Angewandte Chemie International Edition

Cover image for Vol. 49 Issue 36

August 23, 2010

Volume 49, Issue 36

Pages 6229–6457

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. Cover Picture: [An(H2O)9](CF3SO3)3 (An=U–Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory (Angew. Chem. Int. Ed. 36/2010) (page 6229)

      Christos Apostolidis, Bernd Schimmelpfennig, Nicola Magnani, Patric Lindqvist-Reis, Olaf Walter, Richard Sykora, Alfred Morgenstern, Eric Colineau, Roberto Caciuffo, Reinhardt Klenze, Richard G. Haire, Jean Rebizant, Frank Bruchertseifer and Thomas Fanghänel

      Article first published online: 22 JUN 2010 | DOI: 10.1002/anie.201003226

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      Easily prepared and highly soluble actinide(III) salts are of great interest as precursors for actinide complex chemistry. In their Communication on page 6343 ff., P. Lindqvist-Reis and co-workers report how [An(H2O)9]3+(CF3SO3)3 (An=U–Cm, Cf) can be obtained directly from aqueous solution, a remarkable result for the UIII and NpIII salts given their extremely oxidation-sensitive nature. They also discuss the use of these salts as models for hydrated An3+ ions in solution.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. Inside Cover: Innovative Inorganic–Organic Nanohybrid Materials: Coupling Quantum Dots to Carbon Nanotubes (Angew. Chem. Int. Ed. 36/2010) (page 6230)

      Christian Schulz-Drost, Vito Sgobba, Christina Gerhards, Susanne Leubner, Rafael M. Krick Calderon, Andrés Ruland and Dirk M. Guldi

      Article first published online: 22 JUN 2010 | DOI: 10.1002/anie.201003293

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      Photoactive inorganic–organic nanohybrids are constructed from CdTe quantum dots (QDs) and single-walled carbon nanotubes (SWNTs). In their Communication on page 6425 ff. D. M. Guldi and co-workers report that the introduction of surface stabilizers to QDs facilitates both the covalent attachment of a pyrene group and the anchoring onto the SWNTs. Complementary luminescence and ultrafast transient absorption analyses indicate the formation of a charge-separated state; this paves the way for the successful integration into photovoltaic devices.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    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. Author Profile
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. You have free access to this content
      Corrigendum: Strong Two-Photon Excited Fluorescence and Stimulated Emission from an Organic Single Crystal of an Oligo(Phenylene Vinylene) (page 6243)

      Fei Gao, Qing Liao, Zhen-Zhen Xu, Yong-Hao Yue, Qiang Wang, Hao-Li Zhang and Hong-Bing Fu

      Article first published online: 19 AUG 2010 | DOI: 10.1002/anie.201090113

      This article corrects:
  5. News

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. José Barluenga (pages 6250–6252)

      Article first published online: 27 JUL 2010 | DOI: 10.1002/anie.201002717

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      “If I could be anyone for a day, I would be Christopher Columbus at the time he reached America for the first time. If I were not scientist, I would be a veterinary surgeon …” This and more about José Barluenga can be found on page 6250.

  7. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. High Energy Materials. Propellants, Explosives and Pyrotechnics. By Jai Prakash Agrawal. (page 6253)

      Joerg Stierstorfer and Thomas M. Klapötke

      Article first published online: 4 AUG 2010 | DOI: 10.1002/anie.201003666

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      Wiley-VCH, Weinheim 2010. 498 pp., hardcover € 159.00.—ISBN 978-3527326105

  8. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. Homogeneous Catalysis

      State-of-the-Art Catalysts for Hydrogenation of Carbon Dioxide (pages 6254–6257)

      Christopher Federsel, Ralf Jackstell and Matthias Beller

      Article first published online: 27 JUL 2010 | DOI: 10.1002/anie.201000533

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      Efficiency is key: Nozaki and co-workers managed to achieve very high turnover numbers for the reduction of carbon dioxide to formic acid using an active Iridium(III)–pincer complex 1. This Highlight compares Nozaki's work to previously reported state-of-the-art catalysts.

    2. RNA Interference

      Proof of RNA Interference in Humans after Systemic Delivery of siRNAs (pages 6258–6259)

      Jens Kurreck

      Article first published online: 20 JUL 2010 | DOI: 10.1002/anie.201002867

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      Great hope is placed in the use of RNA interference in the development of novel therapeutics. Recently, small interfering RNAs (siRNAs) were delivered to tumor cells of melanoma patients by nanoparticles consisting of a cyclodextrin polymer, and polyethylene glycol coupled to adamantane and transferrin (see picture). It was demonstrated that the target mRNA in the patients was degraded by a specific RNA interference mechanism.

  9. Minireview

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

      BioMOFs: Metal–Organic Frameworks for Biological and Medical Applications (pages 6260–6266)

      Alistair C. McKinlay, Russell E. Morris, Patricia Horcajada, Gérard Férey, Ruxandra Gref, Patrick Couvreur and Christian Serre

      Article first published online: 22 JUL 2010 | DOI: 10.1002/anie.201000048

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      New packaging: A tremendous number of drugs have been developed but not applied further owing to poor bioavailability. To solve this problem, stable nontoxic metal–organic frameworks have been developed as drug-delivery vehicles and even as bioactive species in their own right.

  10. Reviews

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

      Microfluidics in Inorganic Chemistry (pages 6268–6286)

      Ali Abou-Hassan, Olivier Sandre and Valérie Cabuil

      Article first published online: 2 AUG 2010 | DOI: 10.1002/anie.200904285

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      Even flow: Microreactors are a new and convenient tool for liquid–liquid extraction and the optimization of inorganic chemical reactions. Fundamental studies have been carried out by this technique to understand the phenomena of nucleation and growth during chemical processes. Up-to-date data is provided, and the role of microfluidics in the field of inorganic chemistry is discussed.

    2. Drug Delivery

      Poly(ethylene glycol) in Drug Delivery: Pros and Cons as Well as Potential Alternatives (pages 6288–6308)

      Katrin Knop, Richard Hoogenboom, Dagmar Fischer and Ulrich S. Schubert

      Article first published online: 20 JUL 2010 | DOI: 10.1002/anie.200902672

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      All-round talent PEG? Poly(ethylene glycol) (PEG) surrounds us in our everyday lives and, particularly in drug-delivery applications, counts as a gold standard. This omnipresent polymer is explored from different angles—advantages and disadvantages are evaluated together with alternative polymers.

  11. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Minireview
    11. Reviews
    12. Communications
    13. Preview
    1. DNA Structures

      DNA and RNA in Anhydrous Media: Duplex, Triplex, and G-Quadruplex Secondary Structures in a Deep Eutectic Solvent (pages 6310–6314)

      Irena Mamajanov, Aaron E. Engelhart, Heather D. Bean and Nicholas V. Hud

      Article first published online: 12 JUL 2010 | DOI: 10.1002/anie.201001561

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      Hold the water! Deep-eutectic solvents (DESs) are nonvolatile media suitable for a wide range of chemical reactions. The discovery that nucleic acids can form duplex, triplex, and G-quadruplex structures (which in some cases differ from those adopted in aqueous media) in a water-free DES (see picture) opens the enticing possibility that catalytic nucleic acids and enzyme–nucleic acid complexes could also be used in these solvents.

    2. N-Heterocyclic Carbene Complexes

      Reduction of a Chelating Bis(NHC) Palladium(II) Complex to [{μ-bis(NHC)}2Pd2H]+: A Terminal Hydride in a Binuclear Palladium(I) Species Formed under Catalytically Relevant Conditions (pages 6315–6318)

      Peter D. W. Boyd, Alison J. Edwards, Michael G. Gardiner, Curtis C. Ho, Marie-Hélène Lemée-Cailleau, David S. McGuinness, Anung Riapanitra, Jonathan W. Steed, Damien N. Stringer and Brian F. Yates

      Article first published online: 19 AUG 2010 | DOI: 10.1002/anie.201003177

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      Half-way house: The first palladium(I) N-heterocyclic carbene complex has been isolated in high yield by the base-assisted reduction of a palladium(II) precursor. The location of the unique terminal hydride (see picture; PdI cyan, H white, N blue) was established by neutron crystal structure determination, and the solution fluxional behavior of the complex was explored.

    3. Field-Effect Transistors

      High-Performance Langmuir–Blodgett Monolayer Transistors with High Responsivity (pages 6319–6323)

      Yang Cao, Zhongming Wei, Song Liu, Lin Gan, Xuefeng Guo, Wei Xu, Michael L. Steigerwald, Zhongfan Liu and Daoben Zhu

      Article first published online: 14 JUL 2010 | DOI: 10.1002/anie.201001683

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      Molecular field-effect transistors with bulk-like carrier mobility (as high as 0.04 cm2 V−1 s−1), high on/off current ratios (over 106), and high responsivity are formed by the integration of Langmuir–Blodgett techniques with sophisticated micro/nanofabrication. The transistors are formed from self-assembled uniform monolayers of copper phthalocyanine (CuPc) semiconductors and single-layer graphene as planar contacts.

    4. Isomerization

      Tuning the cis/trans Conformer Ratio of Xaa–Pro Amide Bonds by Intramolecular Hydrogen Bonds: The Effect on PPII Helix Stability (pages 6324–6327)

      Michael Kuemin, Yvonne A. Nagel, Sabine Schweizer, Fabien W. Monnard, Christian Ochsenfeld and Helma Wennemers

      Article first published online: 21 JUL 2010 | DOI: 10.1002/anie.201001851

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      The attraction of H-bonding: Proline derivatives with a C4-endo ring pucker and a preference for the trans amide conformer are introduced as building blocks to tune the cis/trans amide conformer ratio in Xaa-Pro bonds within peptides. Noncovalent interactions, such as hydrogen bonding between the substituent at C4 of the proline ring and the amide backbone are key for favoring or disfavoring the trans conformer (see picture).

    5. Nanoparticles

      Low-Symmetry Iron Oxide Nanocrystals Bound by High-Index Facets (pages 6328–6332)

      Jingzhou Yin, Zhinan Yu, Feng Gao, Jianjun Wang, Huan Pang and Qingyi Lu

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201002557

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      Just the shape of it: Tetrakaidecahedral (see picture, left) and oblique parallelepiped (right) α-Fe2O3 polyhedra with exposed high-index facets were obtained in high yield. Magnetic studies show that these two forms of iron oxide have distinct magnetic properties owing to their different shapes and different exposed high-indexed facets.

    6. Bowl-Shaped Radicals

      A Bowl-Shaped ortho-Semiquinone Radical Anion: Quantitative Evaluation of the Dynamic Behavior of Structural and Electronic Features (pages 6333–6337)

      Akira Ueda, Kanako Ogasawara, Shinsuke Nishida, Tomoaki Ise, Tomohiro Yoshino, Shigeaki Nakazawa, Kazunobu Sato, Takeji Takui, Kazuhiro Nakasuji and Yasushi Morita

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201002626

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      Dish it up: The first bowl-shaped o-semiquinone radical with a sodium cation (see picture) has been synthesized, and its 3D spin- and charge-delocalized nature and redox properties have been evaluated. The concave–convex dynamic behavior of the ion pair was also investigated in a quantitative manner using ESR and ENDOR/TRIPLE measurements and sophisticated DFT calculations.

    7. Self-Assembly

      Regulation of a Real-Time Self-Healing Process in Organogel Tissues by Molecular Adhesives (pages 6338–6342)

      Pritam Mukhopadhyay, Norifumi Fujita, Akihiko Takada, Takanori Kishida, Michihiro Shirakawa and Seiji Shinkai

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201001382

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      Say cheeeese! The thixotropic processes that occur in a naphthalenediimide-based organogel can be imaged in real time by TEM and AFM (see picture). The self-assembled 1D fibers disintegrate under mechanical stress and undergo a self-healing process during a resting time to reconstitute the 1D fibers.

    8. Actinide Chemistry

      [An(H2O)9](CF3SO3)3 (An=U–Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory (pages 6343–6347)

      Christos Apostolidis, Bernd Schimmelpfennig, Nicola Magnani, Patric Lindqvist-Reis, Olaf Walter, Richard Sykora, Alfred Morgenstern, Eric Colineau, Roberto Caciuffo, Reinhardt Klenze, Richard G. Haire, Jean Rebizant, Frank Bruchertseifer and Thomas Fanghänel

      Article first published online: 23 JUN 2010 | DOI: 10.1002/anie.201001077

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      Lanthanide-like: X-ray diffraction and density functional theory studies show that [An(H2O)9]3+ ions of the actinides U3+–Cf3+ in crystals of their triflate salts have the same structure and electrostatic bonding as their lanthanide counterparts La3+–Eu3+. Moreover, the nine-coordinate geometry is essentially preserved in solution for the lighter elements (see picture).

    9. CO2 Adsorption

      A Shape-Persistent Organic Molecular Cage with High Selectivity for the Adsorption of CO2 over N2 (pages 6348–6351)

      Yinghua Jin, Bret A. Voss, Richard D. Noble and Wei Zhang

      Article first published online: 21 JUL 2010 | DOI: 10.1002/anie.201001517

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      Carbon capture in an organic cage: A shape-persistent, organic prismatic molecular cage (see structure) was synthesized in one step and high yield from readily accessible starting materials through dynamic covalent chemistry. The resulting cage molecule exhibited high selectivity for the adsorption of CO2 over N2 and thus shows promise as a carbon-capture material.

    10. Single-Molecule Magnets

      Coupling Dy3 Triangles Enhances Their Slow Magnetic Relaxation (pages 6352–6356)

      Ian J. Hewitt, Jinkui Tang, N. T. Madhu, Christopher E. Anson, Yanhua Lan, Javier Luzon, Mael Etienne, Roberta Sessoli and Annie K. Powell

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201002691

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      Two's company: Coupling two Dy3 triangles to give Dy6 (see picture; Dy blue, Cl green, O red) leads to a dramatic enhancement of the barrier height to magnetization reversal. The enhancement has been rationalized by single-crystal magnetometry measurements and ab initio calculations.

    11. Metal–Metal Interactions

      A Mercury[RIGHTWARDS ARROW]Antimony Interaction (pages 6357–6360)

      Tzu-Pin Lin, Casey R. Wade, Lisa M. Pérez and François P. Gabbaï

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201002995

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      Fatal attraction: As a result of a unique iodide push–stibonium pull effect, the dinuclear complex (see picture) displays an unprecedented Hg[RIGHTWARDS ARROW]Sb interaction. The existence of this interaction was examined experimentally and theoretically.

    12. Submicrometer Spheres

      Selective Pulsed Heating for the Synthesis of Semiconductor and Metal Submicrometer Spheres (pages 6361–6364)

      Hongqiang Wang, Alexander Pyatenko, Kenji Kawaguchi, Xiangyou Li, Zaneta Swiatkowska-Warkocka and Naoto Koshizaki

      Article first published online: 2 AUG 2010 | DOI: 10.1002/anie.201002963

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      Canned heat: Inhibition of anisotropic crystal growth is critical for synthesizing semiconductor/metal spheres, but it is kinetically difficult to achieve in methods relying on conventional heating. Selective heating of colloidal nanoparticles by pulsed laser irradiation allows size-tailored semiconductor and metal submicrometer spheres to be synthesized.

    13. Copper Catalysis

      Copper-Promoted and Copper-Catalyzed Intermolecular Alkene Diamination (pages 6365–6368)

      Fatima C. Sequeira, Benjamin W. Turnpenny and Sherry R. Chemler

      Article first published online: 29 JUL 2010 | DOI: 10.1002/anie.201003499

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      Simply copper: Copper(II)-promoted intra- and intermolecular olefin diaminations bring together two differently functionalized amines into a vicinal relationship. High diastereoselectivity was obtained with chiral alkenes and results of the asymmetric catalysis are promising.

    14. Synthetic Methods

      A Direct Entry to Substituted N-Methoxyamines from N-Methoxyamides via N-Oxyiminium Ions (pages 6369–6372)

      Kenji Shirokane, Yusuke Kurosaki, Takaaki Sato and Noritaka Chida

      Article first published online: 29 JUL 2010 | DOI: 10.1002/anie.201001127

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      Take the direct path: Sequential nucleophilic addition of N-methoxyamides using DIBAL and organometallic reagents provided substituted N-methoxyamines in one pot via five-membered chelated intermediates (see scheme, DIBAL=diisobutylaluminum hydride). The reaction allows functionalization of acyclic amides and macrolactams without a preactivation step, which is generally required for inert amide carbonyl groups.

    15. Stereoselectivity

      Enamine versus Oxazolidinone: What Controls Stereoselectivity in Proline-Catalyzed Asymmetric Aldol Reactions? (pages 6373–6377)

      Akhilesh K. Sharma and Raghavan B. Sunoj

      Article first published online: 21 JUL 2010 | DOI: 10.1002/anie.201001588

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      Take the right path: Comparison of the oxazolidinone and enamine pathways in enantioselective aldol reactions by using density functional and ab initio transition states reveals that the oxazolidinone route does not provide the correct stereochemical outcome (see picture), whereas the enamine pathway predicts the correct stereoselectivity.

    16. Asymmetric Amplification

      Asymmetric Amplification in Phosphoric Acid Catalyzed Reactions (pages 6378–6381)

      Nan Li, Xiao-Hua Chen, Shi-Ming Zhou, Shi-Wei Luo, Jin Song, Lei Ren and Liu-Zhu Gong

      Article first published online: 22 JUL 2010 | DOI: 10.1002/anie.201001723

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      Aneeamp: Asymmetric amplification in reactions catalyzed by phosphoric acids arose from the formation of less soluble supramolecular structures (see scheme; O red, P yellow, C gray, H white) of the racemic phosphoric acids that participate in hydrogen bonds with the crystalline water molecules. The finding shows that highly enantioselective reactions can be observed by using non-optically pure phosphoric acids.

    17. Catalytic Intermediates

      Isolation of Catalytic Intermediates in Hydroamination Reactions: Insertion of Internal Alkynes into a Zirconium–Amido Bond (pages 6382–6386)

      David C. Leitch, Courtney S. Turner and Laurel L. Schafer

      Article first published online: 21 JUL 2010 | DOI: 10.1002/anie.201001927

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      Insert alkyne to continue: Reaction of a bis(ureate) zirconium dimethylamido complex with electron-rich alkynes leads to vinylamine insertion products (see scheme). The insertion of C[BOND]C unsaturated bonds into M[BOND]N bonds is proposed as a key step in lanthanide chemistry and, more recently, hydroamination reactions catalyzed by Group 4 metals. For the first time, these elusive intermediates have been isolated and characterized on a catalytically active d0-metal center.

    18. Cross-Coupling

      Zinc Chloride Enhanced Arylations of Secondary Benzyl Trifluoroacetates in the Presence of β-Hydrogen Atoms (pages 6387–6390)

      Hui Duan, Lingkui Meng, Denghui Bao, Heng Zhang, Yao Li and Aiwen Lei

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002116

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      Zinc or swim: Arylation of benzyl trifluoroacetates with arylzinc reagents in the presence of β-hydrogen atoms were realized under mild conditions. Both electron-rich and electron-deficient arene substrates were successfully arylated. This arylation method could offer a very versatile synthetic route to access a series of diversity-oriented diarylalkane motifs. TFA = trifluoroacetyl.

    19. Cyclic Imides

      Synthesis of Cyclic Imides from Simple Diols (pages 6391–6395)

      Jian Zhang, Muthaiah Senthilkumar, Subhash Chandra Ghosh and Soon Hyeok Hong

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201002136

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      There′s something imide so strong: Cyclic imides were synthesized from simple diols with primary amines in a single step using an in-situ-generated ruthenium catalytic system. The atom-economical and operatively simple syntheses of succinimides, phthalimides, and glutarimides, which are important building blocks in natural products and drugs, was also demonstrated.

    20. cine Substitution

      Selective cine Substitution of 1-Arylethenyl Acetates with Arylboron Reagents and a Diene/Rhodium Catalyst (pages 6396–6399)

      Jung-Yi Yu, Ryosuke Shimizu and Ryoichi Kuwano

      Article first published online: 22 JUL 2010 | DOI: 10.1002/anie.201002745

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      When the crowd says Bo: A carbon–carbon bond is selectively formed at the β position of 1-arylethenyl acetate when the alkenyl substrate is reacted with arylboronic acids in the presence of a cycloocta-1,5-diene/rhodium catalyst. The choice of the ligand is crucial for the unusual cine substitution.

    21. Mesoporous Materials

      A Room-Temperature Reactive-Template Route to Mesoporous ZnGa2O4 with Improved Photocatalytic Activity in Reduction of CO2 (pages 6400–6404)

      Shi Cheng Yan, Shu Xin Ouyang, Jun Gao, Ming Yang, Jian Yong Feng, Xiao Xing Fan, Li Juan Wan, Zhao Sheng Li, Jin Hua Ye, Yong Zhou and Zhi Gang Zou

      Article first published online: 22 JUL 2010 | DOI: 10.1002/anie.201003270

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      Multimetal mesoporous materials MGa2O4 (M=Zn, Ni, Co) can be synthesized by ion-exchange reactions of colloidal mesoporous NaGaO2 (see scheme with TEM images), which acts as both template and precursor, so that a template-removal process can be dispensed with.

    22. Water Splitting

      Light-Induced Water Splitting with Hematite: Improved Nanostructure and Iridium Oxide Catalysis (pages 6405–6408)

      S. David Tilley, Maurin Cornuz, Kevin Sivula and Michael Grätzel

      Article first published online: 21 JUL 2010 | DOI: 10.1002/anie.201003110

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      Revved-up rust! Light-induced water splitting over iron oxide (hematite) has been achieved by using a particle-assisted deposition technique and IrO2-based surface catalysis. Photocurrents in excess of 3 mA cm−2 were obtained at +1.23 V versus the reversible hydrogen electrode under AM 1.5 G 100 mW cm−2 simulated sunlight. These photocurrents are unmatched by any other oxide-based photoanode. FTO=fluorine-doped tin oxide.

    23. Heterocyclic Carbenes

      From Bis(N-Alkylimidazole) to Bis(NH–NHC) in Rhenium Carbonyl Complexes (pages 6409–6412)

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

      Article first published online: 29 JUL 2010 | DOI: 10.1002/anie.201002879

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      Two birds, one stone: A deprotonation–protonation sequence using only one molar equivalent of base and acid transforms two N-alkylimidazole molecules into N-heterocyclic carbene ligands (see scheme; black C, gray H, green F, blue N, red O, cyan Re, yellow S).

    24. Gold Catalysis

      Gold(I)-Catalyzed Cycloisomerization of Enynes Containing Cyclopropenes (pages 6413–6417)

      Changkun Li, Yi Zeng, Hang Zhang, Jiajie Feng, Yan Zhang and Jianbo Wang

      Article first published online: 29 JUL 2010 | DOI: 10.1002/anie.201002673

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      Goldenyne: Gold-catalyzed cycloisomerization reactions of propargyl cyclopropenes afford benzene derivatives in a highly efficient manner. The reaction either proceeds through a mechanism with or without double and triple bond cleavage, depending on the substituents (see scheme).

    25. Asymmetric Synthesis

      Organocatalytic Asymmetric Inverse-Electron-Demand Diels–Alder Reaction of Electron-Deficient Dienes and Crotonaldehyde (pages 6418–6420)

      Jun-Long Li, Tai-Ran Kang, Si-Li Zhou, Rui Li, Li Wu and Ying-Chun Chen

      Article first published online: 29 JUL 2010 | DOI: 10.1002/anie.201002912

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      Another pathway for enals: The excellent β,γ-regioselectivity shown in the title reaction under dienamine catalysis efficiently gave highly diastereo- and enantioenriched cyclohexene derivatives with substantial substitution diversity (see scheme; EWG=electron-withdrawing group, TMS=trimethylsilyl).

    26. Ligand Design

      Electron-Donating and Rigid P-Stereogenic Bisphospholane Ligands for Highly Enantioselective Rhodium-Catalyzed Asymmetric Hydrogenations (pages 6421–6424)

      Xiaowei Zhang, Kexuan Huang, Guohua Hou, Bonan Cao and Xumu Zhang

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201002990

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      More electron donating, more rigid: A new highly electron-donating P-stereogenic bisphospholane ligand (ZhangPhos) was synthesized in a practical and highly enantioselective manner from a commercially available chiral source. Better or comparable enantioselectivities and reactivities than TangPhos were achieved in rhodium-catalyzed hydrogenation of various functionalized olefins (see scheme; nbd=3,5-norbornadiene).

    27. Photoactive Devices

      Innovative Inorganic–Organic Nanohybrid Materials: Coupling Quantum Dots to Carbon Nanotubes (pages 6425–6429)

      Christian Schulz-Drost, Vito Sgobba, Christina Gerhards, Susanne Leubner, Rafael M. Krick Calderon, Andrés Ruland and Dirk M. Guldi

      Article first published online: 10 JUN 2010 | DOI: 10.1002/anie.200906891

      Thumbnail image of graphical abstract

      Inorganic meets organic: Covalent bonds (peptide condensation) and noncovalent interactions (π–π stacking) have been employed en route toward versatile donor–acceptor inorganic–organic nanohybrids, QD-pyrene/SWNT. A charge-transfer event within the hybrid transforms the excitonic state of the quantum dot into a charge-transfer state that has a lifetime of several nanoseconds.

    28. Subcomponent Assembly

      Subcomponent Assembly and Transmetalation of Dinuclear Helicates (pages 6430–6433)

      Johannes Dömer, J. Chris Slootweg, Florian Hupka, Koop Lammertsma and F. Ekkehardt Hahn

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201002776

      Thumbnail image of graphical abstract

      Only available as helicates: Dinuclear zinc and nickel complexes bearing previously inaccessible N,S-N,S ligands have been obtained in subcomponent self-assembly reactions from complexes bearing two 2-thiolatobenzaldehyde ligands and 4,4′-diaminodiphenylmethane. Both complexes react with Pd(OAc)2 by transmetalation to give the dinuclear palladium complex (see scheme).

    29. Reactions in Supercritical Water

      Towards Understanding the Catalytic Reforming of Biomass in Supercritical Water (pages 6434–6437)

      Stefan Rabe, Maarten Nachtegaal, Thomas Ulrich and Frédéric Vogel

      Article first published online: 26 JUL 2010 | DOI: 10.1002/anie.201001160

      Thumbnail image of graphical abstract

      A critical point: The function of a working ruthenium catalyst during the reforming of ethanol in supercritical water was studied in situ using X-ray absorption spectroscopy (see picture). The reforming of ethanol over a supported ruthenium catalyst in sub- and supercritical water is suggested to proceed by the same mechanism as steam reforming at low pressures.

      Corrected by:

      Corrigendum: Corrigendum: Towards Understanding the Catalytic Reforming of Biomass in Supercritical Water

      Vol. 51, Issue 11, 2533, Article first published online: 7 MAR 2012

    30. Copper Monooxygenases

      The First Catalytic Tyrosinase Model System Based on a Mononuclear Copper(I) Complex: Kinetics and Mechanism (pages 6438–6442)

      Malte Rolff, Julia Schottenheim, Gerhard Peters and Felix Tuczek

      Article first published online: 22 JUL 2010 | DOI: 10.1002/anie.201000973

      Thumbnail image of graphical abstract

      Ready… steady… go! The copper(I) complex 1 not only catalyzes the oxygenation of di-tert-butylphenol (DTBP-H) to di-tert-butylquinone (DTBQ) in a tyrosinase-like fashion, but also allows the reactive cycle to be studied in a stepwise and controlled manner. This feature opens new insights into the individual stages of the tyrosinase reaction, phenol hydroxylation, and release of the product as quinone. The implications for the enzymatic reaction are discussed.

    31. Spin-Labeled RNA

      Probing Secondary Structures of Spin-Labeled RNA by Pulsed EPR Spectroscopy (pages 6443–6447)

      Giuseppe Sicoli, Falk Wachowius, Marina Bennati and Claudia Höbartner

      Article first published online: 21 JUL 2010 | DOI: 10.1002/anie.201000713

      Thumbnail image of graphical abstract

      Tempo, TEMPO! Spin-labeled RNAs are readily prepared by postsynthetic modification of RNA. This approach provides access to paramagnetic oligonucleotides with position-specific probes in cytidine, adenosine, and guanosine nucleobases (CT, AT, GT, respectively). In this way alternative RNA secondary structures can be investigated by distance measurements using pulsed EPR spectroscopy.

    32. Nacre Paper

      Supramolecular Control of Stiffness and Strength in Lightweight High-Performance Nacre-Mimetic Paper with Fire-Shielding Properties (pages 6448–6453)

      Andreas Walther, Ingela Bjurhager, Jani-Markus Malho, Janne Ruokolainen, Lars Berglund and Olli Ikkala

      Article first published online: 27 JUL 2010 | DOI: 10.1002/anie.201001577

      Thumbnail image of graphical abstract

      Taking the heat: Hard/soft core/shell colloidal building blocks allow large-scale self-assembly to form nacre-mimetic paper. The strength and stiffness of this material can be tailored by supramolecular ionic bonds. These lightweight biomimetic materials show excellent and tunable mechanical properties and heat and fire-shielding capabilities.

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      Preview: Angew. Chem. Int. Ed. 37/2010 (page 6457)

      Article first published online: 19 AUG 2010 | DOI: 10.1002/anie.201090115

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