Angewandte Chemie International Edition

Cover image for Vol. 47 Issue 24

June 2, 2008

Volume 47, Issue 24

Pages 4449–4607

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
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    1. Cover Picture: Au36 Crown: A Macrocyclization Directed by Metal–Metal Bonding Interactions (Angew. Chem. Int. Ed. 24/2008) (page 4449)

      Shu-Yan Yu, Qing-Fu Sun, Terence Kwok-Ming Lee, Eddie Chung-Chin Cheng, Yi-Zhi Li and Vivian Wing-Wah Yam

      Version of Record online: 27 MAY 2008 | DOI: 10.1002/anie.200890111

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      A giant, crown-like Au36ring, featuring continuous metal–metal contacts, forms by a self-assembly which utilizes AuI⋅⋅⋅AuI bonding interactions. The cover picture shows the structure of this system, and the synthesis from ferrocenyldithiocarbamate and gold(I) ions is described by S.-Y. Yu, Y.-Z. Li, V. W.-W. Yam et al. in their Communication on page 4551 ff.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
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    1. Inside Cover: Spirocyclic Oxetanes: Synthesis and Properties (Angew. Chem. Int. Ed. 24/2008) (page 4450)

      Georg Wuitschik, Mark Rogers-Evans, Andreas Buckl, Maurizio Bernasconi, Moritz Märki, Thierry Godel, Holger Fischer, Björn Wagner, Isabelle Parrilla, Franz Schuler, Josef Schneider, André Alker, W. Bernd Schweizer, Klaus Müller and Erick M. Carreira

      Version of Record online: 27 MAY 2008 | DOI: 10.1002/anie.200890112

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      Star constellations like atom positions, suggest connectivity; in place of Orion, piperidone is imagined, and its superimposition with “homospiromorpholine”, described by G. Wuitschik et al. in their Communication on page 4512 ff., is remarkable. Stimulated by the analogy between the van't Hoff description of a ketone and an oxetane, spirocyclic oxetane amines—analogues of ketoamines, lactams, and morpholine with a systematically reclined polar ether unit—are explored.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
    12. Preview
  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. You have free access to this content
  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
    12. Preview
  6. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
    12. Preview
  7. Highlight

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
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    1. Square-Planar Coordinated Iron in the Layered Oxoferrate(II) SrFeO2 (pages 4470–4472)

      Jürgen Köhler

      Version of Record online: 5 MAY 2008 | DOI: 10.1002/anie.200800855

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      A soft reduction: The new layered oxoferrate(II) SrFeO2 (see scheme: Fe red, Sr yellow, C gray) was synthesized by the reduction of the slightly oxygen-deficient perovskite SrFeO3−x at 400 K with CaH2 in a form of topotactical reaction. The square-planar-coordinated iron(II) ions in SrFeO2 exhibit a high-spin d6 configuration with a doubly occupied dmath image orbital. SrFeO2 orders antiferromagnetically at an unusual high Néel temperature of TN=473 K.

  8. Essay

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
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    1. Learning from Molecules in Distress (pages 4474–4481)

      Roald Hoffmann and Henning Hopf

      Version of Record online: 16 APR 2008 | DOI: 10.1002/anie.200705775

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      Going to extremes: Deformed molecules with “planar” carbon atoms, orthogonal double bonds, nonlinear triple bonds, and aromatic rings distorted into a boat structure have interested chemists for decades. This essay traces the reasons for this fascination, and finds them in the psyche of the researcher: the wish to transgress the limits of normalcy, the insatiable curiosity to extend the limits of method and mind, and the eternal human joy to find something new while playing.

  9. Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
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    1. Chiral Olefins as Steering Ligands in Asymmetric Catalysis (pages 4482–4502)

      Christian Defieber, Hansjörg Grützmacher and Erick M. Carreira

      Version of Record online: 5 MAY 2008 | DOI: 10.1002/anie.200703612

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      The conceptually novel class of ligands, the chiral dienes, complement traditional heteroatom-based ligands. In addition to a historical perspective on metal–olefin complexes, this Review summarizes various syntheses of chiral olefins (some are shown in the picture) that have found widespread application as ligands in asymmetric transition-metal-catalyzed processes, such as in the asymmetric conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds.

  10. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Host–Guest Driven Self-Assembly of Linear and Star Supramolecular Polymers (pages 4504–4508)

      Roger M. Yebeutchou, Francesca Tancini, Nicola Demitri, Silvano Geremia, Raniero Mendichi and Enrico Dalcanale

      Version of Record online: 5 MAY 2008 | DOI: 10.1002/anie.200801002

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      Supramolecular plasticity: The remarkable host–guest properties of phosphonate cavitands have been exploited in the self-assembly of supramolecular polymers (see picture) that feature guest-triggered reversibility and template-driven conversion from linear into star-branched forms. The structurally similar but complexation-inefficient thiophosphonate cavitand acts as chain stopper to control the degree of polymerization.

    2. Crystalline Polymer Ultrathin Films from Mesoscopic Precursors (pages 4509–4511)

      Qiong Tong, Marina Krumova and Stefan Mecking

      Version of Record online: 16 MAY 2008 | DOI: 10.1002/anie.200801028

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      Caught on film: Ultrathin (50 nm) films of crystalline polyethylene were prepared at room temperature from prefabricated polymer nanocrystals functioning as building blocks. The very small particle size, in combination with the phenomenon that the amorphous regions are located at the surface exclusively in polymer single crystals, results in efficient interaction between particles in the films.

    3. Spirocyclic Oxetanes: Synthesis and Properties (pages 4512–4515)

      Georg Wuitschik, Mark Rogers-Evans, Andreas Buckl, Maurizio Bernasconi, Moritz Märki, Thierry Godel, Holger Fischer, Björn Wagner, Isabelle Parrilla, Franz Schuler, Josef Schneider, André Alker, W. Bernd Schweizer, Klaus Müller and Erick M. Carreira

      Version of Record online: 9 MAY 2008 | DOI: 10.1002/anie.200800450

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      Wormholes through chemical space: Spirocyclic oxetanes are described as analogues of morpholine and also as topological siblings of their carbonyl counterparts. They are particularly promising in terms of both their physicochemical properties and the ease with which they can be grafted onto molecular structures. The data collected highlight oxetanes as both the hydrophilic sister of a gem-dimethyl unit and the carbonyl group's lipophilic brother.

    4. Synergistic Effects of B/N Doping on the Visible-Light Photocatalytic Activity of Mesoporous TiO2 (pages 4516–4520)

      Gang Liu, Yanning Zhao, Chenghua Sun, Feng Li, Gao Qing Lu and Hui-Ming Cheng

      Version of Record online: 6 MAY 2008 | DOI: 10.1002/anie.200705633

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      Add an N: The visible-light absorption of boron-doped mesoporous TiO2 depends strongly on the state of the dopant (see picture), although the activity can be substantially enhanced by additional doping of nitrogen. The new O-Ti-B-N structure formed on the surface of the photocatalyst is highly active in collecting and separating the charge carriers, thereby greatly enhancing the visible light photocatalytic activity.

      Corrected by:

      Corrigendum: Synergistic Effects of B/N Doping on the Visible-Light Photocatalytic Activity of Mesoporous TiO2

      Vol. 47, Issue 29, 5277, Version of Record online: 7 JUL 2008

    5. α-MnO2 Nanowires: A Catalyst for the O2 Electrode in Rechargeable Lithium Batteries (pages 4521–4524)

      Aurélie Débart, Allan J. Paterson, Jianli Bao and Peter G. Bruce

      Version of Record online: 6 MAY 2008 | DOI: 10.1002/anie.200705648

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      Higher-capacity lithium batteries can be fabricated by using α-MnO2 nanowires as the catalyst in a porous, composite oxygen cathode. In the depicted scanning electron micrograph of a composite positive electrode, deposits of Li2O2, which accumulates during discharge, can be seen within a porous matrix consisting of α-MnO2 and carbon.

    6. Filamentous Artificial Virus from a Self-Assembled Discrete Nanoribbon (pages 4525–4528)

      Yong-beom Lim, Eunji Lee, You-Rim Yoon, Myeong Sup Lee and Myongsoo Lee

      Version of Record online: 7 MAY 2008 | DOI: 10.1002/anie.200800266

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      Therapeutic viruses: A filament-shaped artificial virus is formed by using a preorganized supramolecular nanoribbon as a template. The artificial virus (see picture), which is composed of the nanoribbon, small interfering RNAs (blue, double-helix shape), and hydrophobic guests (red), is highly efficient in delivering genes and drugs to the inside of cells.

    7. Solvent Effect on Color, Band Shape, and Charge-Density Distribution for Merocyanine Dyes Close to the Cyanine Limit (pages 4529–4532)

      Frank Würthner, Graziano Archetti, Ralf Schmidt and Hans-Georg Kuball

      Version of Record online: 5 MAY 2008 | DOI: 10.1002/anie.200800279

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      Solvatochromism elucidated: UV/Vis and electrooptical absorption spectroscopy were used to elucidate the effect of solvent on the electrical and optical properties of three merocyanine dyes. Changes in the shape of the Vis absorption band in solvents of different polarity [e.g., the depicted dye in Et2O (black), AcOEt (blue), and MeCN (orange)] are explained by different excited-state dipole moments of the respective vibronic transitions.

    8. Water-Based Ligand Screening for Paramagnetic Metalloproteins (pages 4533–4537)

      Ivano Bertini, Marco Fragai, Claudio Luchinat and Eleonora Talluri

      Version of Record online: 8 MAY 2008 | DOI: 10.1002/anie.200800327

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      The relaxation rate of water proton nuclei can be used to screen ligands (L; see picture) directed to the metal binding site in paramagnetic metalloproteins by NMR spectroscopy. The very high concentration of water protons provides an enormous sensitivity and permits the use of unprecedentedly low amounts of protein.

    9. Chiral Octupolar Metal–Organoboron NLO Frameworks with (14,3) Topology (pages 4538–4541)

      Yan Liu, Xin Xu, Fakun Zheng and Yong Cui

      Version of Record online: 6 MAY 2008 | DOI: 10.1002/anie.200800586

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      Tunable NLO activity: The title compounds were efficiently assembled from the enantiopure and threefold-symmetric tris(4-pyridylduryl)borane ligand L through coordinative bonds. The Cd–organoboron framework (see picture) exhibits a significant second harmonic generation response and, more importantly, the NLO activity can be tuned by means of different encapsulated counteranions.

    10. Highly Efficient Blue-Emitting Iridium(III) Carbene Complexes and Phosphorescent OLEDs (pages 4542–4545)

      Chiung-Fang Chang, Yi-Ming Cheng, Yun Chi, Yuan-Chieh Chiu, Chao-Chen Lin, Gene-Hsiang Lee, Pi-Tai Chou, Chung-Chia Chen, Chih-Hao Chang and Chung-Chih Wu

      Version of Record online: 6 MAY 2008 | DOI: 10.1002/anie.200800748

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      Bright & blue: A strategy for reducing metal-chelate internal strain enables the preparation of blue emitting iridium(III) carbene complexes (see picture; Ir red, N light blue, F green). The phosphorescent OLED fabricated from one of these complexes shows remarkable CIE coordinates of (0.16, 0.13) and peak efficiencies of 6.0 % photons per electron, 6.3 cd A−1, and 4.0 lm W−1.

    11. Self-Assembly of a Cyclic Zn4O4 Tetramer by Aerobic Oxidation of a Bisoxazoline: A Molecular “Nest” for Nucleophilic OH (pages 4546–4550)

      Béatrice Jacques, Clémence Dro, Stéphane Bellemin-Laponnaz, Hubert Wadepohl and Lutz H. Gade

      Version of Record online: 5 MAY 2008 | DOI: 10.1002/anie.200800870

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      Nesting hydroxide: Coordination and aerobic oxidation of a bisoxazoline Me2box is coupled with self-assembly to form a highly ordered [(Me2box)O4Zn4]4+ complex. The metallamacrocycle acts as a nest-like hydroxide receptor (see scheme, right) and shows catalytic phosphatase activity.

    12. Au36 Crown: A Macrocyclization Directed by Metal–Metal Bonding Interactions (pages 4551–4554)

      Shu-Yan Yu, Qing-Fu Sun, Terence Kwok-Ming Lee, Eddie Chung-Chin Cheng, Yi-Zhi Li and Vivian Wing-Wah Yam

      Version of Record online: 21 APR 2008 | DOI: 10.1002/anie.200801001

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      Lord of the golden rings: A giant, crown-like Au36 ring aggregate with continuous metal–metal contacts (see picture; gold(I) centers are in ball and stick representation) is formed by an AuI⋅⋅⋅AuI bonding interaction directed self-assembly.

    13. Pincer Click Ligands (pages 4555–4558)

      Elaine M. Schuster, Mark Botoshansky and Mark Gandelman

      Version of Record online: 15 MAY 2008 | DOI: 10.1002/anie.200800123

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      It all clicks into place: The use of “click chemistry” has been found to be highly advantageous for the selective and rapid combinatorial synthesis of a family of pincer-type ligands from relatively simple building blocks (see scheme). This synthetic strategy provides access to a range of well-defined transition-metal catalysts which exhibit extremely high catalytic efficiency in the Heck reaction.

    14. Understanding Methane Aromatization on a Zn-Modified High-Silica Zeolite (pages 4559–4562)

      Mikhail V. Luzgin, Vladimir A. Rogov, Sergei S. Arzumanov, Alexander V. Toktarev, Alexander G. Stepanov and Valentin N. Parmon

      Version of Record online: 2 MAY 2008 | DOI: 10.1002/anie.200800317

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      It takes two: A high level of conversion of 13C atoms of methane into the products of methane/propane coaromatization on zeolite Zn/H-BEA has been demonstrated by 13C solid-state NMR spectroscopic analysis and GC-MS. The isotope-labeling experiments show the mechanism consists of the methylation of aromatic compounds formed from the propane followed by ring-expansion/contraction (see scheme).

    15. N-Confused and N-Fused meso-Aryl Sapphyrins (pages 4563–4567)

      Iti Gupta, Alagar Srinivasan, Tatsuki Morimoto, Motoki Toganoh and Hiroyuki Furuta

      Version of Record online: 5 MAY 2008 | DOI: 10.1002/anie.200705984

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      A state of (con)fusion: The introduction of a confused pyrrole ring into a meso-aryl sapphyrin framework destabilizes the macrocycle and forces a fusion reaction to occur. Subsequent metalation with rhenium results in further mutation to form a domino-fused sapphyrin with a fused penta-ring system (see scheme).

    16. A Submicrometer Wire-to-Wheel Metamorphism of Hybrid Tridentate Cyclometalated Platinum(II) Complexes (pages 4568–4572)

      Wei Lu, Stephen Sin-Yin Chui, Kwan-Ming Ng and Chi-Ming Che

      Version of Record online: 8 MAY 2008 | DOI: 10.1002/anie.200704450

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      Wheely springy wires: Freestanding and crystalline submicrometer wires, springs, and wheels are grown in aqueous acetonitrile dispersions starting from the organoplatinum(II) complexes 1 and 2(PF6). The growth mechanism is proposed to involve ligand-substitution reactions and electrostatic and PtII⋅⋅⋅PtII interactions.

    17. Freeze-Align and Heat-Fuse: Microwires and Networks from Nanoparticle Suspensions (pages 4573–4576)

      Haifei Zhang, Jun-Young Lee, Adham Ahmed, Irshad Hussain and Andrew I. Cooper

      Version of Record online: 30 APR 2008 | DOI: 10.1002/anie.200705512

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      Staying in line: Aqueous colloids (particle diameter 10–500 nm) are directionally frozen and freeze-dried to produce aligned microwires, which can be fused together by heat treatment with complete retention of the morphology. The method is generic: by controlling surface charge, the approach can be applied to metals, metal oxides, and organic polymers. A single microwire formed by the assembly of polystyrene colloids is shown.

    18. Reversible Solubilization and Precipitation of Carbon Nanotubes through Oxidation–Reduction Reactions of a Solubilizing Agent (pages 4577–4580)

      Kazuyuki Nobusawa, Atsushi Ikeda, Jun-ichi Kikuchi, Shin-ichiro Kawano, Norifumi Fujita and Seiji Shinkai

      Version of Record online: 28 APR 2008 | DOI: 10.1002/anie.200800095

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      Complex control of solubility: Single-walled nanotubes (SWNTs) can be dissolved in organic solvents by formation of a complex with a 2,2′-bipyridine derivative and Cu through mechanochemical high-speed vibration milling. The conformational change of the CuI/CuII complexes resulting from chemical oxidation–reduction reactions induces different solubilities of the SWNTs because of differences in the π–π stacking interactions.

    19. [Pd(PPh3)4]-Catalyzed Diastereoselective Synthesis of trans-1,2-Diazetidines from 2,3-Allenyl Hydrazines and Aryl Halides (pages 4581–4583)

      Xin Cheng and Shengming Ma

      Version of Record online: 6 MAY 2008 | DOI: 10.1002/anie.200800364

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      Strain, what strain? Pd0-catalyzed cyclization of easily accessed and diversely substituted 2,3-allenyl hydrazines with aryl halides afforded 1,2-diazetidines with two chiral centers in high regio- and diastereoselectively (trans only; see scheme). Optically active 1,2-diazetidines were synthesized by using enantiomerically enriched 2,3-allenyl hydrazines.

    20. The Homoleptic Sandwich Anion [Co(P2C2tBu2)2]: A Versatile Building Block for Phosphaorganometallic Chemistry (pages 4584–4587)

      Robert Wolf, Andreas W. Ehlers, J. Chris Slootweg, Martin Lutz, Dietrich Gudat, Michael Hunger, Anthony L. Spek and Koop Lammertsma

      Version of Record online: 5 MAY 2008 | DOI: 10.1002/anie.200800813

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      A sandwich recipe: Treatment of the anthracene complex [Co(η4-C14H10)2] with tBuC[TRIPLE BOND]P leads to the new diphosphacyclobutadiene sandwich anion 1, which can be converted into the unprecedented phosphaorganometallic complexes 24 upon treatment with different electrophiles (see scheme).

    21. Towards Organocatalytic Polyketide Synthases with Diverse Electrophile Scope: Trifluoroethyl Thioesters as Nucleophiles in Organocatalytic Michael Reactions and Beyond (pages 4588–4591)

      Diego A. Alonso, Shinji Kitagaki, Naoto Utsumi and Carlos F. Barbas III

      Version of Record online: 7 MAY 2008 | DOI: 10.1002/anie.200801088

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      Hot ester nucleophiles! Trifluoroethyl thioesters are effective nucleophiles in direct organocatalytic asymmetric Michael reactions with α,β-unsaturated aldehydes (above). Electronic tuning of thioesters allows for the generation of enolates that also participate in aldol and amination reactions (below).

    22. An Engineered Spider Silk Protein Forms Microspheres (pages 4592–4594)

      Ute K. Slotta, Sebastian Rammensee, Stanislav Gorb and Thomas Scheibel

      Version of Record online: 6 MAY 2008 | DOI: 10.1002/anie.200800683

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      Fibrils or spheres? Spider silk proteins belong to the class of natively unfolded proteins. Depending on the experimental conditions, these proteins form nanofibrils or microspheres following two distinct aggregation pathways. A detailed model describes the assembly mechanism of spider silk proteins into microspheres.

    23. Production of the Antifungal Isochromanone Ajudazols A and B in Chondromyces crocatus Cm c5: Biosynthetic Machinery and Cytochrome P450 Modifications (pages 4595–4599)

      Kathrin Buntin, Shwan Rachid, Maren Scharfe, Helmut Blöcker, Kira J. Weissman and Rolf Müller

      Version of Record online: 6 MAY 2008 | DOI: 10.1002/anie.200705569

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      Unusual biochemistry: The pathway to the antifungal ajudazols (ajudazol A is shown) has been deduced by cloning and sequencing of the gene cluster in the myxobacterium Chondromyces crocatus, coupled with insertional mutagenesis. Ajudazol biosynthesis incorporates several unusual features, including the first P450-catalyzed dehydrogenation identified in bacterial metabolism.

    24. β-Lactones as Privileged Structures for the Active-Site Labeling of Versatile Bacterial Enzyme Classes (pages 4600–4603)

      Thomas Böttcher and Stephan A. Sieber

      Version of Record online: 28 MAR 2008 | DOI: 10.1002/anie.200705768

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      A chemical proteomic strategy has been applied directly to bacterial proteomes, and β-lactones have been identified as important natural product derivatives with a high affinity to various enzyme classes (see picture). This approach may serve as a potent tool for the identification of novel antibacterial targets, the study of their function, and the definition of novel lead structures for the design of enzyme inhibitors.

  11. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlight
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. You have free access to this content

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