Angewandte Chemie International Edition

Cover image for Vol. 46 Issue 18

April 27, 2007

Volume 46, Issue 18

Pages 3157–3379

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. Cover Picture: Prediction of Perception: Probing the hOR17-4 Olfactory Receptor Model with Silicon Analogues of Bourgeonal and Lilial (Angew. Chem. Int. Ed. 18/2007) (page 3157)

      Leszek Doszczak, Philip Kraft, Hans-Peter Weber, Rüdiger Bertermann, Annika Triller, Hanns Hatt and Reinhold Tacke

      Version of Record online: 23 APR 2007 | DOI: 10.1002/anie.200790075

      Smell for yourself by rubbing the cover (and smelling your finger): A lily-of-the-valley accord around sila-bourgeonal is appropriate for the merry month of May. The C/Si exchange in lilial and bourgeonal has only a slight, but distinct influence on the odor and threshold, which was predicted in the electronic surface structures (see the Communication by P. Kraft, H. Hatt, R. Tacke, and co-workers on page 3367 ff). The accord was composed by Caroline Gaillardot, with serenolide (musk) and azurone (salty effect).

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. Inside Cover: Direct Monitoring of Formation and Dissociation of Individual Metal Complexes by Single-Molecule Fluorescence Spectroscopy (Angew. Chem. Int. Ed. 18/2007) (page 3158)

      Alexander Kiel, Janos Kovacs, Andriy Mokhir, Roland Krämer and Dirk-Peter Herten

      Version of Record online: 23 APR 2007 | DOI: 10.1002/anie.200790076

      Single-molecule spectroscopy has proven a versatile tool in biochemistry and molecular biology. In their Communication on page 3363 ff., D. P. Herten et al. describe the first application of this technique to chemical reactions of small molecules by observing the association and dissociation of a Cu2+ complex in real time. By the use of confocal microscopy and by designing a fluorescent metal sensor that can be immobilized on glass slides, they were able to obtain the kinetics of individual complexes in thermodynamic equilibrium.

  3. Graphical Abstract

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
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      Direct Synthesis of 2-(Aminomethyl)indoles through Copper(I)-Catalyzed Domino Three-Component Coupling and Cyclization Reactions (page 3173)

      Hiroaki Ohno, Yusuke Ohta, Shinya Oishi and Nobutaka Fujii

      Version of Record online: 23 APR 2007 | DOI: 10.1002/anie.200790078

      This article corrects:
  5. News

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
    11. Reviews
    12. Communications
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    1. Yoshihiko Ito (1937–2006) (page 3176)

      Masahiro Murakami

      Version of Record online: 23 APR 2007 | DOI: 10.1002/anie.200701275

  7. Book Reviews

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
  8. Highlight

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
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      Dinitrogen Activation by Group 4 Metal Complexes (pages 3180–3183)

      Yasuhiro Ohki and Michael D. Fryzuk

      Version of Record online: 15 MAR 2007 | DOI: 10.1002/anie.200605245

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      Side-on matters: When dinitrogen bridges two Group 4 metal centers in the side-on binding mode, the reactivity of the N2 unit is enhanced, as evidenced by unprecedented reactions with H2, alkynes, silanes, isocyanates, and now carbon dioxide (see scheme). This Highlight summarizes a number of recent breakthroughs in dinitrogen functionalization by bimetallic Group 4 complexes, culminating with the reaction of CO2 with a dihafium dinitrogen derivative.

  9. Minireview

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
    11. Reviews
    12. Communications
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    1. Viruses as Building Blocks for Materials and Devices (pages 3184–3193)

      Martin Fischlechner and Edwin Donath

      Version of Record online: 9 MAR 2007 | DOI: 10.1002/anie.200603445

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      Useful agents: Viruses as nanoparticles of biological origin offer great opportunities for the design of novel materials. Precise control of their surface chemistry, together with the possibility of genetically engineering the inbuilt genome, turns viruses into a unique tool for the fabrication of multifunctional materials and devices.

  10. Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
    11. Reviews
    12. Communications
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    1. Distal Charge Transport in Peptides (pages 3196–3210)

      Edward W. Schlag, Sheh-Yi Sheu, Dah-Yen Yang, Heinrich L. Selzle and Sheng Hsien Lin

      Version of Record online: 20 MAR 2007 | DOI: 10.1002/anie.200601623

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      Far-reaching consequences: Charge transfer in peptides and proteins often leads to reactivity at a distal point. This process involves very fast facile molecular motions on a time scale of 100 fs, which is unique to peptides. The principal motions are found to be the dihedral motions between neighboring amino acids around the Ramachandran angles (ψ and ϕ in the model peptide; green C, gray H, blue N, red O).

    2. Minimalist Active-Site Redesign: Teaching Old Enzymes New Tricks (pages 3212–3236)

      Miguel D. Toscano, Kenneth J. Woycechowsky and Donald Hilvert

      Version of Record online: 23 APR 2007 | DOI: 10.1002/anie.200604205

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      Reduce, reuse, recycle: Enzymes catalyze a wide variety of chemical reactions. However, suitable enzymatic catalysts are lacking for many useful transformations. New catalytic activities arise from mutations in the active site, suggesting that the pool of existing enzymes can be a promising starting point for the creation of catalysts for nonbiological reactions. Often, a single point mutation is sufficient to endow an enzyme with a new function.

  11. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Reviews
    9. Highlight
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. Coexistence of Ferroelectricity and Ferromagnetism in a Rubidium Manganese Hexacyanoferrate (pages 3238–3241)

      Shin-ichi Ohkoshi, Hiroko Tokoro, Tomoyuki Matsuda, Hitomi Takahashi, Hiroshi Irie and Kazuhito Hashimoto

      Version of Record online: 7 MAR 2007 | DOI: 10.1002/anie.200604452

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      Multiferroic material: RbI0.82MnII0.20MnIII0.80[FeII(CN)6]0.80[FeIII(CN)6]0.14⋅H2O (see picture; MnII red octahedra, FeIII red spheres, MnIII blue octahedra, FeII blue spheres, CN white lines, gaps are Fe vacancies; H2O omitted) displays both ferroelectricity, explained by a mixing of FeII, FeIII, Fe vacancies, MnII, and Jahn–Teller-distorted MnIII centers, and ferromagnetism, caused by a parallel ordering of the magnetic spins of MnIII.

    2. Copper-Promoted Cycloaddition of Diazocarbonyl Compounds and Acetylides (pages 3242–3244)

      Xiangbing Qi and Joseph M. Ready

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200700069

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      HOMO-logous: The copper-mediated cycloaddition of alkynes with diazo carbonyl compounds to give pyrazoles is reminiscent of the copper-catalyzed cycloaddition of alkynes and azides. The formation of the copper acetylide is proposed to narrow the energy gap between the highest occupied molecular orbital (HOMO) of the alkyne and the lowest unoccupied molecular orbital (LUMO) of the diazo compound.

    3. Thermal Cycloaddition Facilitated by Orthogonal π–π Organization through Conformational Transfer in a Swivel-Cruciform Oligo(phenylenevinylene) (pages 3245–3248)

      Leilei Tian, Feng He, Houyu Zhang, Hai Xu, Bing Yang, Chunyu Wang, Ping Lu, Muddasir Hanif, Fei Li, Yuguang Ma and Jiacong Shen

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200603878

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      Extremely mild conditions are required for an intramolecular thermal [2+2] cycloaddition in the swivel-cruciform molecule 1. As a result of the relatively free rotation about the biphenyl bond in 1 (see picture, left) a conformation is accessible in which the alkene bonds of the two ortho substituents are brought into proximity in the required orthogonal arrangement, and the intramolecular cycloadduct (right) is formed at room temperature.

    4. Photochromism of a Methyl Viologen Bismuth(III) Chloride: Structural Variation Before and After UV Irradiation (pages 3249–3251)

      Gang Xu, Guo-Cong Guo, Ming-Sheng Wang, Zhang-Jing Zhang, Wen-Tong Chen and Jin-Shun Huang

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200700122

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      Color scheme: Reversibly photochromic crystals of (MV)Bi2Cl8 (methyl viologen, MV2+: N,N′-dimethyl-4,4′-bipyridinium) show structural variations before and after UV irradiation. Color reversion is accomplished by heating in air (see picture). ([Bi2Cl8]2−) double-octahedral chains serve as electron donors to in situ generated MV2+ dications.

    5. Isoxazole-Directed Pinacol Rearrangement: Stereocontrolled Approach to Angular Stereogenic Centers (pages 3252–3254)

      Keisuke Suzuki, Hiroshi Takikawa, Yoshifumi Hachisu and Jeffrey W. Bode

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200605138

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      Underappreciated and neglected, isoxazoles are extremely good at stabilizing α cations. This ability is exploited in a method for the stereocontrolled introduction of angular substituents as found in polyketide-derived polycyclic natural products, such as 1. In a two-step process, the stereoselective addition of a nucleophile to the ketol 2 is followed by a regio- and stereospecific pinacol rearrangement. Bn=benzyl; R=allyl, aryl, heteroaryl, vinyl.

    6. Asymmetric Tetraprotonation of γ-[(SiO4)W10O32]8− Triggers a Catalytic Epoxidation Reaction: Perspectives in the Assignment of the Active Catalyst (pages 3255–3258)

      Andrea Sartorel, Mauro Carraro, Alessandro Bagno, Gianfranco Scorrano and Marcella Bonchio

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200605120

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      Water in the lagoon: A fast catalytic epoxidation of both terminal and internal double bonds was promoted by the regioselective tetraprotonation of the polyoxometalate γ-[(SiO4)W10O32]8− (see picture), which leads to the localization of two water molecules on the reactive lacunary site. This mechanism was supported by evidence from kinetic, spectroscopic, and computational studies.

    7. Mixed-Valence Li/Fe-Based Metal–Organic Frameworks with Both Reversible Redox and Sorption Properties (pages 3259–3263)

      Gérard Férey, Franck Millange, Mathieu Morcrette, Christian Serre, Marie-Liesse Doublet, Jean-Marc Grenèche and Jean-Marie Tarascon

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200605163

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      There's more to LiFe: When used as an electrode in a lithium half cell, the metal–organic framework [LixFeIIxFeIII1−x(OH)0.8F0.2L] (L=O2CC6H4CO2) shows a reversible redox process around 3.0 V versus Li+/Li0 with interesting capacity retention and rate capability (see voltage profile for a [LixFe(OH)0.8F0.2L] half cell; inset: representation of lithium insertion upon oxidation to Li+).

    8. High-Yield Synthesis of Single-Crystalline Gold Nano-octahedra (pages 3264–3268)

      Cuncheng Li, Kevin L. Shuford, Q.-Han Park, Weiping Cai, Yue Li, Eun Je Lee and Sung Oh Cho

      Version of Record online: 23 MAR 2007 | DOI: 10.1002/anie.200604167

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      Pieces of eight: Single-crystalline Au nano-octahedra with well-defined shape and tunable size can be synthesized by a modified polyol process. The octahedral Au nanocrystals have sharp corners and display optical properties that are sensitive to the crystal sizes and the truncation of the tips.

    9. In Situ Synthesis and Assembly of Gold Nanoparticles Embedded in Glass-Forming Liquid Crystals (pages 3269–3274)

      V. Ajay Mallia, Praveen Kumar Vemula, George John, Ashavani Kumar and Pulickel M. Ajayan

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200604218

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      Going through a phase: By using simple glass-forming liquid crystals (LCs) in situ, gold nanoparticles (GNPs) were synthesized shape selectively and assembled spontaneously to generate ribbonlike patterns that are replicas of native LC organizations. This remarkable approach afforded boomerang- and V-shaped GNPs.

    10. Cross-Linking Yield Variation of a Potent Matrix Metalloproteinase Photoaffinity Probe and Consequences for Functional Proteomics (pages 3275–3277)

      Arnaud David, David Steer, Sarah Bregant, Laurent Devel, Anastasios Makaritis, Fabrice Beau, Athanasios Yiotakis and Vincent Dive

      Version of Record online: 23 MAR 2007 | DOI: 10.1002/anie.200604408

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      Probing proteinases: A radioactive photoaffinity probe exhibiting subnanomolar potency towards matrix metalloproteinases (MMPs) has been developed (see structure). High sensitivity in the detection of particular MMPs has been obtained; however, high variation in the cross-linking yield of MMPs with this probe may limit its ability to detect all MMP active forms in biological samples. This result suggests that a cocktail of optimized probes should be developed.

    11. Assembly of Metal–Organic Frameworks (MOFs) Based on Indium-Trimer Building Blocks: A Porous MOF with soc Topology and High Hydrogen Storage (pages 3278–3283)

      Yunling Liu, Jarrod F. Eubank, Amy J. Cairns, Juergen Eckert, Victor Ch. Kravtsov, Ryan Luebke and Mohamed Eddaoudi

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200604306

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      The key to soc-cess: The trimer building block [In3O(CO2)6] and a tetracarboxylate organic linker assemble into a novel porous metal–organic framework (see picture; In green, C gray, N blue, O red; cavity: yellow sphere) having an unprecedented soc topology (soc=square–octahedron) and high H2 uptake.

    12. Fiber Formation by Highly CO2-Soluble Bisureas Containing Peracetylated Carbohydrate Groups (pages 3284–3287)

      Ik-Hyeon Paik, Deepak Tapriyal, Robert M. Enick and Andrew D. Hamilton

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200604844

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      Like dissolves like: Bisureas containing environmentally benign CO2-philic groups derived from peracetylated gluconic acid dissolve in supercritical CO2 at 298 K and 62 MPa. Upon depressurization of the CO2, the initially powdery bisureas (left image) form microfibrillar foams (right image).

    13. Montmorillonite-Entrapped Sub-nanoordered Pd Clusters as a Heterogeneous Catalyst for Allylic Substitution Reactions (pages 3288–3290)

      Takato Mitsudome, Kenta Nose, Kohsuke Mori, Tomoo Mizugaki, Kohki Ebitani, Koichiro Jitsukawa and Kiyotomi Kaneda

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200604644

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      Caught making a change: Stable sub-nanoordered Pd clusters within the interlayer spaces of montmorillonite efficiently catalyze heterogeneous allylic substitution reactions in which the coordinatively unsaturated Pd atoms enable facile formation of π-allylpalladium intermediates (see scheme). The catalyst is reusable without any loss of activity or selectivity.

    14. Palladium-Catalyzed Three-Component Synthesis of 3-(Diarylmethylene)oxindoles through a Domino Sonagashira/Carbopalladation/C[BOND]H Activation/C[BOND]C Bond-Forming Sequence (pages 3291–3295)

      Artur Pinto, Luc Neuville and Jieping Zhu

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200605192

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      3-3-1 Formation: [Pd(PPh3)4]/CuI serves as an efficient catalyst for the reaction of three readily available starting materials to give 3-(diarylmethylene)indolin-2-ones 3 through a sequence of intermolecular Sonagashira reaction/intermolecular carbopalladation/C[BOND]H activation/C[BOND]C bond formation (see scheme). Three C[BOND]C bonds are thereby formed as a result of three distinct catalytic cycles with one catalyst. DMF=N,N-dimethylformamide.

    15. Rhenium- and Gold-Catalyzed Coupling of Aromatic Aldehydes with Trimethyl(phenylethynyl)silane: Synthesis of Diethynylmethanes (pages 3296–3299)

      Yoichiro Kuninobu, Eri Ishii and Kazuhiko Takai

      Version of Record online: 23 MAR 2007 | DOI: 10.1002/anie.200700183

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      Very couply! Coupling reactions of propargyl or benzyl alcohols with allyl- or alkynylsilanes proceed efficiently using [{ReBr(CO)3(thf)}2] as catalyst. Additionally, diethynylmethane derivatives were obtained by the reaction of aromatic aldehydes with trimethyl(phenylethynyl)silane in the presence of both the rhenium complex and AuCl (see scheme).

    16. Intramolecular Spin Transfer in a Spiro-Fused Bis(triarylamine) (pages 3300–3303)

      Yasukazu Hirao, Masashi Urabe, Akihiro Ito and Kazuyoshi Tanaka

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200603360

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      Intriguing electronic properties were observed for the radical cation 1+ of a spiro-fused bis(triarylamine). In a new example of intramolecular spin transfer (IST) in organic intervalence systems connected by a non-π-conjugated bridging unit, the as-prepared radical cation 1+ exhibited thermally activated IST. Furthermore, it was found that 1+ decomposes slowly to the tri-p-anisylamine radical cation.

    17. Hopping of Thiolate Ligands between Au Nanoparticles Revealed by EPR Spectroscopy (pages 3304–3307)

      Mouna Zachary and Victor Chechik

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200604070

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      Jump up and down: EPR spectroscopy was used to monitor hopping of spin-labeled ligands between Au nanoparticles. The slow interparticle exchange affects approximately 20 % of the binding sites on the nanoparticle surface. The kinetic analysis showed that this reaction follows a dissociative mechanism with ligand desorption in the rate-determining step. EPR=electron paramagnetic resonance.

    18. Inhibition of Lipid A Stimulated Activation of Human Dendritic Cells and Macrophages by Amino and Hydroxylamino Monosaccharides (pages 3308–3312)

      Francesco Peri, Francesca Granucci, Barbara Costa, Ivan Zanoni, Chiara Marinzi and Francesco Nicotra

      Version of Record online: 23 MAR 2007 | DOI: 10.1002/anie.200604932

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      Innovative mimics of lipid A were synthesized and shown to efficiently inhibit lipid A induced cytokine production in human dendritic cells and macrophages. These compounds, which consist of a D-glucose unit functionalized with an amine, ammonium, or hydroxylamine group and a five-membered ring at C6 (see structures) are promising leads for antisepsis-drug development owing to their lack of toxicity and their selectivity for the TLR4 receptor.

    19. Reverse Micelles in Carbon Dioxide with Ionic-Liquid Domains (pages 3313–3315)

      Jiehua Liu, Siqing Cheng, Jianling Zhang, Xiaoying Feng, Xiangang Fu and Buxing Han

      Version of Record online: 20 MAR 2007 | DOI: 10.1002/anie.200605019

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      The fluorinated surfactantN-ethyl perfluorooctylsulfonamide can form reverse micelles with an ionic liquid as the inner component in supercritical CO2. These reverse micelles can solubilize salts and gold nanoparticles can be formed with HAuCl4 (see TEM image). The micellar systems may combine some of the advantages of supercritical CO2 and ionic liquids as solvents with benefits for potential applications.

    20. Stereospecific Alkyne Reduction: Novel Activity of Old Yellow Enzymes (pages 3316–3318)

      André Müller, Rainer Stürmer, Bernhard Hauer and Bettina Rosche

      Version of Record online: 23 MAR 2007 | DOI: 10.1002/anie.200605179

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      Old enzyme, new trick: An environmentally sustainable alternative for the regio- and stereoselective reduction of the alkyne bond is the biotransformation by “Old Yellow Enzyme” (OYE). This “old” enzyme, first isolated in 1932, catalyzes the trans-selective hydrogenation of the carbon–carbon triple bond under mild conditions.

    21. Fabrication of Au Nanowires of Uniform Length and Diameter Using a Monodisperse and Rigid Biomolecular Template: Collagen-like Triple Helix (pages 3319–3322)

      Hanying Bai, Ke Xu, Yujia Xu and Hiroshi Matsui

      Version of Record online: 13 MAR 2007 | DOI: 10.1002/anie.200605213

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      Collagen implants: The unique molecular properties of the collagen-like triple helix, generated and amplified by recombinant technology, enable the formation of rigid rod-shaped molecules that are ideally suited as biomolecular-nanowire templates. Biomineralization of Au on the triple helix (see picture) produces monodisperse Au nanowires with dimensions 4x40 nm2.

    22. An Efficient, Facile, and General Synthesis of 1H-Indazoles by 1,3-Dipolar Cycloaddition of Arynes with Diazomethane Derivatives (pages 3323–3325)

      Tienan Jin and Yoshinori Yamamoto

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200700101

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      Take your pick: Both N-unsubstituted and 1-aryl 1H-indazoles are available in good to high yields through the [3+2] cycloaddition of benzynes derived from o-silylaryl triflates with diazomethane derivatives (see scheme). In the presence of KF/[18]crown-6, the N-unsubstituted 1H-indazole is formed, whereas the 1-arylated product is obtained regioselectively with CsF and an excess of the triflate.

    23. Stereoselective Synthesis of 2,4,6-Trisubstituted Tetrahydropyrans by the Use of Cyclopropanols as Homoenols (pages 3326–3328)

      Hyung Goo Lee, Ivan L. Lysenko and Jin Kun Cha

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200700172

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      A convenient method for preparing all-cis 2,4,6-trisubstituted tetrahydropyrans and the corresponding 2,6-trans isomers has been developed. This trimethylsilyl triflate mediated coupling of cyclopropanols with a 2-hydroxyalkyl side chain to aldehydes (see scheme) is also suitable for the coupling of two large subunits to generate structural complexity in a rapid and highly convergent manner.

    24. Catalytic Asymmetric Conjugate Reduction of β,β-Disubstituted α,β-Unsaturated Sulfones (pages 3329–3332)

      Tomás Llamas, Ramón Gómez Arrayás and Juan C. Carretero

      Version of Record online: 23 MAR 2007 | DOI: 10.1002/anie.200700296

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      Access to a chiral sulfone: Asymmetric conjugate reduction of β,β-disubstituted α,β-unsaturated 2-pyridylsulfones with silanes under CuI/binap catalysis provides chiral sulfones with excellent chemical yields and enantioselectivities (see scheme). These enantioenriched 2-pyridylsulfones are versatile intermediates in the preparation of a wide variety of functionalized chiral compounds. binap=2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl.

    25. Photoisomerizable Heterodienes Derived from a Phosphine Borane (pages 3333–3336)

      Magnus W. P. Bebbington, Sébastien Bontemps, Ghenwa Bouhadir and Didier Bourissou

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200605078

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      Stable relations: Reaction of phenylazide with a phosphine borane derivative gives rise to an intramolecularly stabilized phosphazide 1 (R=iPr, R′=mesityl) that undergoes an unprecedented photoisomerization process associated with a change from an Nα[RIGHTWARDS ARROW]B to an Nβ[RIGHTWARDS ARROW]B interaction (see scheme). The generality and possible reversibility of such phenomena are demonstrated with the related phosphazine adduct 2.

    26. Metallo-ROS in Alzheimer's Disease: Oxidation of Neurotransmitters by CuII-β-Amyloid and Neuropathology of the Disease (pages 3337–3341)

      Giordano F. Z. da Silva and Li-June Ming

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200604421

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      A clear mind: The CuII–β-amyloid (Aβ) complex has been shown to exhibit enzyme-like metal-centered oxidative and hydroxylation catalyses. Metal-centered oxidation of various neurotransmitters by CuAβ under biomimetic conditions has verified the bio-relevance of the metal-centered catalyses and is expected to provide a chemical basis for the better understanding of the etiology of Alzheimer's disease. ROS=reactive oxygen species.

    27. Self-Patterning of Hydrophobic Materials into Highly Ordered Honeycomb Nanostructures at the Air/Water Interface (pages 3342–3345)

      Dawei Fan, Xiangfeng Jia, Peiqin Tang, Jingcheng Hao and Tianbo Liu

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200604180

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      Patterns of behavior: Complexes of the cluster {Mo72Fe30} and the surfactant dioctadecyldimethylammonium chloride (DODMACl) produced in CHCl3 form patterns with a honeycomb structure at the air/water interface after evaporation of the solvent (see SEM image). The concentration of DODMACl in CHCl3 is critical to whether the {Mo72Fe30} macroanions remain in the aqueous or CHCl3 phase.

    28. Conversion of a Disilenide into a Silene: Silyl-Anion-Substituted Silene by a Sila-Peterson-Type Reaction from an sp2-Type Silyl Anion (pages 3346–3348)

      Shigeyoshi Inoue, Masaaki Ichinohe and Akira Sekiguchi

      Version of Record online: 16 FEB 2007 | DOI: 10.1002/anie.200605140

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      From Si[DOUBLE BOND]Si to Si[DOUBLE BOND]C: Silyl-anion-substituted silene 2 was synthesized as air- and moisture-sensitive yellow crystals by the reaction of the disilenyl lithium derivative 1 with adamantanone (see scheme). The physical properties of 2 suggest a silene-type structure containing a silicon–carbon double bond, with no contribution from 1,2-disilaallyl-anion-type and disilene-type structures.

    29. Stable Cyclic Silenes from Reaction of Disilenides with Carboxylic Acid Chlorides (pages 3349–3352)

      Iulia Bejan, Denis Güclü, Shigeyoshi Inoue, Masaaki Ichinohe, Akira Sekiguchi and David Scheschkewitz

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200700067

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      Pyramidal silicon centers within the Si[DOUBLE BOND]C bond are the most prominent feature of the first cyclic silenes stable at room temperature, as exhibited by X-ray diffraction (see structure) and calculations. They are quantitatively formed by reaction of lithium disilenides, disila analogues of vinyllithium compounds, with acid chlorides, and are relatively inert, for example, towards the addition of MeOH.

    30. Triethyl Phosphite Mediated Domino Reaction: Direct Conversion of ω-Nitroalkenes Into N-Heterocycles (pages 3353–3355)

      Elena Merişor, Jürgen Conrad, Iris Klaiber, Sabine Mika and Uwe Beifuss

      Version of Record online: 20 MAR 2007 | DOI: 10.1002/anie.200605260

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      Dominos on cycles: Several N-heterocycles, such as 3,4-dihydro-2H-1,4-benzoxazines, 1,2,3,4-tetrahydroquinoxalines, and 1,2,3,4-tetrahydroquinolines, can be obtained through a novel domino reaction mediated by triethyl phosphite under the influence of microwave irradiation (MW) in a single step from nitroaromatic compounds (see scheme).

    31. Cell-Free Transcription/Translation from PCR-Amplified DNA for High-Throughput NMR Studies (pages 3356–3358)

      Peter S. C. Wu, Kiyoshi Ozawa, Siew P. Lim, Subhash G. Vasudevan, Nicholas E. Dixon and Gottfried Otting

      Version of Record online: 22 MAR 2007 | DOI: 10.1002/anie.200605237

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      Quick and clean: Excellent protein yields in cell-free protein synthesis can be obtained by using polymerase chain reaction (PCR) amplified DNA templates, provided that the templates are designed for cyclization. This eliminates time-consuming cloning steps and allows one to go from complementary DNA to the protein NMR spectrum in 24 h.

    32. Matrix Effect on Motional Coupling and Long-Range Transport of Cations in Zeolites (pages 3359–3362)

      Edgar Jordan, Dirk Wilmer and Hubert Koller

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200605049

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      Different cation conduction mechanisms in the zeolites cancrinite and sodalite were revealed by the combination of impedance and solid-state NMR spectroscopies. Cancrinite is a one-dimensional conductor as a result of its channels, which are made up of stacked 12-rings, whereas the cation transport in sodalite takes place in three dimensions.

    33. Direct Monitoring of Formation and Dissociation of Individual Metal Complexes by Single-Molecule Fluorescence Spectroscopy (pages 3363–3366)

      Alexander Kiel, Janos Kovacs, Andriy Mokhir, Roland Krämer and Dirk-Peter Herten

      Version of Record online: 2 APR 2007 | DOI: 10.1002/anie.200604965

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      For the observation of the coordination states of individual copper(II) chelate complexes in thermodynamic equilibrium (see picture; TMR=tetramethylrhodamine), single-molecule fluorescence spectroscopy can be used. Application of time-resolved single-molecule spectroscopy opens new prospects for the investigation of reactions in the coordination sphere of metal complexes.

      Corrected by:

      Corrigendum: Direct Monitoring of Formation and Dissociation of Individual Metal Complexes by Single-Molecule Fluorescence Spectroscopy

      Vol. 46, Issue 27, 5049, Version of Record online: 22 JUN 2007

    34. Prediction of Perception: Probing the hOR17-4 Olfactory Receptor Model with Silicon Analogues of Bourgeonal and Lilial (pages 3367–3371)

      Leszek Doszczak, Philip Kraft, Hans-Peter Weber, Rüdiger Bertermann, Annika Triller, Hanns Hatt and Reinhold Tacke

      Version of Record online: 2 APR 2007 | DOI: 10.1002/anie.200605002

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      Sense and sensibility: Silicon analogues of the lily-of-the-valley odorants lilial and bourgeonal demonstrate that the electronic surface structure determines the interaction of an odorant with its olfactory receptor. The subtle changes in the stereoelectronic properties enable a comparison of in vivo, in vitro, and in silico data. Odor thresholds, as well as the swimming behavior of sperm cells, correlate well with the binding energies obtained from a computational model of the hOR17-4 receptor.

    35. Unexpected Structures of Aluminum Oxide Clusters in the Gas Phase (pages 3372–3375)

      Marek Sierka, Jens Döbler, Joachim Sauer, Gabriele Santambrogio, Mathias Brümmer, Ludger Wöste, Ewald Janssens, Gerard Meijer and Knut. R. Asmis

      Version of Record online: 27 MAR 2007 | DOI: 10.1002/anie.200604823

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      No family resemblance: IR photodissociation experiments and DFT optimizations implementing a genetic algorithm suggest that small aluminum oxide clusters have unusual structures in the gas phase. For example, the structure proposed for [(Al2O3)4]+ (see picture; Al black, O gray) has no features in common with bulk alumina phases.

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