Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

August 8, 2011

Volume 50, Issue 33

Pages 7449–7703

  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. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Cover Picture: Total Synthesis of (+)-Omphadiol (Angew. Chem. Int. Ed. 33/2011) (page 7449)

      Gang Liu and Prof. Dr. Daniel Romo

      Article first published online: 14 JUL 2011 | DOI: 10.1002/anie.201104527

      Thumbnail image of graphical abstract

      A high ratio of C[BOND]C bond-forming steps and a high degree of stereocontrol characterizes the first total synthesis of (+)-omphadiol. In their Communication on page 7537 ff., D. Romo and G. Lui report a facile conversion of (R)-carvone, from the spearmint plant, into omphadiol, from the jack-o'-lantern mushroom, via a versatile bicyclic β-lactone. Several one-pot or sequential processes and the absence of protecting groups contribute to the brevity of the synthesis.

  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. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Inside Cover: Molecular Lanthanoid–Transition-Metal Cluster through C[BOND]H Bond Activation by Polar Metal–Metal Bonds (Angew. Chem. Int. Ed. 33/2011) (page 7450)

      Dr. Mikhail V. Butovskii, Dr. Oleg L. Tok, Dr. Viktor Bezugly, Dr. Frank R. Wagner and Prof. Dr. Rhett Kempe

      Article first published online: 8 JUL 2011 | DOI: 10.1002/anie.201104288

      Thumbnail image of graphical abstract

      Multiple C[BOND]H bond activations give molecular lanthanoid–transition-metal clusters from heterobimetallic organometallic complexes. In their Communication on page 7695 ff. F. R. Wagner, R. Kempe, and co-workers show there is an increase in the delocalization of the metal–metal bonding electrons suggesting a possible transition sequence from the bimetallic complex to the intermetallic phase. (Background: photomontage (by Jana Kempe) of the Festspielhaus (Bayreuth) and the Semperoper (Dresden).)

  3. Back 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. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Back Cover: Artificial Molecular Clamp: A Novel Device for Synthetic Polymerases (Angew. Chem. Int. Ed. 33/2011) (page 7450)

      Dr. Yoshinori Takashima, Dr. Motofumi Osaki, Prof. Dr. Yoshihiro Ishimaru, Dr. Hiroyasu Yamaguchi and Prof. Dr. Akira Harada

      Article first published online: 5 JUL 2011 | DOI: 10.1002/anie.201104186

      Thumbnail image of graphical abstract

      A synthetic polymerase including a cyclodextrin dimer is used to produce high-molecular-weight polymers. In their Communication on page 7524 ff., A. Harada and co-workers report that one CD moiety (green) of the dimer acts as the active site of the polymerization, whereas the other moiety (purple) serves as an artifical molecular clamp that propagates the polymerization by holding the polymer chain (blue). This system is reminiscent of the DNA polymerase shown in the background of the picture.

  4. Editorial

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. You have free access to this content
      Editorial: The Importance of Chemistry for the Future of the Pharma Industry (pages 7452–7453)

      Prof. Dr. Hanno Wild, Dr. Dirk Heimbach and Dr. Christoph Huwe

      Article first published online: 5 AUG 2011 | DOI: 10.1002/anie.201103888

  5. Graphical Abstract

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Emmanuel Lacôte (page 7474)

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201103453

      Thumbnail image of graphical abstract

      “The biggest problem that scientists face is willful scientific illiteracy. My biggest motivation is seeing my students leading the hunt …” This and more about Emmanuel Lacôte can be found on page 7474.

  8. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Vom Mikrofilm zur Wissensmaschine. Emanuel Goldberg – zwischen Medientechnik und Politik. By Michael Buckland. (page 7475)

      Horst Hennig

      Article first published online: 14 JUL 2011 | DOI: 10.1002/anie.201102476

      Thumbnail image of graphical abstract

      AVINUS-Verlag, Berlin 2010. 380 pp., hardcover € 38.00.—ISBN 978-3869380155

  9. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Enzymes

      Expanding the Enzyme Toolbox for Biocatalysis (pages 7476–7478)

      Dr. Jacob E. Vick and Prof. Dr. Claudia Schmidt-Dannert

      Article first published online: 4 JUL 2011 | DOI: 10.1002/anie.201100070

      Thumbnail image of graphical abstract

      We've got talent: New enzymes with novel reactivity are constantly added to the enzyme toolbox as exemplified by the berberine bridge enzyme (BBE). Analogues of 2, which are bioactive, have been successfully made from analogues of 1 using BBE. Such new enzymes hold the promise of convenient synthesis of potentially useful nonnatural products.

    2. Oxidative Cross-Coupling

      Palladium-Catalyzed Selective Dehydrogenative Cross-Couplings of Heteroarenes (pages 7479–7481)

      Dr. Xavier Bugaut and Prof. Dr. Frank Glorius

      Article first published online: 8 JUL 2011 | DOI: 10.1002/anie.201103106

      Thumbnail image of graphical abstract

      A nice couple: Two heteroaryls bearing no prefunctionalization can be cross-coupled efficiently through PdII catalysis to afford the biheteroaryl. The selectivity of this transformation probably finds its origin in the two mechanistically different metalation steps of C[BOND]H bonds.

  10. Essay

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Surface Patterning

      Cantilever-Free Scanning Probe Molecular Printing (pages 7482–7485)

      Louise R. Giam and Prof. Chad A. Mirkin

      Article first published online: 22 JUN 2011 | DOI: 10.1002/anie.201100839

      Thumbnail image of graphical abstract

      25 and 30 years after the invention of AFM and STM, respectively, cantilever-free scanning probe lithography tools such as polymer pen lithography (see picture) mark an important development in the evolution of molecular printing. These simple, robust, and inexpensive approaches allow researchers to create nanoscale and microscale features of various organic and inorganic materials on surfaces in arbitrary patterns.

  11. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Cross-Coupling

      Tosylhydrazones: New Uses for Classic Reagents in Palladium-Catalyzed Cross-Coupling and Metal-Free Reactions (pages 7486–7500)

      Prof. José Barluenga and Dr. Carlos Valdés

      Article first published online: 11 JUL 2011 | DOI: 10.1002/anie.201007961

      Thumbnail image of graphical abstract

      Never too old to rock 'n' roll: The investigation of tosylhydrazones—widely used intermediates in organic synthesis—as coupling partners in palladium-catalyzed and metal-free cross-coupling reactions has led to the discovery of powerful C[BOND]C and C[BOND]O bond-forming transformations. These reactions offer novel possibilities for the unconventional modification of carbonyl compounds (see examples of product types; Ts=p-toluenesulfonyl).

  12. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Flow Chemistry

      Deciding Whether To Go with the Flow: Evaluating the Merits of Flow Reactors for Synthesis (pages 7502–7519)

      Dr. Ryan L. Hartman, Jonathan P. McMullen and Prof. Klavs F. Jensen

      Article first published online: 27 JUN 2011 | DOI: 10.1002/anie.201004637

      Thumbnail image of graphical abstract

      Flow or batch? The fine chemicals and pharmaceutical industries are transforming how their products are manufactured, where economically favorable, from traditional batchwise processes to continuous flow. This evolution is impacting synthetic chemistry on all scales—from the laboratory to full production. This Review discusses the relative merits of batch and microflow reactors for performing synthetic chemistry in the laboratory.

  13. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. X-ray/Neutron Crystallography

      Identification of the Elusive Hydronium Ion Exchanging Roles with a Proton in an Enzyme at Lower pH Values (pages 7520–7523)

      Dr. Andrey Y. Kovalevsky, Dr. B. L. Hanson, Dr. S. A. Mason, Dr. T. Yoshida, Dr. S. Z. Fisher, Dr. M. Mustyakimov, Dr. V. T. Forsyth, Dr. M. P. Blakeley, Dr. D. A. Keen and Dr. Paul Langan

      Article first published online: 23 MAY 2011 | DOI: 10.1002/anie.201101753

      Thumbnail image of graphical abstract

      Visible to neutrons: Although thought to be involved in biological processes, hydronium ions had never been identified in biomacromolecular crystallographic structures. A hydronium ion has now been found by neutron and X-ray crystallography to interchange with metal cofactors in the active site of an enzyme. Under more acidic conditions, the hydronium ion is dehydrated to a proton, and the binding site collapses (see picture).

    2. Supramolecular Catalysis

      Artificial Molecular Clamp: A Novel Device for Synthetic Polymerases (pages 7524–7528)

      Dr. Yoshinori Takashima, Dr. Motofumi Osaki, Prof. Dr. Yoshihiro Ishimaru, Dr. Hiroyasu Yamaguchi and Prof. Dr. Akira Harada

      Article first published online: 8 JUL 2011 | DOI: 10.1002/anie.201102834

      Thumbnail image of graphical abstract

      Synthetic polymerases composed of a cyclodextrin (CD) dimer yield high-molecular-weight polymers of cyclic esters without using solvents and co-catalysts. One CD moiety is attached to the active site of a supramolecular catalyst and propagates the polymerization by serving as artificial molecular clamp (see picture). The other CD moiety initiates the ring-opening polymerization.

    3. Dinickel Complexes

      Reversible Halide-Modulated Nickel–Nickel Bond Cleavage: Metal–Metal Bonds as Design Elements for Molecular Devices (pages 7529–7532)

      Steven T. Chao, Nadia C. Lara, Sibo Lin, Michael W. Day and Prof. Theodor Agapie

      Article first published online: 27 JUN 2011 | DOI: 10.1002/anie.201102797

      Thumbnail image of graphical abstract

      The dinickel chloride affair: In dinuclear nickel(I) complexes supported by a tris(phosphinoaryl)benzene and stabilized by metal–arene interactions, chloride addition causes reversible Ni[BOND]Ni bond cleavage that induces 180° rotation around an aryl–aryl bond (see scheme). A dinickel–chloride moiety was found to rotate around the bridging arene by a mechanism involving breaking and forming Ni[BOND]P bonds.

    4. Heterogeneous Catalysis

      Catalytic Oxidation of Silanes by Carbon Nanotube–Gold Nanohybrids (pages 7533–7536)

      Dr. Jubi John, Dr. Edmond Gravel, Dr. Agnès Hagège, Dr. Haiyan Li, Dr. Thierry Gacoin and Dr. Eric Doris

      Article first published online: 5 JUL 2011 | DOI: 10.1002/anie.201101993

      Thumbnail image of graphical abstract

      Turning over silanes: The first nanotube-based catalytic system for silane oxidation is reported (see scheme). The reusable gold–nanotube hybrid cleanly oxidizes both alkyl and aryl silanes in high yields, under mild reaction conditions, and compares most favorably to any other catalytic system in terms of overall efficacy and turnover values.

    5. Total Synthesis

      Total Synthesis of (+)-Omphadiol (pages 7537–7540)

      Gang Liu and Prof. Dr. Daniel Romo

      Article first published online: 14 JUL 2011 | DOI: 10.1002/anie.201102289

      Thumbnail image of graphical abstract

      A smooth transition from (R)-carvone to a β-lactone and then to (+)-omphadiol characterizes the first total synthesis of this sesquiterpene, which was achieved in ten steps and 18 % overall yield. All six contiguous stereogenic centers were introduced in a highly diastereoselective manner. Key steps include a nucleophile-promoted aldol lactonization, a single-pot, sequential intra-/intermolecular dialkylation, a tandem olefin isomerization/RCM, and a cyclopropanation with unusual facial selectivity.

    6. Protein–Mineral Interactions

      Single-Molecule Determination of the Face-Specific Adsorption of Amelogenin’s C-Terminus on Hydroxyapatite (pages 7541–7545)

      Dr. Raymond W. Friddle, Keith Battle, Vasily Trubetskoy, Dr. Jinhui Tao, Dr. E. Alan Salter, Prof. Janet Moradian-Oldak, Dr. James J. De Yoreo and Prof. Andrzej Wierzbicki

      Article first published online: 27 JUN 2011 | DOI: 10.1002/anie.201100181

      Thumbnail image of graphical abstract

      On the face of it: An atomic force microscopy tip, functionalized with Amelogenin protein (Amel), is used to directly determine the single-molecule, face-specific free energy of Amel binding to crystalline hydroxyapatite (see picture). The experimental values compare well with those from molecular dynamics simulations and enable the key interactions controlling face-specific binding to be identified.

    7. Nanotechnology

      Simultaneous Concentration and Separation of Proteins in a Nanochannel (pages 7546–7550)

      Dr. David W. Inglis, Prof. Ewa M. Goldys and Dr. Nils P. Calander

      Article first published online: 27 JUN 2011 | DOI: 10.1002/anie.201100236

      Thumbnail image of graphical abstract

      Balancing the forces: Conductivity gradient focusing in a nanochannel achieves simultaneous separation and concentration of proteins without a temperature gradient, membrane, matrix, ampholytes, or external pump. The electrophoretic force (see picture; red arrow) that dominates at the low-salt side (−) balances the electro-osmotic force (blue) at the high-salt side (+).

    8. Redox Proteomics

      Highly Selective Fluorescent Probe for Vicinal-Dithiol-Containing Proteins and In Situ Imaging in Living Cells (pages 7551–7556)

      Chusen Huang, Qin Yin, Prof. Dr. Weiping Zhu, Prof. Dr. Yi Yang, Xin Wang, Prof. Dr. Xuhong Qian and Prof. Dr. Yufang Xu

      Article first published online: 30 JUN 2011 | DOI: 10.1002/anie.201101317

      Thumbnail image of graphical abstract

      It pays to be direct: In a rapid and specific approach to the detection of vicinal-dithiol-containing proteins (VDPs), the use of a fluorescent probe (see picture) enabled the direct readout of fluorescence. This approach based on fluorescence polarization, electrophoresis, and the direct imaging of VDPs permits the noninvasive study of VDPs both in vitro and in living cells and offers insight into their potential roles in cell function.

    9. Biosensors

      Quantitative 3D Analysis of Nitric Oxide Diffusion in a 3D Artery Model Using Sensor Particles (pages 7557–7561)

      Dr. Michya Matsusaki, Suzuka Amemori, Koji Kadowaki and Prof. Mitsuru Akashi

      Article first published online: 30 JUN 2011 | DOI: 10.1002/anie.201008204

      Thumbnail image of graphical abstract

      NO blood lost: Three-dimensional analysis of nitric oxide (NO) diffusion in a blood vessel in response to drug stimulation was achieved by using 3D artery models including NO sensor particles (see picture). The quantity and diffusion distance of NO in the five-layered models were almost the same as those for the in vivo blood vessel response. This method enables an in vitro bioassay of tissue responses instead of animal experiments.

    10. Porous Networks

      Two-Dimensional Molecular Porous Networks Formed by Trimesic Acid and 4,4′-Bis(4-pyridyl)biphenyl on Au(111) through Hierarchical Hydrogen Bonds: Structural Systematics and Control of Nanopore Size and Shape (pages 7562–7566)

      Hailin Liang, Wei Sun, Xin Jin, Heng Li, Jianlong Li, Prof. Dr. Xinquan Hu, Prof. Dr. Boon K. Teo and Prof. Dr. Kai Wu

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201101477

      Thumbnail image of graphical abstract

      Pores for thought: The pore size and pore shape (including “rectangular”, triangular, tetragonal, diamond, pentagonal, and hexagonal) in binary molecular porous networks formed by trimesic acid (TMA) and 4,4′-bis(4-pyridyl)biphenyl (BPBP) molecules on Au(111) is tuned simply through changing the TMA:BPBP ratio (see picture).

    11. Frustrated Lewis Pairs

      Capture of NO by a Frustrated Lewis Pair: A New Type of Persistent N-Oxyl Radical (pages 7567–7571)

      Allan Jay P. Cardenas, Brooks J. Culotta, Prof. Timothy H. Warren, Prof. Dr. Stefan Grimme, Dipl.-Chem. Annika Stute, Dr. Roland Fröhlich, Dr. Gerald Kehr and Prof. Dr. Gerhard Erker

      Article first published online: 1 JUL 2011 | DOI: 10.1002/anie.201101622

      Thumbnail image of graphical abstract

      NO your pairs: The intramolecular frustrated Lewis pair (FLP) Mes2PCH2CH2B(C6F5)2 captures NO to give the novel N-oxyl radical P/B-FLP-NO. (see scheme). Coordination of NO to the FLP incites H-atom abstraction reactivity with cyclohexene and ethylbenzene to give P/B-FLP-NOH and the O-functionalized P/B-FLP-NOR species.

    12. Molecular Machines

      Template-Induced Screw Motions within an Aromatic Amide Foldamer Double Helix (pages 7572–7575)

      Dr. Yann Ferrand, Quan Gan, Dr. Brice Kauffmann, Prof. Hua Jiang and Dr. Ivan Huc

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201101697

      Thumbnail image of graphical abstract

      Screwed in place: An anti-parallel double-helical aromatic oligoamide foldamer was shown to bind to a series of rodlike guests of various lengths upon the winding of the duplex around the guests (see scheme). Solid-state crystal structures of the host–guest complexes show that the two strands of the duplex undergo a relative screw motion to adjust the distance between hydrogen-bond donors located at the end of one of their extremities so that they bind to hydrogen-bond acceptors of the guest.

    13. NMR Spectroscopy

      Structural Discrimination in Small Molecules by Accurate Measurement of Long-Range Proton–Carbon NMR Residual Dipolar Couplings (pages 7576–7580)

      Pablo Trigo-Mouriño, Armando Navarro-Vázquez, Jinfa Ying, Roberto R. Gil and Ad Bax

      Article first published online: 12 JUL 2011 | DOI: 10.1002/anie.201101739

      Thumbnail image of graphical abstract

      Accurate measurement of long-range CH residual dipolar couplings (RDCs; 2DCH and 3DCH) by a new selective J-scaled HSQC experiment significantly improves the structural discrimination power of RDCs in small molecules with multiple stereogenic centers. The current approach was demonstrated with 10-epi-8-deoxycumambrin B, a tricyclic natural compound with five stereogenic centers (see figure; SVD=singular value decomposition).

    14. Cancer Therapeutics

      Multifunctional Nanoparticles for Targeted Chemophotothermal Treatment of Cancer Cells (pages 7581–7586)

      Dr. Sun-Mi Lee, Huiyul Park, Joung-Woo Choi, Prof. Young Nyun Park, Prof. Chae-Ok Yun and Prof. Kyung-Hwa Yoo

      Article first published online: 30 JUN 2011 | DOI: 10.1002/anie.201101783

      Thumbnail image of graphical abstract

      Drug and heat delivery to tumors by active targeting with Herceptin-conjugated doxorubicin-loaded poly(ethylene glycol)–poly(lactic-co-glycolic acid)–Au half-shell nanoparticles (HER-DOX-PLGA-Au H-S NPs) is more effective than passive targeting with their HER-free counterparts (DOX-PLGA-Au H-S NPs). Thus, on NIR irradiation, higher intratumoral temperatures were reached in tumor-bearing mice that were treated with the HER-conjugated particles (see picture).

    15. Functional Nanocrystals

      A Simple Reducing Approach Using Amine To Give Dual Functional EuSe Nanocrystals and Morphological Tuning (pages 7587–7591)

      Chuanxi Wang, Dan Zhang, Lin Xu, Yingnan Jiang, Prof. Fengxia Dong, Prof. Bai Yang, Prof. Kui Yu and Prof. Quan Lin

      Article first published online: 4 JUL 2011 | DOI: 10.1002/anie.201102780

      Thumbnail image of graphical abstract

      Amine for improvement: A non-injection approach using an amine as a reducing agent is developed to produce spherical EuSe nanocrystals (NCs) exhibiting blue emission (peaking at 403 nm with 2.8 % quantum yield) and room-temperature magnetic coercivity of 80.2 Oe (see scheme). The NC morphologies can be controlled easily to be hollow, spherical, or rodlike.

    16. Gold Cations

      The Interaction of Gold(I) Cations with 1,3-Dienes (pages 7592–7595)

      Rajashekharayya A. Sanguramath, Dr. Thomas N. Hooper, Dr. Craig P. Butts, Prof. Michael Green, Prof. John E. McGrady and Dr. Christopher A. Russell

      Article first published online: 5 JUL 2011 | DOI: 10.1002/anie.201102750

      Thumbnail image of graphical abstract

      Slip-sliding away: Gold(I) cations bind to only one double bond of a 1,3-diene unit but can glide over the C4 backbone on a low-activation-energy pathway. However, the binding mode is influenced by substituents on the diene backbone, which also induces a significantly higher barrier to migration.

    17. Ultrafast Dynamics

      Photoinduced Symmetry-Breaking Charge Separation: The Direction of the Charge Transfer (pages 7596–7598)

      Vesna Markovic, Diego Villamaina, Dr. Igor Barabanov, Dr. Latevi Max Lawson Daku and Prof. Dr. Eric Vauthey

      Article first published online: 4 JUL 2011 | DOI: 10.1002/anie.201102601

      Thumbnail image of graphical abstract

      Even flow: Photoinduced symmetry-breaking charge separation takes place in a few picoseconds in a 1,3-bis(perylene)propane dyad in polar solvents. Polarized transient absorption measurements show that the direction of the charge flow is random and entirely governed by the fluctuations of the solvent orientation around the dyad.

    18. Catalytic Amination

      Improved Ruthenium-Catalyzed Amination of Alcohols with Ammonia: Synthesis of Diamines and Amino Esters (pages 7599–7603)

      Sebastian Imm, Sebastian Bähn, Prof. Dr. Min Zhang, Lorenz Neubert, Dr. Helfried Neumann, Dr. Florian Klasovsky, Dr. Jan Pfeffer, Dr. Thomas Haas and Prof. Dr. Matthias Beller

      Article first published online: 5 JUL 2011 | DOI: 10.1002/anie.201103199

      Thumbnail image of graphical abstract

      Diamination of diols: The first homogeneously catalyzed diaminations of primary and secondary diols with ammonia give the corresponding diamines. Other primary as well as secondary alcohols including hydroxy-substituted esters can also be efficiently converted to primary amines. This atom-efficient and selective amination method proceeds in an ammonia atmosphere without additional hydrogen sources.

    19. Natural Products

      A Short and Efficient Synthesis of Neodysiherbaine A by Using Catalytic Oxidative Cyclization (pages 7604–7606)

      Prof. Timothy J. Donohoe, Paul C. M. Winship, Matthew R. Tatton and Dr. Peter Szeto

      Article first published online: 27 JUN 2011 | DOI: 10.1002/anie.201102525

      Thumbnail image of graphical abstract

      To the point: The synthesis of the title compound was achieved with 24 % overall yield through a sequence that has just seven linear steps (see scheme). Key points are the facial selectivity displayed by an oxocarbenium ion derived from a ribopyranose system and an osmium-catalyzed oxidative cyclization that is compatible with several acid-sensitive groups.

    20. Carbenes

      Electronic Properties and Reactivity of an Isolable Phosphagermaheterocyclic Carbene (pages 7607–7610)

      Dr. Dumitru Ghereg, Sonia Ladeira, Dr. Nathalie Saffon, Dr. Jean Escudié and Prof. Dr. Heinz Gornitzka

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201102500

      Thumbnail image of graphical abstract

      A highly reactive phosphagermacarbene (PGeHC) was synthesized by [3+2] cycloaddition between phosphagermaallene Tip(tBu)Ge[DOUBLE BOND]C[DOUBLE BOND]PMes* (Tip= 2,4,6-triisopropylphenyl; Mes*=2,4,6-tris-tert-butylphenyl) and diphenylketene. It forms complexes with [{Rh(CO)2Cl}2] and Me3P, and undergoes a Wittig-type reaction with diphenylketene (see scheme).

    21. Metal–Metal Bonds

      Theory-Guided Experiments on the Mechanistic Elucidation of the Reduction of Dinuclear Zinc, Manganese, and Cadmium Complexes (pages 7611–7615)

      Duan-Yen Lu, Prof. Dr. Jen-Shiang K. Yu, Ting-Shen Kuo, Dr. Gene-Hsiang Lee, Prof. Dr. Yu Wang and Prof. Dr. Yi-Chou Tsai

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201102296

      Thumbnail image of graphical abstract

      Two Mn[BOND]Mn-bonded dimanganese complexes, as well as the tetracadmium complex shown in the picture, were obtained by reduction of [M2{μ-κ2-Me2Si(NDipp)2}2] (M=Mn, Cd; Dipp=2,6-iPr2C6H3). Their structures are consistent with those of calculated intermediates in the reduction of [Zn2{μ-κ2-Me2Si(NDipp)2}2].

    22. Homogeneous Catalysis

      La/Ag Heterobimetallic Cooperative Catalysis: A Catalytic Asymmetric Conia-Ene Reaction (pages 7616–7619)

      Akinobu Matsuzawa, Tomoyuki Mashiko, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201102114

      Thumbnail image of graphical abstract

      A dual catalyst system: The cooperative function of a hard and soft Lewis acid (LaIII and AgI, respectively) in a catalyst system that includes an amide-based ligand 1 is crucial for simultaneous activation of intramolecular 1,3-dicarbonyl and alkyne moieties to afford enantioenriched cyclopentane derivatives (see scheme).

    23. Asymmetric Catalysis

      A Facile Pathway to Enantiomerically Enriched 3-Hydroxy-2-Oxindoles: Asymmetric Intramolecular Arylation of α-Keto Amides Catalyzed by a Palladium–DifluorPhos Complex (pages 7620–7623)

      Dr. Liang Yin, Prof. Dr. Motomu Kanai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 1 JUN 2011 | DOI: 10.1002/anie.201102158

      Thumbnail image of graphical abstract

      Less metal wastes: The first catalytic, enantioselective intramolecular aryl-transfer reaction of aryl triflates to ketones has been developed (see scheme; R1=R2=aromatic and aliphatic). This method features overall practicality, including substrate stability and accessibility (protecting-group free) plus no need for the use of stoichiometric amounts of metals.

    24. Multicomponent Reactions

      Dynamic One-Pot Three-Component Catalytic Asymmetric Transformation by Combination of Hydrogen-Bond-Donating and Amine Catalysts (pages 7624–7630)

      Dr. Shuangzheng Lin, Luca Deiana, Dr. Gui-Ling Zhao, Prof. Dr. Junliang Sun and Prof. Dr. Armando Córdova

      Article first published online: 24 JUN 2011 | DOI: 10.1002/anie.201101966

      Thumbnail image of graphical abstract

      In control: The first dynamic one-pot three-component asymmetric transformation between aldehydes, protected α-cyanoglycine esters, and enals catalyzed by a combination of a simple hydrogen-bond-donating catalyst and a chiral amine catalyst is disclosed. Polysubstituted proline derivatives, which have a quaternary α stereocenter, were synthesized with high endo-, diastereo-, and enantioselectivities (93–99 % ee).

    25. Natural Products

      Total Synthesis of Dinophysistoxin-2 and 2-epi-Dinophysistoxin-2 and Their PPase Inhibition (pages 7631–7635)

      Yucheng Pang, Chao Fang, Prof. Michael J. Twiner, Dr. Christopher O. Miles and Prof. Craig J. Forsyth

      Article first published online: 1 JUL 2011 | DOI: 10.1002/anie.201101741

      Thumbnail image of graphical abstract

      The first total syntheses of the title compounds highlight novel assemblies of the C1–C14 and C28–C38 domains, including an unexpected diastereoselectivity in the Sharpless asymmetric dihydroxylation of an alkene at C1[DOUBLE BOND]C2. PPase inhibition assays revealed that 2-epi-DTX-2 is at least 1 to 2 orders of magnitude less potent than DTX-2, thus indicating that the configuration at C2 in DTX-2 is crucial for potent inhibition (see picture).

    26. Microwave Chemistry

      Activation and Deactivation of a Chemical Transformation by an Electromagnetic Field: Evidence for Specific Microwave Effects in the Formation of Grignard Reagents (pages 7636–7640)

      Bernhard Gutmann, Alexander M. Schwan, Benedikt Reichart, Christian Gspan, Prof. Dr. Ferdinand Hofer and Prof. Dr. C. Oliver Kappe

      Article first published online: 7 JUN 2011 | DOI: 10.1002/anie.201100856

      Thumbnail image of graphical abstract

      It's field density, not temperature! Modifying the electric field strength in a microwave experiment can completely change the outcome of a reaction. Whereas a low field strength in Grignard reagent formation from Mg metal and aryl halide leads to acceleration of the initiation step, using a high field strength at the same temperature suppresses Mg insertion, favoring solvent decomposition and passivation of the Mg metal (see scheme).

    27. Natural Products

      Total Synthesis of the Chlorine-Containing Hapalindoles K, A, and G (pages 7641–7644)

      Aroop Chandra and Prof. Dr. Jeffrey N. Johnston

      Article first published online: 7 JUL 2011 | DOI: 10.1002/anie.201100957

      Thumbnail image of graphical abstract

      A common approach: Overall brevity in the synthesis of the title compounds (see scheme) is achieved by a sequential electrophilic aromatic substitution of indole and a regio- and diastereoselective intermolecular Diels–Alder cycloaddition to establish the key precursor—a neopentyl chloride. A stereoselective Ritter reaction and dehydration are used for the installation of the isonitrile unit.

    28. Protein Chemical Synthesis

      Protein Chemical Synthesis by Ligation of Peptide Hydrazides (pages 7645–7649)

      Ge-Min Fang, Yi-Ming Li, Fei Shen, Yi-Chao Huang, Jia-Bin Li, Yun Lin, Hong-Kui Cui and Prof. Dr. Lei Liu

      Article first published online: 6 JUN 2011 | DOI: 10.1002/anie.201100996

      Thumbnail image of graphical abstract

      pH determines selectivity: The ligation of peptide hydrazides is a new method for protein chemical synthesis that is complementary to native chemical ligation. Peptide hydrazides may be the long-sought reagent equivalent to a “thioester synthon”, one that is stable to the conditions of native chemical ligation.

    29. Heterogeneous Catalysis

      You have full text access to this OnlineOpen article
      Theory of the Kinetics of Chemical Potentials in Heterogeneous Catalysis (pages 7650–7654)

      Dr. Jun Cheng and Prof. Dr. P. Hu

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201101459

      Thumbnail image of graphical abstract

      Simple and powerful: The reaction kinetics at surfaces of heterogeneous catalysts is reformulated in terms of the involved chemical potentials. Based on this formulism, an approach of searching for good catalysts is proposed without recourse to extensive calculations of reaction barriers and detailed kinetic analyses. (see picture; R=reactant, I=surface intermediate, P=product, and equation image=standard chemical potential).

    30. Trifluoromethylation

      Simple, Stable, and Easily Accessible Well-Defined CuCF3 Aromatic Trifluoromethylating Agents (pages 7655–7659)

      Dr. Olesya A. Tomashenko, Eduardo C. Escudero-Adán, Dr. Marta Martínez Belmonte and Dr. Vladimir V. Grushin

      Article first published online: 22 JUN 2011 | DOI: 10.1002/anie.201101577

      Thumbnail image of graphical abstract

      Give me an F: Exceptionally easy to make in over 90 % yield (see scheme) and air-stable in the solid state, [(Ph3P)3Cu(CF3)] is a remarkable example of a rarely encountered well-defined Cu(I) trifluoromethylating agent and a convenient starting material for the synthesis of other CuCF3 complexes, such as [(phen)Cu(PPh3)(CF3)].

    31. Anticoagulant Nanoparticles

      Gold Nanoparticles Presenting Hybridized Self-Assembled Aptamers That Exhibit Enhanced Inhibition of Thrombin (pages 7660–7665)

      Yen-Chun Shiang, Chia-Lun Hsu, Prof. Chih-Ching Huang and Prof. Huan-Tsung Chang

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201101718

      Thumbnail image of graphical abstract

      DNA hybridization of thrombin-binding aptamers (TBAs) to form a self-assembled arranged monolayer on gold nanoparticles (Au NPs) was used to control the coagulation activity of thrombin. The hTBA15/hTBA29/cDNA-Au NPs provided flexibility and a suitable orientation and distance between the hTBA15 and hTBA29 units for bivalent binding, allowing strong interactions with thrombin and extremely high anticoagulant potency.

    32. N-Heterocyclic Carbenes

      Double C[BOND]H Bond Activation of C(sp3)H2 Groups for the Preparation of Complexes with Back-to-Back Bisimidazolinylidenes (pages 7666–7669)

      Amparo Prades, Dr. Macarena Poyatos, Dr. José A. Mata and Prof. Eduardo Peris

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201101806

      Thumbnail image of graphical abstract

      Two-headed carbenes: N-heterocyclic carbene complexes of rhodium and iridium were obtained by the double C[BOND]H activation of CH2 groups in N heterocycles (see structure: C gray, N blue, Cl green, Ir pink). The reaction constitutes a valuable approach to new carbene ligands with unprecedented architectures.

    33. Synthetic Methods

      Assembly of Substituted 2-Alkylquinolines by a Sequential Palladium-Catalyzed C[BOND]N and C[BOND]C Bond Formation (pages 7670–7673)

      Prof. Dr. Yoshio Matsubara, Saori Hirakawa, Prof. Dr. Yoshihiro Yamaguchi and Prof. Dr. Zen-ichi Yoshida

      Article first published online: 22 JUN 2011 | DOI: 10.1002/anie.201102076

      Thumbnail image of graphical abstract

      Diversity: A range of substituted 2-alkylquinolines can be prepared in a general and efficient synthetic approach that employs mild reaction conditions (see scheme). The synthesis is based on a sequential palladium-catalyzed C[BOND]N and C[BOND]C bond formation, followed by palladium-catalyzed aromatization, and results in the formation of the desired compounds in one step.

    34. Isotope Effects

      No Contribution of an Inductive Effect to Secondary Deuterium Isotope Effects on Acidity (pages 7674–7676)

      Prof. Charles L. Perrin and Agnes Flach

      Article first published online: 24 JUN 2011 | DOI: 10.1002/anie.201102125

      Thumbnail image of graphical abstract

      Effect and cause: Secondary deuterium isotope effects on the acidity of the deuterated compounds 14 were measured by using an NMR titration method applicable to a mixture and capable of very high accuracy. Variable-temperature experiments show that these isotope effects are due only to changes in vibrational frequencies. These findings refute an inductive origin for these isotope effects.

    35. Organometallic Complexes

      Reactivity of a Scandium Terminal Imido Complex Towards Unsaturated Substrates (pages 7677–7680)

      Jiaxiang Chu, Erli Lu, Zhixiao Liu, Prof. Dr. Yaofeng Chen, Dr. Xuebing Leng and Dr. Haibin Song

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201102267

      Thumbnail image of graphical abstract

      A complex complex: The reactions of a scandium terminal imido complex with a series of unsaturated substrates, including CO2, PhCN, methyl methacrylate (MMA), cyclopentadiene, PhNCO, and propylene oxide, are presented (see scheme). A variety of intriguing products are formed from this complex. Ar=2,6-(iPr)2C6H3.

    36. Asymmetric Catalysis

      Chiral Sulfoxide-Olefin Ligands: Completely Switchable Stereoselectivity in Rhodium-Catalyzed Asymmetric Conjugate Additions (pages 7681–7685)

      Guihua Chen, Jiangyang Gui, Dr. Liangchun Li and Prof. Dr. Jian Liao

      Article first published online: 1 JUL 2011 | DOI: 10.1002/anie.201102586

      Thumbnail image of graphical abstract

      Have it both ways: A novel class of chiral sulfoxide-olefin ligands was synthesized from a single chiral source. These ligands were evaluated in rhodium-catalyzed 1,4-additions of arylboronic acids to electron-deficient olefins, and remarkable olefin-directed reversal of stereoselectivity (up to >99 % ee, R isomer; 98 % ee, S isomer) was observed when the reversal ligand pair L1 (branched olefin) and L2 (linear olefin) were utilized (see scheme).

    37. Arylation Reactions

      Lewis Acid Promoted Benzylic Cross-Couplings of Pyridines with Aryl Bromides (pages 7686–7690)

      Dr. Stéphanie Duez, M. Sc. Andreas K. Steib, M. Sc. Sophia M. Manolikakes and Prof. Dr. Paul Knochel

      Article first published online: 30 JUN 2011 | DOI: 10.1002/anie.201103074

      Thumbnail image of graphical abstract

      Either ZnCl2, Sc(OTf)3 , or BF3⋅OEt2 can promote the palladium-catalyzed arylation of methylpyridines and related heterocycles (see example). The complexation of the Lewis acid to the nitrogen atom in the heterocycle facilitates the reductive elimination, leading to various arylated pyridines in high yields. BF3⋅OEt2 was also found to promote highly regioselective metalations in the case of 2,4-lutidine.

    38. Phytochemistry

      A Desulfatation–Oxidation Cascade Activates Coumarin-Based Cross-Linkers in the Wound Reaction of the Giant Unicellular Alga Dasycladus vermicularis (pages 7691–7694)

      Dr. Matthew Welling, Prof. Dr. Cliff Ross and Prof. Dr. Georg Pohnert

      Article first published online: 30 JUN 2011 | DOI: 10.1002/anie.201100908

      Thumbnail image of graphical abstract

      Plugged up: A rapid and efficient cascade of desulfatation, oxidation, and cross-linking mediates wound sealing in the giant-celled alga Dasycladus vermicularis (see picture). UV and fluorescence studies and mass spectrometry show the wound plug is a coumarin-based polymer.

    39. Metal–Metal Bonding

      Molecular Lanthanoid–Transition-Metal Cluster through C[BOND]H Bond Activation by Polar Metal–Metal Bonds (pages 7695–7698)

      Dr. Mikhail V. Butovskii, Dr. Oleg L. Tok, Dr. Viktor Bezugly, Dr. Frank R. Wagner and Prof. Dr. Rhett Kempe

      Article first published online: 29 JUN 2011 | DOI: 10.1002/anie.201102363

      Thumbnail image of graphical abstract

      Cp glue: A chiral four-coordinate organolanthanoid complex, which has an unsupported metal–metal bond, reacts to give a lanthanoid–transition-metal cluster with two-electron multicenter metal–metal bonds (see structure). The reaction proceeds through C[BOND]H bond activation by the polar metal–metal bonds and affords a 1,2-dimetallation of one Cp ligand of the metallocene moiety.

    40. Muscle Contraction

      Photocontrol of Contracting Muscle Fibers (pages 7699–7702)

      Dr. Christian Hoppmann, Dr. Peter Schmieder, Petra Domaing, Gabriela Vogelreiter, Jenny Eichhorst, Dr. Burkhard Wiesner, Prof. Dr. Ingo Morano, Prof. Dr. Karola Rück-Braun and Dr. Michael Beyermann

      Article first published online: 7 JUL 2011 | DOI: 10.1002/anie.201101398

      Thumbnail image of graphical abstract

      A twitch in time: Light-directed inhibition of the interaction between α-1-syntrophin and neuronal NO synthase (nNOS) in living skeletal muscle with a cell-permeable photoswitchable nNOS-derived peptide ligand results in photocontrol of muscle performance and nitric oxide signaling.

  14. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Editorial
    6. Graphical Abstract
    7. News
    8. Author Profile
    9. Book Review
    10. Highlights
    11. Essay
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. You have free access to this content
      Preview: Angew. Chem. Int. Ed. 34/2011 (page 7703)

      Article first published online: 5 AUG 2011 | DOI: 10.1002/anie.201190066

SEARCH

SEARCH BY CITATION