The first solvent-free oxide methanesulfonates of V, Mo, U, and Re were prepared by solvothermal reactions of the corresponding oxides (V, Mo, Re) or the acetate (U) with methanesulfonic acid, and their crystal structures determined. Thermal decomposition under O2 leads to the metal oxides in the highest oxidation state, while decomposition under N2 leads to reduced oxides and sulfides of the elements. The picture shows the layered structure of VO(CH3SO3)2 and SEM images of the VO2 product of the decomposition of V2O3(CH3SO3)4 under inert gas.

    18. Drug Delivery

      Highly Porous, Water-Soluble, Superparamagnetic, and Biocompatible Magnetite Nanocrystal Clusters for Targeted Drug Delivery (pages 12802–12808)

      Fuping Dong, Dr. Wanping Guo, Prof. Jae-Ho Bae, Prof. Sun-Hee Kim and Prof. Chang-Sik Ha

      Article first published online: 27 SEP 2011 | DOI: 10.1002/chem.201101110

      Thumbnail image of graphical abstract

      Make it porous: Highly porous magnetite nanocrystal clusters were fabricated by using a solvothermal process and drugs were loaded into these clusters to form a new drug-delivery system (see picture). This multifunctional system shows low cytotoxicity and sustained drug-release properties, which revealed potential applications in a magnetic-targeted drug-delivery system.

    19. Domino Reactions

      Solvent/Base Effects in the Selective Domino Synthesis of Phenanthridinones That Involves High-Valent Palladium Species: Experimental and Theoretical Studies (pages 12809–12819)

      Dr. Ludovic Donati, Pascale Leproux, Elise Prost, Prof. Sylvie Michel, Prof. François Tillequin, Prof. Vincent Gandon and Dr. François-Hugues Porée

      Article first published online: 27 SEP 2011 | DOI: 10.1002/chem.201101354

      Thumbnail image of graphical abstract

      Domino theory: The domino reaction of o-bromobenzamides 1 in the presence of K2CO3 and [PdCl2(PPh3)2] granted a selective access to phenanthridinones 2 or to the new 1-carboxamide phenanthridinones 3 depending on the solvent (see scheme). Investigations showed a direct correlation between the base dissociation and the solvent polarity on the selectivity.

    20. Fluorescent Probes

      A Microenvironment-Sensitive Fluorescent Pyrimidine Ribonucleoside Analogue: Synthesis, Enzymatic Incorporation, and Fluorescence Detection of a DNA Abasic Site (pages 12820–12827)

      Arun A. Tanpure and Dr. Seergazhi G. Srivatsan

      Article first published online: 28 SEP 2011 | DOI: 10.1002/chem.201101194

      Thumbnail image of graphical abstract

      Uridine blue: T7 RNA polymerase effectively incorporates a polarity-sensitive fluorescent pyrimidine ribonucleotide analogue to produce emissive RNA oligonucleotides. The enzymatically generated fluorescent oligoribonucleotide reporter positively signals the presence of a DNA abasic site (see picture).

  8. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    9. Preview
    1. You have free access to this content
      Preview: Chem. Eur. J. 46/2011 (page 12831)

      Article first published online: 25 OCT 2011 | DOI: 10.1002/chem.201190231

SEARCH

SEARCH BY CITATION