Angewandte Chemie International Edition

Cover image for Vol. 50 Issue 29

July 11, 2011

Volume 50, Issue 29

Pages 6421–6671

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Highlight
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Cover Picture: Dibridgehead Diphosphines that Turn Themselves Inside Out (Angew. Chem. Int. Ed. 29/2011) (page 6421)

      Dr. Michael Stollenz, Dr. Michał Barbasiewicz, Dr. Agnieszka J. Nawara-Hultzsch, Dipl.-Chem. Tobias Fiedler, Ryan M. Laddusaw, Dr. Nattamai Bhuvanesh and Prof. Dr. John A. Gladysz

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201103784

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      Macrocyclic bicyclic molecules in which the three flexible diphosphine chains linking the bridgehead atoms undergo a topological process (homeomorphic isomerization) involving passing one chain through the ring formed by the other two, thereby turning the compound inside-out with apparent pyramidal inversion, are described by J. A. Gladysz and co-workers in their Communication on page 6647 ff. Modifying alchemical symbolism and in memory of Kekulé's famous dream, the diphosphines are represented by three Ouroboros snakes that form a cage by seizing each other's tails instead of their own.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. News
    10. Highlight
    11. Essay
    12. Minireview
    13. Review
    14. Communications
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    1. Inside Cover: A Facile Palladium-Mediated Contraction of Benzene to Cyclopentadiene: Transformations of Palladium(II) p-Benziporphyrin (Angew. Chem. Int. Ed. 29/2011) (page 6422)

      Bartosz Szyszko, Prof. Lechosław Latos-Grażyński and Dr. Ludmiła Szterenberg

      Article first published online: 30 JUN 2011 | DOI: 10.1002/anie.201103966

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      The fundamental reactivity of the benzene unit can be altered by metal⋅⋅⋅(C[BOND]C) interactions that arise from encapsulating the specific donor center (C C N N N) in the porphyrinic core of palladium(II) p-benziporphyrin. In their Communication on page 6587 ff., L. Latos-Grażyński and co-workers describe the remarkable, facile palladium(II)-mediated contraction of p-phenylene to cyclopentadiene to afford 21-carbaporphyrin complexes.

  3. Back Cover

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    4. Back Cover
    5. Editorial
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    11. Essay
    12. Minireview
    13. Review
    14. Communications
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    1. Back Cover: Cryogenic Magnetocaloric Effect in a Ferromagnetic Molecular Dimer (Angew. Chem. Int. Ed. 29/2011) (page 6422)

      Dr. Marco Evangelisti, Dr. Olivier Roubeau, Dr. Elias Palacios, Dr. Agustín Camón, Thomas N. Hooper, Dr. Euan K. Brechin and Dr. Juan J. Alonso

      Article first published online: 7 JUN 2011 | DOI: 10.1002/anie.201103406

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      By taking advantage of a relatively high magnetic density combined with a dominant ferromagnetism, gadolinium acetate tetrahydrate displays an unprecedentedly large cryogenic magnetocaloric effect. The remarkable temperature drops, reported by M. Evangelisti and co-workers in their Communication on page 6606 ff., suggest that this molecular nanomagnet can be employed as an efficient magnetic refrigerant for low-temperature applications (picture by O. Roubeau).

  4. Editorial

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    11. Essay
    12. Minireview
    13. Review
    14. Communications
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    1. You have free access to this content
      Chemistry’s Role in Regenerative Energy (pages 6424–6426)

      Prof. Dr. Robert Schlögl

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201103415

  5. Graphical Abstract

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    11. Essay
    12. Minireview
    13. Review
    14. Communications
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  6. News

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  7. Author Profile

    1. Top of page
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    5. Editorial
    6. Graphical Abstract
    7. News
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    11. Essay
    12. Minireview
    13. Review
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    1. Stefan Bräse (page 6444)

      Article first published online: 30 JUN 2011 | DOI: 10.1002/anie.201102769

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      “When I was eighteen I wanted to be a prosecutor. My first experiment was making sodium out of sodium chloride (electrolysis using my toy train set) …” This and more about Stefan Bräse can be found on page 6444.

  8. News

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  9. Highlight

    1. Top of page
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    5. Editorial
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    11. Essay
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    13. Review
    14. Communications
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    1. Salt Effects

      Split Personality of Lithium Chloride: Recent Salt Effects in Organometallic Recipes (pages 6448–6450)

      Dr. Eva Hevia and Prof. Robert E. Mulvey

      Article first published online: 22 JUN 2011 | DOI: 10.1002/anie.201102054

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      Jekyll and Hyde: Pinches of LiCl can catalyze orthometalations of halogen-substituted arenes and addition reactions of unsaturated esters, mediated by lithium diisopropylamide. Larger salt portions can transform weak organometallic bases (e.g., Grignard reagents, zincates) into “turbo” reagents of high reactivity and functional group tolerance. But the presence of LiCl, especially as an overlooked metathesis by-product can be detrimental to other catalytic reactions.

  10. Essay

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    1. History of Chemistry

      A. M. Zaitsev: Lasting Contributions of a Synthetic Virtuoso a Century after his Death (pages 6452–6458)

      Prof. Dr. David E. Lewis

      Article first published online: 15 JUN 2011 | DOI: 10.1002/anie.201100215

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      A lasting legacy: A. M. Zaitsev (1841–1910) was a professor at Kazan University in Russia and discovered the sulfoxides and sulfonium salts. He synthesized the first lactone, expanded the synthesis of alcohols using alkylzinc nucleophiles, and carried out the first oxidation of an alkene with potassium permanganate. His students included three important organic chemists of the next generation: Wagner, Reformatskii, and Arbuzov.

  11. Minireview

    1. Top of page
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    1. Epigenetics

      5-Hydroxymethylcytosine, the Sixth Base of the Genome (pages 6460–6468)

      Dipl.-Chem. Martin Münzel, Dipl.-Chem. Daniel Globisch and Prof. Dr. Thomas Carell

      Article first published online: 17 JUN 2011 | DOI: 10.1002/anie.201101547

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      The sixth sense: 5-Hydroxymethylcytosine (hmC) was recently discovered as a new constituent of mammalian DNA, and besides 5-methylcytosine it is the only other modified base in higher organisms. This discovery shows that methylation of cyctosine is not a final step in gene silencing, but that further functionalization of the methyl group occurs.

  12. Review

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    13. Review
    14. Communications
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    1. Ambident Reactivity

      Farewell to the HSAB Treatment of Ambident Reactivity (pages 6470–6505)

      Prof. Dr. Herbert Mayr, Dr. Martin Breugst and Dr. Armin R. Ofial

      Article first published online: 1 JUL 2011 | DOI: 10.1002/anie.201007100

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      Hard or soft? The prediction of ambident reactivity by the concept of hard and soft acids and bases fails in the majority of cases and has to be abandoned. In this Review an alternative approach is presented to rationalize the regioselectivities of ambident systems which differentiates between kinetic and thermodynamic product control as well as between reactions proceeding with and without activation energy. The predictive power of qualitative Marcus theory is demonstrated.

  13. Communications

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    1. Three-Dimensional Polymer Structures

      Fabrication of Arbitrary Three-Dimensional Polymer Structures by Rational Control of the Spacing between Nanobrushes (pages 6506–6510)

      Dr. Xuechang Zhou, Dr. Xiaolong Wang, Youde Shen, Zhuang Xie and Prof. Zijian Zheng

      Article first published online: 9 JUN 2011 | DOI: 10.1002/anie.201102518

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      3D polymer structures can be fabricated by rational control of the spacing between nanosized polymer brushes. Each nanobrush can be precisely patterned by combination of dip-pen nanodisplacement lithography and surface-initiated atom transfer radical polymerization (SI-ATRP; see picture). Complex 3D topographic images of the Mona Lisa have been obtained in this way.

    2. Protein Trans-Splicing

      Kinetic Control of One-Pot Trans-Splicing Reactions by Using a Wild-Type and Designed Split Intein (pages 6511–6515)

      Neel H. Shah, Dr. Miquel Vila-Perelló and Prof. Tom W. Muir

      Article first published online: 8 JUN 2011 | DOI: 10.1002/anie.201102909

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      Charge-swapping of key intermolecular ion clusters in the naturally split DnaE intein from Nostoc punctiforme (NpuWT) alters split intein binding affinities and trans-splicing kinetics. This concept was used to engineer the new split intein NpuMUT with low cross-reactivity to NpuWT. This intein pair can be used to catalyze multiple trans-splicing reactions in one pot with kinetically controlled selectivity (see picture).

    3. Protein–DNA Recognition

      Protein–DNA Recognition Triggered by a DNA Conformational Switch (pages 6516–6518)

      Dr. Benjamin Bouvier, Dr. Krystyna Zakrzewska and Dr. Richard Lavery

      Article first published online: 30 MAY 2011 | DOI: 10.1002/anie.201101417

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      Making the switch: The analysis of molecular dynamics simulations of the SRY-protein–DNA complex shows that, when the SRY protein approaches the correct DNA target sequence, it triggers a DNA conformational switch and allows the passage from a nonspecifically bound to a specifically bound state (see picture; dAXC=distance between DNA and SRY protein).

    4. Drug Design

      You have full text access to this OnlineOpen article
      A Potent Trivalent Sialic Acid Inhibitor of Adenovirus Type 37 Infection of Human Corneal Cells (pages 6519–6521)

      Dr. Sara Spjut, Dr. Weixing Qian, Johannes Bauer, Rickard Storm, Dr. Lars Frängsmyr, Prof. Thilo Stehle, Prof. Niklas Arnberg and Prof. Mikael Elofsson

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201101559

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      Wouldn′t it be useful to have three arms? It came in handy for a trivalent sialic acid inhibitor, which blocked all three binding pockets of a trimeric adenoviral fiber-knob protein and thus prevented cell attachment and the subsequent infection of human corneal epithelial cells. The picture shows the terminal sialic acid moietes of the inhibitor bound to the top of the fiber head (C yellow, O red, N blue; the spacers and scaffold are not shown).

    5. Bioactive Surfaces

      Bio-orthogonal “Double-Click” Chemistry Based on Multifunctional Coatings (pages 6522–6526)

      Xiaopei Deng, Dr. Christian Friedmann and Prof. Dr. Joerg Lahann

      Article first published online: 7 JUN 2011 | DOI: 10.1002/anie.201101581

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      Double “click”: Two different molecules can be sequentially immobilized on defined areas of the same surface by utilizing the different reactivity of activated and non-activated alkynyl groups (see picture). The reactions were carried out at room temperature in water, with the first immobilization step being catalyst-free and the second step requiring CuI as a catalyst.

    6. Peptide Folding

      Total Synthesis of the Analgesic Conotoxin MrVIB through Selenocysteine-Assisted Folding (pages 6527–6529)

      Dr. Aline Dantas de Araujo, Dr. Brid Callaghan, Dr. Simon T. Nevin, Dr. Norelle L. Daly, Prof. David J. Craik, Melissa Moretta, Dr. Gene Hopping, Prof. Macdonald J. Christie, Prof. David J. Adams and Prof. Paul F. Alewood

      Article first published online: 31 MAY 2011 | DOI: 10.1002/anie.201101642

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      Secs for your folding problems: Selenocysteine (Sec) residues were used to drive the folding of conotoxin MrVIB, a previously “unfoldable” miniprotein with therapeutic potential (see picture). This simple strategy should generally facilitate the folding of peptides and proteins with multiple disulfide bonds.

    7. Metal-Organic Frameworks

      Single Pyramid Magnets: Dy5 Pyramids with Slow Magnetic Relaxation to 40 K (pages 6530–6533)

      Dr. Robin J. Blagg, Dr. Christopher A. Muryn, Prof. Eric J. L. McInnes, Dr. Floriana Tuna and Prof. Richard E. P. Winpenny

      Article first published online: 7 JUN 2011 | DOI: 10.1002/anie.201101932

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      Single-molecule magnets: A square-pyramidal pentametallic dysprosium cluster (see picture) was synthesized and showed slow magnetic relaxation at temperatures as high as 40 K. The thermal energy barrier to relaxation of magnetization of this single-molecule magnet is 530 K and is the largest yet observed for any d- or f-block cluster compound.

    8. Protein Biosensors

      Development of a Selective, Sensitive, and Reversible Biosensor by the Genetic Incorporation of a Metal-Binding Site into Green Fluorescent Protein (pages 6534–6537)

      Dr. Niraikulam Ayyadurai, Nadarajan Saravanan Prabhu, Kanagavel Deepankumar, Prof. Sun-Gu Lee, Heon-Ho Jeong, Prof. Chang-Soo Lee and Prof. Hyungdon Yun

      Article first published online: 7 JUN 2011 | DOI: 10.1002/anie.201008289

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      There when the light goes out: A copper biosensor was created by the introduction of the metal-chelating noncanonical amino acid L-DOPA in place of L-tyrosine into green fluorescent protein by genetic-code engineering (see picture). The specific binding of Cu2+ in vitro by the modified protein was reversible and resulted in fluorescence quenching in proportion to the amount of Cu2+ present. EDTA=ethylenediaminetetraacetic acid.

    9. Nanocrystal Purification

      An Efficient and Low-Cost Method for the Purification of Colloidal Nanoparticles (pages 6538–6542)

      Dr. John D. Bass, Dr. Xin Ai, Dr. Abdulaziz Bagabas, Dr. Philip M. Rice, Dr. Teya Topuria, Dr. J. Campbell Scott, Dr. Fahhad H. Alharbi, Dr. Ho-Cheol Kim, Dr. Qing Song and Dr. Robert D. Miller

      Article first published online: 27 MAY 2011 | DOI: 10.1002/anie.201100112

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      What a clean-up! A scalable method for the purification of nanoparticles in nonaqueous media has been developed that is based on reversible electrophoretic deposition (see picture). In this electropurification process, nanoparticles of varying size, shape, composition, and ligand environment can be electrodeposited onto an electrode surface, washed, and subsequently redispersed in as little as two minutes.

    10. Metal–Organic Frameworks

      Dramatically Different Conductivity Properties of Metal–Organic Framework Polymorphs of Tl(TCNQ): An Unexpected Room-Temperature Crystal-to-Crystal Phase Transition (pages 6543–6547)

      Dr. Carolina Avendano, Zhongyue Zhang, Dr. Akira Ota, Dr. Hanhua Zhao and Prof. Kim R. Dunbar

      Article first published online: 7 JUN 2011 | DOI: 10.1002/anie.201100372

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      Just add water: Tl(TCNQ) polymorphs with very different charge-transport properties have been isolated, one of which undergoes a remarkable crystal-to-crystal phase transition to the second phase when exposed to ambient water vapor (see picture; TCNQ=tetracyanoquinodimethane).

    11. NMR Spectroscopy

      Fast Multidimensional NMR Spectroscopy Using Compressed Sensing (pages 6548–6551)

      Dr. Daniel J. Holland, Mark J. Bostock, Prof. Dr. Lynn F. Gladden and Dr. Daniel Nietlispach

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201100440

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      Make it snappy! The use of compressed sensing to reconstruct multidimensional NMR spectra enables significant reductions in recording time. Thus, 3D HNCA (blue) and HN(CO)CA spectra (green) of sufficient quality for rapid protein-backbone assignment were reconstructed from only 16 % of the fully sampled data. The generality of the method and its robustness to noise should make it more broadly applicable, for example, to solid-state NMR spectroscopy.

    12. Oligomer Synthesis

      A Palladium-Catalyzed Multicomponent Coupling Approach to π-Conjugated Oligomers: Assembling Imidazole-Based Materials from Imines and Acyl Chlorides (pages 6552–6556)

      Ali R. Siamaki, Marc Sakalauskas and Prof. Bruce A. Arndtsen

      Article first published online: 31 MAY 2011 | DOI: 10.1002/anie.201100558

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      Just like tinkertoys: An alternative approach to access imidazole-containing π-conjugated materials is presented. The imidazole core was assembled at the same time as the oligomer by the palladium-catalyzed multicomponent coupling of imines, diimines, and di(acyl chloride)s, thus providing access to families of new conjugated materials, each formed in a one-step, catalytic reaction (see scheme; Ts=4-toluenesulfonyl).

    13. Perovskite Catalysts

      An Oxygen-Deficient Perovskite as Selective Catalyst in the Oxidation of Alkyl Benzenes (pages 6557–6561)

      Dr. A. Aguadero, Dr. H. Falcon, Dr. J. M. Campos-Martin, Prof. Dr. S. M. Al-Zahrani, Prof. Dr. J. L. G. Fierro and Prof. Dr. J. A. Alonso

      Article first published online: 31 MAY 2011 | DOI: 10.1002/anie.201007941

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      Extraordinary reaction rates and selectivity for the conversion of alkyl aromatic compounds, such as p-xylene, in terephthalic acid were observed for a heterogeneous perovskite catalyst of composition (La,Sr)0.5(Mn,Co)0.5O2.38 (see picture). The oxygen-deficient catalyst was prepared by reduction of the oxygen-stoichiometric parent compound.

    14. Self-Assembly

      Janus-Like 3D Tectons: Self-Assembled 2D Arrays of Functional Units at a Defined Distance from the Substrate (pages 6562–6566)

      Dr. David Bléger, Dr. Fabrice Mathevet, Dr. David Kreher, Prof. André-Jean Attias, Amandine Bocheux, Dr. Sylvain Latil, Dr. Ludovic Douillard, Dr. Céline Fiorini-Debuisschert and Dr. Fabrice Charra

      Article first published online: 10 JUN 2011 | DOI: 10.1002/anie.201008212

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      Janus faces: The Janus-like 3D tecton is a doubly functionalized molecular building block that consists of two different faces (see picture, gray: A and blue: B) linked by a rigid spacer. A is designed to act as a pedestal capable of guiding 2D self-assembly on the substrate, while B is a functional entity. This versatile approach allows for the creation of periodic arrays of functional units at a defined distance from the conductive substrate.

    15. Tumor Imaging

      High-Contrast Fluorescence Imaging of Tumors In Vivo Using Nanoparticles of Amphiphilic Brush-Like Copolymers Produced by ROMP (pages 6567–6570)

      Dr. Koji Miki, Akinori Kimura, Kazuaki Oride, Yoshiaki Kuramochi, Prof. Hideki Matsuoka, Dr. Hiroshi Harada, Prof. Masahiro Hiraoka and Prof. Kouichi Ohe

      Article first published online: 7 JUN 2011 | DOI: 10.1002/anie.201101005

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      Nanoparticles at work: High-contrast tumor imaging of mice was performed by using copolymers with hydrophobic and hydrophilic polymer brushes that form cross-linked assemblies and show a highly stable core surface in aqueous media (see picture). Cyclic RGD peptides and glucosamine moieties were localized on the surface of the assemblies and acted as targeting agents (TA) that enhanced the accumulation of the assemblies in tumor tissues.

    16. Organogold Compounds

      [Au(CF3)(CO)]: A Gold Carbonyl Compound Stabilized by a Trifluoromethyl Group (pages 6571–6574)

      Sonia Martínez-Salvador, Prof. Dr. Juan Forniés, Dr. Antonio Martín and Dr. Babil Menjón

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201101231

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      Fluorination operates for good: A trifluoromethyl group is able to stabilize the title compound (see picture; Au yellow, C gray, F green, O red), which formed by low-temperature treatment of [PPh4][Au(CF3)2] with BF3⋅OEt2. A trigonal environment is adopted by each molecule with aurophilic interactions with three near-neighbors in a global triskelion arrangement.

    17. Graphene

      Asymmetrically Functionalized Graphene for Photodependent Diode Rectifying Behavior (pages 6575–6578)

      Dr. Dingshan Yu, Enoch Nagelli, Dr. Rajesh Naik and Prof. Liming Dai

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201101305

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      Both sides of the sheet: A simple method is described for functionalizing the two surfaces of individual graphene sheets with different nanoparticles in either a patterned or nonpatterned fashion. Graphene sheets with ZnO and Au nanoparticles on their opposite surfaces show a strong photodependent diodelike rectifying behavior (see picture; pink spheres=ZnO, green cubes=Au, blue triangle=AFM tip).

    18. Negative Thermal Expansion

      Giant Negative Thermal Expansion in the Iron Perovskite SrCu3Fe4O12 (pages 6579–6582)

      Prof. Dr. Ikuya Yamada, Kazuki Tsuchida, Prof. Dr. Kenya Ohgushi, Naoaki Hayashi, Dr. Jungeun Kim, Dr. Naruki Tsuji, Prof. Dr. Ryoji Takahashi, Prof. Dr. Masafumi Matsushita, Prof. Dr. Norimasa Nishiyama, Prof. Dr. Toru Inoue, Prof. Dr. Tetsuo Irifune, Dr. Kenichi Kato, Dr. Masaki Takata and Prof. Dr. Mikio Takano

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201102228

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      Big and cold: Strong internal compression of the Sr ion in the novel perovskite SrCu3Fe4O12 (see structure) leads to giant negative thermal expansion (NTE) between 170 and 270 K. Mössbauer spectroscopy shows charge disproportionation of FeIV to FeIII and FeV below 200 K. Thus, the isoelectric substitution of the A-site cation can induce a drastic change of the structural and electronic properties in ACu3Fe4O12 perovskites.

    19. Helical Structures

      Conversion of Cobalt(II) Porphyrin into a Helical Cobalt(III) Complex of Acyclic Pentapyrrole (pages 6583–6586)

      Katsunori Yamanishi, Masamichi Miyazawa, Takeshi Yairi, Shintaro Sakai, Dr. Naoko Nishina, Prof. Yasuhiro Kobori, Prof. Mitsuru Kondo and Fumio Uchida

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201102144

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      The turn of the screw: The CoII complex of a porphyrin ligand with a pendant ortho-amidophenyl group converted into a helical CoIII complex with an acyclic pentapyrrole ligand upon addition of a coordinating base and exposure to O2 (see picture, Co pink, N blue, O red, C gray). The enantiomers of the complex were separated and characterized, and preferential induction of an (M)-helical complex by addition of chiral bases was demonstrated.

    20. Porphyrinoids

      A Facile Palladium-Mediated Contraction of Benzene to Cyclopentadiene: Transformations of Palladium(II) p-Benziporphyrin (pages 6587–6591)

      Bartosz Szyszko, Prof. Lechosław Latos-Grażyński and Dr. Ludmiła Szterenberg

      Article first published online: 31 MAY 2011 | DOI: 10.1002/anie.201102218

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      Feeling the contractions: Addition of palladium(II) and a hydroxide ion to a C–C double bond, β elimination, and competing cheletropic extrusion of carbon oxide and 1,2-hydride shift reactions lead to the contraction of p-phenylene to form a cyclopentadiene unit. This reaction results in the formation of a 21-carbaporphyrin from a palladium(II) p-benziporphyrin (see picture; C red/gray, N blue, Pd orange).

    21. Dynamic Chemistry

      Racemase Activity of B. cepacia Lipase Leads to Dual-Function Asymmetric Dynamic Kinetic Resolution of α-Aminonitriles (pages 6592–6595)

      Dr. Pornrapee Vongvilai, Mats Linder, Morakot Sakulsombat, Dr. Maria Svedendahl Humble, Prof. Per Berglund, Prof. Tore Brinck and Prof. Olof Ramström

      Article first published online: 1 JUN 2011 | DOI: 10.1002/anie.201007373

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      Applaudable promiscuity: Racemase-type activity discovered for B. cepacia lipase with N-substituted α-aminonitriles is proposed to involve a C[BOND]C bond-breaking/forming mechanism in the hydrolase site of the enzyme, as supported by experimental data and calculations. This promiscuous activity in combination with the transacylation activity of the enzyme enabled the asymmetric synthesis of N-methyl α-aminonitrile amides in high yield (see scheme).

    22. Synthetic Methods

      Rhodium(I)-Catalyzed Ene–Allene–Allene [2+2+2] Cycloadditions: Stereoselective Synthesis of Complex trans-Fused Carbocycles (pages 6596–6600)

      Andrew T. Brusoe and Prof.  Erik J. Alexanian

      Article first published online: 27 MAY 2011 | DOI: 10.1002/anie.201100272

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      A complex situation: The title reaction was utilized for the construction of a variety of trans-fused hydrindanes and decalins in a highly convergent manner (see scheme; binap=2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl, Tf=trifluoromethanesulfonate), with three σ bonds, two rings, and up to four contiguous stereocenters generated in a regio- and stereoselective fashion.

      Corrected by:

      Corrigendum: Corrigendum: Rhodium(I)-Catalyzed Ene–Allene–Allene [2+2+2] Cycloadditions: Stereoselective Synthesis of Complex trans-Fused Carbocycles

      Vol. 52, Issue 13, 3552, Article first published online: 20 MAR 2013

    23. Enantiomer Discrimination

      Visual Chiral Recognition through Enantioselective Metallogel Collapsing: Synthesis, Characterization, and Application of Platinum–Steroid Low-Molecular-Mass Gelators (pages 6601–6605)

      Dr. Tao Tu, Weiwei Fang, Xiaoling Bao, Xinbao Li and Prof. Karl Heinz Dötz

      Article first published online: 27 MAY 2011 | DOI: 10.1002/anie.201100620

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      Seeing is believing: The visual chiral recognition of (R)- and (S)-binap has been realized through an enantioselective breakdown of metallogels prepared from novel aromatic–linker–steroidal-type pincer platinum gelators. Van der Waals interactions, π stacking, and metal–metal bonding are responsible for the aggregation and chiral recognition.

    24. Magnetocaloric Effect

      Cryogenic Magnetocaloric Effect in a Ferromagnetic Molecular Dimer (pages 6606–6609)

      Dr. Marco Evangelisti, Dr. Olivier Roubeau, Dr. Elias Palacios, Dr. Agustín Camón, Thomas N. Hooper, Dr. Euan K. Brechin and Dr. Juan J. Alonso

      Article first published online: 7 JUN 2011 | DOI: 10.1002/anie.201102640

      Thumbnail image of graphical abstract

      Molecoolers: An unprecedentedly large cryogenic magnetocaloric effect is observed in gadolinium acetate tetrahydrate (see picture, Gd pink, O red, C gray). The change in its magnetic entropy is ascribed to the high magnetic density combined with dominant ferromagnetism. For the first time in a molecular complex, direct measurements of the magnetocaloric effect corroborate indirect estimates based on heat capacity and magnetization.

    25. Asymmetric Catalysis

      Asymmetric Binary Acid Catalysis: A Regioselectivity Switch between Enantioselective 1,2- and 1,4-Addition through Different Counteranions of InIII (pages 6610–6614)

      Jian Lv, Dr. Long Zhang, Yueming Zhou, Prof. Zongxiu Nie, Prof. Sanzhong Luo and Prof. Jin-Pei Cheng

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201101254

      Thumbnail image of graphical abstract

      You can count on the anion: Simply swapping the anions of an indium Lewis acid leads to a remarkable regioselectivity switch between asymmetric 1,2- and 1,4-addition reactions. N-protected indoles and β,γ-unsaturated α-keto esters gave adducts with excellent enantioselectivity (see scheme).

    26. Cyclic Polymers

      Cyclic Polymers with Pendent Carbazole Units: Enhanced Fluorescence and Redox Behavior (pages 6615–6618)

      Xing Zhu, Prof. Dr. Nianchen Zhou, Dr. Zhengbiao Zhang, Prof. Dr. Baoquan Sun, Prof. Dr. Yonggang Yang, Dr. Jian Zhu and Prof. Dr. Xiulin Zhu

      Article first published online: 30 MAY 2011 | DOI: 10.1002/anie.201101303

      Thumbnail image of graphical abstract

      Circle the wagons: Well-defined cyclic poly(4-vinylbenzylcarbazole) (cyclic PVBCZ) polymers with differing molecular weights were prepared efficiently by successive atom-transfer radical polymerization (ATRP) and a click reaction (see picture; Σ=azide, Δ=alkynyl groups). The cyclic PVBCZ displayed a higher glass transition temperature than its linear precursor and has a higher fluorescence emission.

    27. Solar Cells

      A High-Efficiency Panchromatic Squaraine Sensitizer for Dye-Sensitized Solar Cells (pages 6619–6621)

      Yanrong Shi, Rebecca B. M. Hill, Dr. Jun-Ho Yum, Amalie Dualeh, Dr. Stephen Barlow, Prof. Michael Grätzel, Prof. Seth R. Marder and Dr. Mohammad K. Nazeeruddin

      Article first published online: 30 MAY 2011 | DOI: 10.1002/anie.201101362

      Thumbnail image of graphical abstract

      Squarely efficient: A squaraine sensitizer (see picture) shows an outstanding power conversion efficiency of 6.74 % in liquid dye-sensitized solar cells and 2.69 % in solid-state dye-sensitized solar cells. The high efficiencies are related to both the bathochromic shift of the absorption maximum compared to other squaraine sensitizers, and to the presence of additional absorptions that lead to high absorptivity over much of the visible spectrum.

    28. Silver Nanoparticles

      Activation of Thiols at a Silver Nanoparticle Surface (pages 6622–6625)

      Dr. Wei Gan, Bolei Xu and Prof. Hai-Lung Dai

      Article first published online: 1 JUN 2011 | DOI: 10.1002/anie.201101430

      Thumbnail image of graphical abstract

      Reactions of thiols that are used to modify nanoparticle (NP) properties at the surface of noble-metal NPs involve an activation process. By detecting second harmonic generation from the Ag NP surface, the activation energy Ea for the adsorption of 1,2-benzenedithiol onto silver nanoparticles in colloids was determined to be 8.4 kcal mol−1 (see picture), which may arise from the transition state (T.S.) in the bonding reaction.

    29. Olefin Functionalization

      Alternative Pathways for Heck Intermediates: Palladium-Catalyzed Oxyarylation of Homoallylic Alcohols (pages 6626–6629)

      Dr. Chen Zhu and Prof. Dr. John R. Falck

      Article first published online: 8 JUN 2011 | DOI: 10.1002/anie.201101857

      Thumbnail image of graphical abstract

      The oxidative Heck arylation of homoallylic alcohols affords adducts in good yields and regioselectivities owing largely to coordination between the catalyst and hydroxy group (see scheme). Moreover, the Heck intermediate can be intercepted by an intramolecular palladium-catalyzed olefin oxyannulation, thus leading to a wide range of α-aryltetrahydrofurans, including highly functionalized scaffolds.

    30. Nitrogen Atom Transfer

      Snapshots of Complete Nitrogen Atom Transfer from an Iron(IV) Nitrido Complex (pages 6630–6633)

      Jeremiah J. Scepaniak, Dr. Ranko P. Bontchev, Dr. Dennis L. Johnson and Prof. Jeremy M. Smith

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201102028

      Thumbnail image of graphical abstract

      Degrees of separation: The extent of nitrogen atom transfer from iron(IV) nitrido complexes to unsaturated substrates is dictated by the supporting tris(carbene)borate ligand. This transfer step can be coupled to a subsequent group transfer reaction, creating a cycle for the synthesis of an unsymmetrical carbodiimide (see scheme).

    31. Photophysics

      Conformational Effects on the Dynamics of Internal Conversion in Boron Dipyrromethene Dyes in Solution (pages 6634–6637)

      Dr. Gordon J. Hedley, Dr. Arvydas Ruseckas, Prof. Anthony Harriman and Prof. Ifor D. W. Samuel

      Article first published online: 10 JUN 2011 | DOI: 10.1002/anie.201101219

      Thumbnail image of graphical abstract

      Twisting the light away: Internal conversion between the S2 and S1 excited singlet states is rapid in the target dyes (see picture) but shows a clear sensitivity to rotational flexibility of the meso-phenyl ring. Steric crowding by methyl groups at the 4,7-positions leads to a curved S2 potential-energy surface punctured with nonlocal pinholes coupled to the S1 surface. Removal of these groups flattens the potential-energy surface, promoting barrierless crossing to the S1 surface.

    32. Aryne Chemistry

      A Multicomponent Coupling Reaction Induced by Insertion of Arynes into the C[DOUBLE BOND]O Bond of Formamide (pages 6638–6642)

      Dr. Eito Yoshioka, Dr. Shigeru Kohtani and Prof. Hideto Miyabe

      Article first published online: 27 MAY 2011 | DOI: 10.1002/anie.201102088

      Thumbnail image of graphical abstract

      And aryne makes three: The three-component coupling of arynes, DMF, and active methylenes has provided an efficient method for the synthesis of 2H-chromene and coumarin derivatives (see scheme). The sequential multistep reactions are driven by the release of strain energy in the arynes and intermediates, and this finding was supported by thermodynamics.

    33. Rotaxanes

      A Metal-Free “Threading-Followed-by-Shrinking” Protocol for Rotaxane Synthesis (pages 6643–6646)

      Sheng-Yao Hsueh, Jia-Ling Ko, Prof. Chien-Chen Lai, Yi-Hung Liu, Prof. Shie-Ming Peng and Prof. Sheng-Hsien Chiu

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201101524

      Thumbnail image of graphical abstract

      Shrinking ring size: Synthesis of a [2]rotaxane has employed photoextrusion of SO2 from the arylmethyl sulfone motif of a [2]pseudorotaxane. A dumbbell-shaped guest molecule allows a shrinking reaction to decrease the number of atoms in the ring skeleton of the macrocyclic component of the [2]pseudorotaxane (see picture).

    34. Macrobicyclic Phosphanes

      Dibridgehead Diphosphines that Turn Themselves Inside Out (pages 6647–6651)

      Dr. Michael Stollenz, Dr. Michał Barbasiewicz, Dr. Agnieszka J. Nawara-Hultzsch, Dipl.-Chem. Tobias Fiedler, Ryan M. Laddusaw, Dr. Nattamai Bhuvanesh and Prof. Dr. John A. Gladysz

      Article first published online: 3 JUN 2011 | DOI: 10.1002/anie.201100893

      Thumbnail image of graphical abstract

      Molecular contortionists can lurk in unexpected places. The title compounds undergo equilibria that appear to involve straightforward pyramidal inversions at the phosphorus atoms, but in reality the stereoisomers interconvert by turning themselves inside out (see scheme)!

    35. Surface Chemistry

      Superoleophobic Coatings with Ultralow Sliding Angles Based on Silicone Nanofilaments (pages 6652–6656)

      Dr. Junping Zhang and Prof. Stefan Seeger

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201101008

      Thumbnail image of graphical abstract

      Superoleophobic surfaces were fabricated by using organosilanes. The surfaces feature high contact angles and ultralow sliding angles for various nonpolar liquids, excellent transparency, and chemical and environmental stability. The microstructure and superoleophobicity of the surfaces can be regulated simply by the water concentration in toluene used during the coating procedure.

    36. P4 Activation

      Synthesis of Anionic Iron Polyphosphides by Reaction of White Phosphorus with “Cp*Fe (pages 6657–6660)

      Dipl.-Chem. Eva-Maria Schnöckelborg, Dr. Jan J. Weigand and Prof. Dr. Robert Wolf

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201101038

      Thumbnail image of graphical abstract

      Transforming P4: The reaction of the anionic Cp*Fe equivalent 1 with white phosphorus is a promising new approach toward P4 activation. The reaction proceeded under mild conditions and enabled the synthesis of remarkable anionic polyphosphido complexes. Two new iron polyphosphides 2 and 3 were isolated and characterized by X-ray crystallography, 31P NMR spectroscopy, and quantum chemical calculations.

    37. Ionic Liquids

      The Influence of Hydrogen-Bond Defects on the Properties of Ionic Liquids (pages 6661–6665)

      Dr. Tim Peppel, Dipl.-Chem. Christian Roth, Dr. Koichi Fumino, Dr. Dietmar Paschek, Prof. Dr. Martin Köckerling and Prof. Dr. Ralf Ludwig

      Article first published online: 31 MAY 2011 | DOI: 10.1002/anie.201100199

      Thumbnail image of graphical abstract

      Counterintuitive: The preformation of ion pairs can explain the low melting points of imidazolium-based ionic liquids (ILs) and the resulting expanded range of working temperatures. This quasi-ion-pair formation is possible for ILs having cations with only one interaction site leading to local and directional hydrogen bonds with the corresponding anion (see structure; O red, N blue, F green, S yellow).

    38. Crystal Transformation

      Pure α-Metallated Benzyllithium from a Single-Crystal-to-Single-Crystal Transition (pages 6666–6669)

      Tanja Tatic, Stefanie Hermann, Dr. Michael John, Dr. Antoine Loquet, Dr. Adam Lange and Prof. Dr. Dietmar Stalke

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201102068

      Thumbnail image of graphical abstract

      Crystal cannibalization: In a solution-mediated single-crystal-to-single-crystal transition the colorless starting material [{Me2N(CH2)2OMe}⋅(LiCH2SiMe3)]2 converts in toluene into yellow crystals of the benzyllithium tetramer [{Me2N(CH2)2OMe}⋅(LiCH2C6H5)]4 (see picture, microscope photograph of the transforming crystals). A straightforward convenient access to commercially interesting benzyllithium in ligand-stabilized form is thus provided.

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      Article first published online: 5 JUL 2011 | DOI: 10.1002/anie.201190058

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