Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 33

August 13, 2012

Volume 51, Issue 33

Pages 8123–8391

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
    1. You have free access to this content
      Cover Picture: Spectroscopic Observation of a Group 12 Oxyfluoride: A Matrix-Isolation and Quantum-Chemical Investigation of Mercury Oxyfluorides (Angew. Chem. Int. Ed. 33/2012) (page 8123)

      Prof. Lester Andrews, Prof. Xuefeng Wang, Dr. Yu Gong, Dipl.-Chem. Tobias Schlöder, Dr. Sebastian Riedel and Marvin J. Franger

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201205441

      Thumbnail image of graphical abstract

      Mercury amalgam dental fillingsprovide a source for laser-ablated mercury atoms as reaction partners with OF2 to produce mercury difluoride and two major oxyfluorides, as shown by S. Riedel et al. in their Communication on page 8235 ff. Assignments for OHgF and FOHgF trapped in solid neon and argon in the IR spectrum were supported by calculations. Unpaired electron spin resides on oxygen in OHgF, with mercury in the +II oxidation state.

    2. You have free access to this content
      Inside Cover: Surface Wetting in Liquid–Liquid–Solid Triphase Systems: Solid-Phase-Independent Transition at the Liquid–Liquid Interface by Lewis Acid–Base Interactions (Angew. Chem. Int. Ed. 33/2012) (page 8124)

      Dr. Mingjie Liu, Dr. Zhongxin Xue, Prof. Huan Liu and Prof. Lei Jiang

      Article first published online: 17 JUL 2012 | DOI: 10.1002/anie.201205174

      Thumbnail image of graphical abstract

      Lewis acid–base interactions at the oil–water interface can greatly decrease the liquid–liquid interfacial tension and induce an oleophilic-to-superoleophobic wetting transition on a nonresponsive microstructured surface. In their Communication on page 8348 ff., L. Jiang and co-workers report a strategy for tunable surface wettability that is independent of the solid phase. Oil-water-solid triphase systems may find new applications in chemical reactions.

    3. You have free access to this content
      Inside Back Cover: Optimized Use of Reversible Binding for Fast and Selective NMR Localization of Caged XenonZ202481 (Angew. Chem. Int. Ed. 33/2012) (page 8393)

      Martin Kunth, Jörg Döpfert, Dr. Christopher Witte, Federica Rossella and Dr. Leif Schröder

      Article first published online: 18 JUL 2012 | DOI: 10.1002/anie.201205177

      Thumbnail image of graphical abstract

      Hyperpolarized 129Xe trapped in cryptophane cages in different solvents experiences different NMR chemical shifts; in one case they are separated by 131 Hz. In their Communication on page 8217 ff., L. Schröder et al. present an encoding method with optimal use of hyperpolarization for snapshot imaging with high spectral selectivity.

    4. You have free access to this content
      Back Cover: Template-Directed Synthesis in 3′- and 5′-Direction with Reversible Termination (Angew. Chem. Int. Ed. 33/2012) (page 8394)

      Dipl.-Chem. Andreas Kaiser, Dipl.-Chem. Sebastian Spies, Dr. Tanja Lommel and Prof. Clemens Richert

      Article first published online: 12 JUL 2012 | DOI: 10.1002/anie.201204827

      Thumbnail image of graphical abstract

      Simultaneous chemical primer extension in both 3′- and 5′-direction is reported by C. Richert et al. in their Communication on page 8299 ff. The use of magnetic beads as a solid support and azidomethyloxycarbonyl moieties as protecting groups provided control over the extension steps directed by a DNA sequence. The method combines features of replication and of automated DNA synthesis.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
  4. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
    1. Wolfgang A. Herrmann (pages 8148–8149)

      Article first published online: 15 MAY 2012 | DOI: 10.1002/anie.201201341

      Thumbnail image of graphical abstract

      “The greatest scientific advance of the last decade was the decoding of the human genome. When I was eighteen I wanted to become a chemist, and so I did. …” This and more about Wolfgang A. Herrmann can be found on page 8148.

  5. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
  6. Meeting Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
    1. Orbital Approach to the Electronic Structure of Solids. By Enric Canadell, Marie-Liesse Doublet and Christophe Iung. (page 8155)

      Wojciech Grochala

      Article first published online: 10 JUL 2012 | DOI: 10.1002/anie.201203709

      Thumbnail image of graphical abstract

      Oxford University Press, Oxford 2012. 364 pp., hardcover, £ 45.00.—ISBN 978-0199534937

  8. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
    1. Gold Catalysis

      Dinuclear Gold Catalysis: Are Two Gold Centers Better than One? (pages 8156–8159)

      Adrián Gómez-Suárez and Prof. Dr. Steven P. Nolan

      Article first published online: 18 JUL 2012 | DOI: 10.1002/anie.201203587

      Thumbnail image of graphical abstract

      A common golden thread: The exact role of dinuclear gold species in catalysis has recently attracted considerable attention. Such well-defined complexes can now be isolated and fully characterized and may assist in elucidating the exact action of gold centers in gold-catalyzed reactions. In view of the latest developments in this area, possibilities now abound in terms of mechanistic exploration and novel catalyst design.

    2. Templated Catalysis

      A Molecular Tête-à-Tête Arranged by a Designed Adaptor Protein (pages 8160–8162)

      Christoph Meyer and Dr. Maja Köhn

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201203345

      Thumbnail image of graphical abstract

      Come together: The joining of two miniature proteins binding different protein targets in a synthetic adaptor protein is a novel way to induce proximity between proteins. The formation of a ternary complex was shown to cause the phosphorylation of a noninherent substrate (hDM2) by the kinase Hck. The approach holds promise to become a genetically encodable system to redirect enzyme activities in vivo.

    3. Homogeneous Catalysis

      Switchable Catalysis (pages 8163–8165)

      Prof. Dr. Ulrich Lüning

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201204567

      Thumbnail image of graphical abstract

      On/off catalysts: Control over catalysis can be gained when the catalysts can be switched between an active and a nonactive state by external stimuli. In recent examples, orthogonal signals—light, pH, or the addition of ions—are used for the switching.

  9. Minireview

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
    1. Protein–Protein Interactions

      Protein Tango: The Toolbox to Capture Interacting Partners (pages 8166–8176)

      Dr. Anna Rutkowska and Priv.-Doz. Dr. Carsten Schultz

      Article first published online: 11 JUN 2012 | DOI: 10.1002/anie.201201717

      Thumbnail image of graphical abstract

      In pairs: The key to understand living systems is enciphered in protein–protein interaction networks. For unraveling its complexity, a potent toolbox of small molecules (cross-linkers and chemical inducers of dimerization) is available to sense and induce the dynamic interaction processes in living cells.

  10. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
    1. Electroluminescence

      Luminescent Ionic Transition-Metal Complexes for Light-Emitting Electrochemical Cells (pages 8178–8211)

      Dr. Rubén D. Costa, Prof. Dr. Enrique Ortí, Dr. Henk J. Bolink, Filippo Monti, Dr. Gianluca Accorsi and Dr. Nicola Armaroli

      Article first published online: 6 AUG 2012 | DOI: 10.1002/anie.201201471

      Thumbnail image of graphical abstract

      LECtric lighting: The expansion of artificial illumination and the need for more efficient appliances is stimulating innovative lighting concepts. Light-emitting electrochemical cells (LECs) based on luminescent transition-metal complexes (see picture) stand out as promising devices for lighting panels, thanks to recent advances in their design, driving conditions, and their overall performance.

  11. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
    1. Asymmetric Catalysis

      Platinum-Catalyzed Asymmetric Hydrogenation: Spectroscopic Evidence for an O-H-O Hydrogen-Bond Interaction between Substrate and Modifier (pages 8212–8216)

      Fabian Meemken, Dr. Nobutaka Maeda, Prof. Dr. Konrad Hungerbühler and Prof. Dr. Alfons Baiker

      Article first published online: 27 JUN 2012 | DOI: 10.1002/anie.201203007

      Thumbnail image of graphical abstract

      The mighty cinchonidine: A diastereomeric surface complex in the asymmetric hydrogenation of ketopantolactone on chirally modified Pt is monitored by in situ ATR-IR spectroscopy, in combination with modulation excitation spectroscopy and phase-sensitive detection. Cinchonidine bound to the surface with its quinoline ring is shown to induce the chiral environment through a C9[BOND]O⋅⋅⋅H⋅⋅⋅O[DOUBLE BOND]C interaction (see scheme).

    2. Biosensors

      Optimized Use of Reversible Binding for Fast and Selective NMR Localization of Caged Xenon (pages 8217–8220)

      Martin Kunth, Jörg Döpfert, Dr. Christopher Witte, Federica Rossella and Dr. Leif Schröder

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201202481

      Thumbnail image of graphical abstract

      The NMR signal of hyperpolarized 129Xe trapped in cryptophane cages in different solvents experiences different chemical shifts. An encoding method is presented that involves the optimal use of reversible Xe binding and efficiently uses hyperpolarization. This method is utilized in nanomolar imaging, subsecond imaging, and time-resolved studies while maintaining high spectral selectivity.

    3. Trifluoromethylation

      Transition-Metal-Free Trifluoromethylaminoxylation of Alkenes (pages 8221–8224)

      Dr. Yi Li and Prof. Dr. Armido Studer

      Article first published online: 25 JUL 2012 | DOI: 10.1002/anie.201202623

      Thumbnail image of graphical abstract

      No transition metal! Fluorinated hypervalent-iodine reagents react with TEMPONa in the presence of an alkene under mild conditions to give the corresponding perfluoroalkylaminoxylation products. These radical addition/trapping reactions occur with high stereoselectivity using commercially available reagents, and the product alkoxyamines are readily transformed into the corresponding alcohols.

    4. N2 Activation

      Heterolytic Outer-Sphere Cleavage of H2 for the Reduction of N2 in the Coordination Sphere of Transition Metals—A DFT Study (pages 8225–8229)

      Dr. Markus Hölscher and Prof. Dr. Walter Leitner

      Article first published online: 10 JUL 2012 | DOI: 10.1002/anie.201202025

      Thumbnail image of graphical abstract

      Cleaved by frustration, an H2 molecule inserts into the void between the components of the frustrated Lewis pair 1, which consists of a dicationic ruthenium pincer complex as the Lewis acid and (tBu)3P as the Lewis base. The end-on-coordinated N2 in 1 accepts the hydride, and this is the initial step, which could, in principle, lead to the complete reduction of N2 to NH3.

    5. C[BOND]H Activation

      Selective Rhodium(III)-Catalyzed Cross-Dehydrogenative Coupling of Furan and Thiophene Derivatives (pages 8230–8234)

      Nadine Kuhl, Dr. Matthew N. Hopkinson and Prof. Dr. Frank Glorius

      Article first published online: 6 JUL 2012 | DOI: 10.1002/anie.201203792

      Thumbnail image of graphical abstract

      A hot couple: An unprecedented rhodium(III)-catalyzed cross-dehydrogenative coupling (CDC) of various furan and thiophene derivatives leads to valuable 2,2′-bi(heteroaryl) products in good yields and selectivities (see scheme). In addition, pyrroles and indoles can also be used as coupling partners, giving C3-arylated products.

    6. High Oxidation States

      Spectroscopic Observation of a Group 12 Oxyfluoride: A Matrix-Isolation and Quantum-Chemical Investigation of Mercury Oxyfluorides (pages 8235–8238)

      Prof. Lester Andrews, Prof. Xuefeng Wang, Dr. Yu Gong, Dipl.-Chem. Tobias Schlöder, Dr. Sebastian Riedel and Marvin J. Franger

      Article first published online: 18 JUL 2012 | DOI: 10.1002/anie.201204331

      Thumbnail image of graphical abstract

      Getting to the root of Hg: Experiments with amalgams as a source for laser-ablated Hg atoms as reaction partners with OF2 gave strong HgF2 IR absorptions and new bands in the Hg[BOND]F stretching region for OHgF and FOHgF molecules trapped in solid neon and argon. Assignment of these new bands to the first oxyfluoride of mercury, OHgF, and to the FOHgF insertion product is supported by quantum-chemical methods.

    7. Higher Fullerenes

      Four Isomers of C96 Fullerene Structurally Proven as C96Cl22 and C96Cl24 (pages 8239–8242)

      Prof. Dr. Shangfeng Yang, Tao Wei, Prof. Dr. Erhard Kemnitz and Prof. Dr. Sergey I. Troyanov

      Article first published online: 4 JUL 2012 | DOI: 10.1002/anie.201201775

      Thumbnail image of graphical abstract

      Direct proof of the cage connectivities of four isomers of C96, the highest isolable empty fullerene, has been achieved. C96 fractions, which were isolated from fullerene soot by recycling HPLC, were chlorinated and the resulting single crystals of C96Cl22 and C96Cl24 were studied by X-ray diffraction using synchrotron radiation. D2-C96(183)Cl24 (see structure; gray C, green Cl) was obtained in two crystalline modifications.

    8. Asymmetric Catalysis

      Asymmetric Epoxidation of Conjugated Olefins with Dioxygen (pages 8243–8246)

      Shota Koya, Yota Nishioka, Hirotaka Mizoguchi, Dr. Tatsuya Uchida and Prof. Tsutomu Katsuki

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201201848

      Thumbnail image of graphical abstract

      A complex situation: Asymmetric epoxidation of conjugated olefins was achieved at room temperature using ruthenium complex 1 as the catalyst and air as the oxidant to give epoxides in up to 95 % ee (see scheme). When the product was acid sensitive, the reaction was carried out at 0 °C under oxygen.

    9. Iron–Sulfur Clusters

      Isolation and Characterization of Stable Iron(I) Sulfide Complexes (pages 8247–8250)

      Meghan M. Rodriguez, Dr. Bryan D. Stubbert, Prof. Christopher C. Scarborough, Dr. William W. Brennessel, Dr. Eckhard Bill and Prof. Patrick L. Holland

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201202211

      Thumbnail image of graphical abstract

      The first examples of iron(I) sulfide complexes are presented, in contrast with the +2 and +3 oxidation states that are well-known in synthetic and biological systems. Spectroscopic and computational studies show a high-spin d7 configuration at the metal. Alkali metal cations play a key role in supporting the unusually low oxidation state.

    10. Biaryl Synthesis

      Cobalt-Catalyzed Direct Arylation and Benzylation by C[BOND]H/C[BOND]O Cleavage with Sulfamates, Carbamates, and Phosphates (pages 8251–8254)

      M. Sc. Weifeng Song and Prof. Dr. Lutz Ackermann

      Article first published online: 12 JUL 2012 | DOI: 10.1002/anie.201202466

      Thumbnail image of graphical abstract

      Inexpensive cobalt catalysts enable the first direct arylation and benzylation of (hetero)arenes with aryl carbamates, sulfamates, and phosphates with ample scope. The non-radical C[BOND]H/C[BOND]O arylation reaction even proved viable at ambient temperature.

    11. Organometallic Chemistry

      Synthesis and Reactivity of a Cationic Platinum(II) Alkylidene Complex (pages 8255–8258)

      Jesus Campos, Dr. Riccardo Peloso and Prof. Ernesto Carmona

      Article first published online: 6 JUL 2012 | DOI: 10.1002/anie.201202655

      Thumbnail image of graphical abstract

      Often proposed, hard to catch: The bis(platinacycle) trans-[Pt{P[2,6-(CH2)(Me)C6H3]iPr2}2] experiences α-hydride abstraction by action of Ph3C+PF6 to yield a trans-alkyl–alkylidene species. The electrophilicity of its {Pt[DOUBLE BOND]CH}+ unit is demonstrated by ylide formation by reaction with Lewis bases, stepwise hydrogenation, and carbene cross-coupling with N2C(H)CO2Et (see scheme).

    12. Amido/Imido Complexes

      The Dehydrogenation of Alcohols through a Concerted Bimetallic Mechanism Involving an Amido-Bridged Diiridium Complex (pages 8259–8263)

      Dipl.-Chem. Inmaculada Mena, Dr. Miguel A. Casado, Dr. Víctor Polo, Dr. Pilar García-Orduña, Prof. Fernando J. Lahoz and Prof. Luis A. Oro

      Article first published online: 9 JUL 2012 | DOI: 10.1002/anie.201202936

      Thumbnail image of graphical abstract

      From amido to imido: A dinuclear amido-bridged iridium complex promotes the dehydrogenation of alcohols, affording unusual mixed amido/imido Ir4 and bis(imido) Ir3 clusters. Theoretical calculations suggest that bridging μ-NH2 linkages are crucial to achieve the formation of hydrido amine diiridium species, as a result of a concerted net hydrogen transfer through a proposed eight-membered dimetallacycle.

    13. Asymmetric Catalysis

      Catalytic Asymmetric Claisen Rearrangement of Enolphosphonates: Construction of Vicinal Tertiary and All-Carbon Quaternary Centers (pages 8264–8267)

      Jiajing Tan, Dr. Cheol-Hong Cheon and Prof. Hisashi Yamamoto

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201203092

      Thumbnail image of graphical abstract

      A copper-catalyzed enantioselective Claisen rearrangement of easily accessible enolphosphonates using the commercially available PhBOX as the chiral ligand was developed. A wide range of rearrangement products with contiguous tertiary and all-carbon quaternary centers were obtained in excellent yields and stereoselectivities. The α-ketophosphonate substituent in the products could be easily transformed into other functional groups.

    14. Alkyl Migration

      A Versatile Ligand Platform that Supports Lewis Acid Promoted Migratory Insertion (pages 8268–8271)

      Dr. Amaruka Hazari, Dr. Jay A. Labinger and Prof. John E. Bercaw

      Article first published online: 6 JUL 2012 | DOI: 10.1002/anie.201203264

      Thumbnail image of graphical abstract

      A helping hand: Incorporation of Group 2 Lewis acids into a macrocycle appended to a phosphine ligand attached to a rhenium carbonyl complex promotes otherwise unfavorable transformations of coordinated CO (see scheme; M=Ca, Sr). These Lewis acids form relatively weak M[BOND]O bonds, thereby enabling release of organic products from the metal center.

    15. Frustrated Lewis Pairs

      H2 Activation and Hydride Transfer to Olefins by Al(C6F5)3-Based Frustrated Lewis Pairs (pages 8272–8275)

      Gabriel Ménard and Prof. Dr. Douglas W. Stephan

      Article first published online: 9 JUL 2012 | DOI: 10.1002/anie.201203362

      Thumbnail image of graphical abstract

      Frustrated delivery: Frustrated Lewis pairs derived from tBu3P and Al(C6F5)3 activate H2 to give [tBu3PH][(μ-H)(Al(C6F5)3)2], which reacts with unactivated olefins to give RAl(C6F5)2 (R=Et or Cy) and [tBu3PH][Al(C6F5)4]. The proposed mechanism involves olefin activation by aluminum, which is supported by the isolation of the cyclohexene complex [Al(C6F5)3⋅(C6H10)].

    16. Synthetic Methods

      N-Heterocyclic Carbene Catalyzed Homoenolate-Addition Reaction of Enals and Nitroalkenes: Asymmetric Synthesis of 5-Carbon-Synthon δ-Nitroesters (pages 8276–8280)

      Dr. Biswajit Maji, Li Ji, Siming Wang, Seenuvasan Vedachalam, Dr. Rakesh Ganguly and Dr. Xue-Wei Liu

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201203449

      Thumbnail image of graphical abstract

      Synthesizing synthons: The highly enantioselective title reaction is described. It employs catalytic amounts of N-heterocyclic carbene precursors and transforms a broad range of nitroalkenes, such as nitrodienes, nitroenynes, and nitrostyrenes, through reaction with a broad range of enals, into δ-nitroesters via homoenolate intermediates (see scheme).

    17. Macrocycles

      1,3,5-Benzenetriamine Double- and Triple-Decker Molecules (pages 8281–8285)

      Daisuke Sakamaki, Dr. Akihiro Ito, Prof. Dr. Kazuyoshi Tanaka, Dr. Ko Furukawa, Prof. Dr. Tatsuhisa Kato and Dr. Motoo Shiro

      Article first published online: 6 JUL 2012 | DOI: 10.1002/anie.201203451

      Thumbnail image of graphical abstract

      Double- and triple-decker oligoarylamines have been prepared and characterized by X-ray crystallography for the first time (see picture; C black, N blue). The N-dianisylaminophenyl-substituted double decker exhibited the multiredox activity, and the oxidized species were confirmed to be in high-spin states on the basis of pulsed ESR spectroscopy.

    18. Asymmetric Hydrogenation

      Enantioselective Iridium-Catalyzed Hydrogenation of 3,4-Disubstituted Isoquinolines (pages 8286–8289)

      Dr. Lei Shi, Zhi-Shi Ye, Liang-Liang Cao, Ran-Ning Guo, Yue Hu and Prof. Yong-Gui Zhou

      Article first published online: 11 JUL 2012 | DOI: 10.1002/anie.201203647

      Thumbnail image of graphical abstract

      Reining in the outliers: An efficient approach for enantioselective hydrogenation of 3,4-disubstituted isoquinolines was successfully developed. When isoquinolines are treated with [Ir(cod)Cl]2/(R)-synphos in the presence of 1-bromo-3-chloro-5,5-dimethyl-hydantoin (BCDMH), the chiral 3,4-disubstituted tetrahydroisoquinoline derivatives are obtained with ee values as high as 96 % (see scheme; cod=1,5-cyclooctadiene).

    19. Synthetic Methods

      Enantioselective Synthesis of Tertiary α-Hydroxyketones from Unfunctionalized Ketones: Palladium-Catalyzed Asymmetric Allylic Alkylation of Enolates (pages 8290–8293)

      Prof.Prof. Barry M. Trost, Dr. Raffael Koller and Dr. Benjamin Schäffner

      Article first published online: 24 JUL 2012 | DOI: 10.1002/anie.201203663

      Thumbnail image of graphical abstract

      Aiming high: The title reaction for the synthesis of tertiary α-hydroxyketones is reported. Protected 1,2-enediol carbonates, the starting materials, were accessed from simple and readily available enol carbonates. Highly functionalized tertiary α-hydroxyketones can be obtained in high yield with excellent enantioselectivity using this method (see scheme).

    20. Metal–Metal Bonds

      Low-Coordinate Iron(I) and Manganese(I) Dimers: Kinetic Stabilization of an Exceptionally Short Fe[BOND]Fe Multiple Bond (pages 8294–8298)

      Lea Fohlmeister, Shengsi Liu, Dr. Christian Schulten, Dr. Boujemaa Moubaraki, Dr. Andreas Stasch, Dr. John D. Cashion, Prof. Keith S. Murray, Prof. Laura Gagliardi and Prof. Cameron Jones

      Article first published online: 9 JUL 2012 | DOI: 10.1002/anie.201203711

      Thumbnail image of graphical abstract

      Not just any old iron! The reduction of a bulky guanidinato iron(II) bromide complex yields a three-coordinate iron(I) dimer that possesses the shortest Fe–Fe interaction (2.127 Å) reported to date. Magnetic, Mössbauer, and computational studies show the unprecedented compound to contain two high-spin iron(I) centers with significant multiple-bond character. A related dimer containing a rare example of an unsupported, carbonyl-free Mn[BOND]Mn bond is also described.

    21. DNA-Directed Synthesis

      Template-Directed Synthesis in 3′- and 5′-Direction with Reversible Termination (pages 8299–8303)

      Dipl.-Chem. Andreas Kaiser, Dipl.-Chem. Sebastian Spies, Dr. Tanja Lommel and Prof. Clemens Richert

      Article first published online: 9 JUL 2012 | DOI: 10.1002/anie.201203859

      Thumbnail image of graphical abstract

      Extending both ways: A method for DNA-templated synthesis on solid support is described. Controlled, stepwise chain extension was demonstrated both in the direction favored by nature (3′-extension; see scheme) and in the direction typical for conventional DNA synthesizers (5′-extension).

    22. Acylation

      Chemoselective N-Acylation of Indoles and Oxazolidinones with Carbonylazoles (pages 8304–8308)

      Stephen T. Heller, Erica E. Schultz and Prof. Richmond Sarpong

      Article first published online: 11 JUL 2012 | DOI: 10.1002/anie.201203976

      Thumbnail image of graphical abstract

      Unique reactivity: In the presence of more reactive amine and alcohol functional groups and of carboxylic acids, the chemoselective N-acylation of indoles (see scheme) and oxazolidinones is achieved by taking advantage of the unique reactivity of carbonylazole acylating agents with catalytic amounts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

    23. Asymmetric Allylation

      Enantioselective Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines with Allylboron Reagents (pages 8309–8313)

      Dr. Yunfei Luo, Hamish B. Hepburn, Nawasit Chotsaeng and Dr. Hon Wai Lam

      Article first published online: 11 JUL 2012 | DOI: 10.1002/anie.201204004

      Thumbnail image of graphical abstract

      Chiral allylrhodium nucleophiles: The highly diastereo- and enantioselective title reaction of a range of cyclic imines with various potassium allyltrifluoroborates most likely proceeds via allylrhodium(I) intermediates, and represents the first rhodium-catalyzed enantioselective nucleophilic allylation of π electrophiles with allylboron compounds.

    24. Synthetic Methods

      Direct Transformation of Secondary Amides into Secondary Amines: Triflic Anhydride Activated Reductive Alkylation (pages 8314–8317)

      Kai-Jiong Xiao, Dr. Ai-E Wang and Prof. Dr. Pei-Qiang Huang

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201204098

      Thumbnail image of graphical abstract

      Versatile and mild: The first general method for the title transformation has been developed (see scheme; 2-F-Py=2-fluoropyridine; Tf=trifluorosulfonyl). The amines are synthesized in good yields and the ketimine intermediates can be isolated before the reduction. This method should find applications in the synthesis of nitrogen-containing bioactive molecules and medicinal agents.

    25. Copper-Catalyzed Aerobic Dehydrogenative Cyclization of N-Methyl-N-phenylhydrazones: Synthesis of Cinnolines (pages 8318–8321)

      Dr. Guangwu Zhang, Jinmin Miao, Yan Zhao and Prof. Dr. Haibo Ge

      Article first published online: 10 JUL 2012 | DOI: 10.1002/anie.201204339

      Thumbnail image of graphical abstract

      O2 leading the way: The title reaction proceeds through an oxidation/cyclization sequence, thus representing the first copper-catalyzed coupling reaction of hydrazones through a Cmath image[BOND]H bond functionalization process (see scheme; DMF=N,N′-dimethylformamide, Py=pyridine). The method provides an environmentally friendly and atom-efficient approach to biologically active cinnoline derivatives.

    26. Asymmetric Synthesis

      Enantioselective Synthesis of α-Alkyl-β-ketoesters: Asymmetric Roskamp Reaction Catalyzed by an Oxazaborolidinium Ion (pages 8322–8325)

      Lizhu Gao, Byung Chul Kang, Prof. Dr. Geum-Sook Hwang and Prof. Dr. Do Hyun Ryu

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201204350

      Thumbnail image of graphical abstract

      Breaking kamp: A catalytic route toward chiral α-alkyl-β-ketoesters using the title reaction of α-alkyl diazoester with aldehydes has been developed (see scheme). The reaction proceeds with high to excellent enantioselectivities and this methodology was applied to a concise two-step synthesis of the natural pheromone sitophilate.

    27. Artificial Receptors

      Imprinted Polymers Displaying High Affinity for Sulfated Protein Fragments (pages 8326–8329)

      MSc Sudhirkumar Shinde, Dr. Anton Bunschoten, Dr. John A. W. Kruijtzer, Prof. Dr. Rob M. J. Liskamp and Priv.-Doz. Dr. Börje Sellergren

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201201314

      Thumbnail image of graphical abstract

      Leaving a lasting impression: Molecularly imprinted polymers (MIPs) featuring neutral binding sites for phosphotyrosine (P) is also shown to have affinity for sulfotyrosine (S) and a sulfotyrosine-containing peptide. The MIPs were capable of selectively capturing both a phosphorylated and a sulfated peptide in a mixture and could release the peptides separately based on elution conditions.

    28. Helical Structures

      Inorganic Double-Helix Structures of Unusually Simple Lithium–Phosphorus Species (pages 8330–8333)

      Alexander S. Ivanov, Dr. Andrew J. Morris, Prof. Dr. Konstantin V. Bozhenko, Prof. Dr. Chris J. Pickard and Prof. Dr. Alexander I. Boldyrev

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201201843

      Thumbnail image of graphical abstract

      Theoretical evidence: The existence of inorganic double-helix structures at the atomic level is theoretically predicted. An unbiased quantum-chemical search for the global minimum structures of LixPx (x=5–9) species is performed. For the Li7P7–Li9P9 stoichiometries the global minimum structure has a peculiar double-helix form.

    29. NMR Spectroscopy

      Polyacetylenes as Enantiodifferentiating Alignment Media (pages 8334–8338)

      Dipl.-Chem. Nils-Christopher Meyer, Dipl.-Ing. Alexis Krupp, Dipl.-Ing. Volker Schmidts, Prof. Dr. Christina M. Thiele and Prof. Dr. Michael Reggelin

      Article first published online: 24 JUL 2012 | DOI: 10.1002/anie.201201891

      Thumbnail image of graphical abstract

      Orientation help: Valine-derived polyacetylenes are introduced as enantiomer-differentiating alignment media. The F2-coupled HSQC-type NMR spectra of both enantiomers of isopinocampheol (IPC) display narrow line widths allowing for the precise extraction of residual dipolar couplings (black contour plot: (+)-IPC in an isotropic phase, blue: (−)-IPC in an anisotropic phase, and red: (+)-IPC in an anisotropic phase; J=coupling constant).

    30. Drug Delivery

      Peptide-Mediated Blood–Brain Barrier Transport of Polymersomes (pages 8339–8342)

      Julia V. Georgieva, René P. Brinkhuis, Katica Stojanov, Dr. Carel A. G. M. Weijers, Prof. Dr. Han Zuilhof, Prof. Dr. Floris P. J. T. Rutjes, Prof. Dr. Dick Hoekstra, Prof. Dr. Jan C. M. van Hest and Dr. Inge S. Zuhorn

      Article first published online: 11 JUL 2012 | DOI: 10.1002/anie.201202001

      Thumbnail image of graphical abstract

      A polymeric nanocarrier: Polymersomes tagged with a dodecamer peptide that recognizes gangliosides GM1 and GT1b are shown to cross the blood–brain barrier, both in an in vitro model and in vivo (see picture). The combination of polymeric vesicles with a small GM1-binding peptide and GM1/GT1b gangliosides as targeting sites for blood–brain barrier transport is unprecedented.

    31. Membrane Proteins

      You have full text access to this OnlineOpen article
      GRecon: A Method for the Lipid Reconstitution of Membrane Proteins (pages 8343–8347)

      Dr. Thorsten Althoff, Dr. Karen M. Davies, Dr. Sabrina Schulze, Friederike Joos and Prof. Dr. Werner Kühlbrandt

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201202094

      Thumbnail image of graphical abstract

      Density gradients with increasing concentrations of cyclodextrin and detergent-destabilized liposomes are loaded with detergent-solubilized membrane proteins in a new approach for reconstituting membrane proteins. During centrifugation, the detergent is gradually replaced by the lipid. This gentle method separates proteoliposomes from empty liposomes and is particularly suitable for the lipid reconstitution of large, fragile membrane proteins.

    32. Surface Chemistry

      Surface Wetting in Liquid–Liquid–Solid Triphase Systems: Solid-Phase-Independent Transition at the Liquid–Liquid Interface by Lewis Acid–Base Interactions (pages 8348–8351)

      Dr. Mingjie Liu, Dr. Zhongxin Xue, Prof. Huan Liu and Prof. Lei Jiang

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201202293

      Thumbnail image of graphical abstract

      Interfacial phenomena: A solid-phase-independent strategy for tuning the surface wettability is presented. Lewis acid–base interactions at the oil–water interface can greatly decrease the liquid–liquid interfacial tension and induce oleophilic to superoleophobic wetting transition on a nonresponsive microstructured surface (see picture).

    33. Chemical Interface Damping in Single Gold Nanorods and Its Near Elimination by Tip-Specific Functionalization (pages 8352–8355)

      Peter Zijlstra, Pedro M. R. Paulo, Kuai Yu, Qing-Hua Xu and Prof. Michel Orrit

      Article first published online: 6 JUL 2012 | DOI: 10.1002/anie.201202318

      Thumbnail image of graphical abstract

      Tip-functionalized nanorods: Single-particle spectroscopy shows that functionalization of small gold nanorods with thiol groups leads to a broadening of the plasmon resonance by chemical interface damping. By specifically functionalizing the tips of the nanorod (see picture) this broadening is nearly eliminated while the sensing performance is maintained relative to fully functionalized particles.

    34. Multiferroics

      Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule-Based Magnets (pages 8356–8360)

      Dr. Emilio Pardo, Prof. Dr. Cyrille Train, Hongbo Liu, Lise-Marie Chamoreau, Dr. Brahim Dkhil, Prof. Dr. Kamal Boubekeur, Prof. Dr. Francesc Lloret, Prof. Dr. Keitaro Nakatani, Dr. Hiroko Tokoro, Prof. Dr. Shin-ichi Ohkoshi and Prof. Dr. Michel Verdaguer

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201202848

      Thumbnail image of graphical abstract

      Multiferroic materials: A novel class of multiferroics based on organic–inorganic hybrid materials is synthesized. The ferromagnetic properties originate from the coordination network, whereas the ferroelectricity results from the polar organic ions (see picture, M=magnetization and P=polarization).

    35. Dinuclear Metalloradicals

      Dinuclear Metalloradicals Featuring Unsupported Metal–Metal Bonds (pages 8361–8364)

      Dr. Edwin F. van der Eide, Dr. Ping Yang, Dr. Eric D. Walter, Dr. Tianbiao Liu and Dr. R. Morris Bullock

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201203531

      Thumbnail image of graphical abstract

      No support required: Unlike the unobservable radical cations [{CpM(CO)3}2].+ (M=W, Mo), derivatives [{CpM(CO)2(PMe3)}2].+ are stable enough to be isolated and characterized. Experimental and theoretical studies show that the shortened M[BOND]M bonds are of order 1 1/2, and that they are not supported by bridging ligands. The unpaired electron is delocalized over the M[BOND]M cores, with a spin density of about 45 % on each metal atom.

    36. Peptide Inhibitor

      An Inhibitor of Glutathione S-Transferase Omega 1 that Selectively Targets Apoptotic Cells (pages 8365–8368)

      Nicholas J. Pace, Daniel R. Pimental and Prof. Eranthie Weerapana

      Article first published online: 6 JUL 2012 | DOI: 10.1002/anie.201203730

      Thumbnail image of graphical abstract

      On (cell) suicide watch: The increased permeability of apoptotic cells was used to identify a peptide-based, covalent inhibitor (NJP2) for glutathione S-transferase omega (GSTO1) that is highly selective for apoptotic cells, with no inhibition of healthy cells (see scheme). This apoptosis-specific peptide could also be used for imaging programmed cell death.

    37. Structure Elucidation

      Design of Flexible Lewis Acidic Sites in Porous Coordination Polymers by using the Viologen Moiety (pages 8369–8372)

      Dr. Masakazu Higuchi, Kohei Nakamura, Dr. Satoshi Horike, Dr. Yuh Hijikata, Dr. Nobuhiro Yanai, Tomohiro Fukushima, Dr. Jungeun Kim, Dr. Kenichi Kato, Prof. Dr. Masaki Takata, Daisuke Watanabe, Shinji Oshima and Prof. Dr. Susumu Kitagawa

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201203834

      Thumbnail image of graphical abstract

      Charged up: A novel porous coordination polymer with a charged organic surface (COS) comprising a zwitterionic organic linker, viologen, has been synthesized. The COS shows strong Lewis acidity accompanied with flexibility, and the isosteric heat of H2 adsorption is 9.5 kJ mol−1, which is comparable to that of open metal sites (OMSs).

    38. Controlled Release

      Functional Mesoporous Silica Nanoparticles for Photothermal-Controlled Drug Delivery In Vivo (pages 8373–8377)

      Dr. Hong Yan, Dr. Cathleen Teh, Dr. Sivaramapanicker Sreejith, Dr. Liangliang Zhu, Anna Kwok, Weiqin Fang, Xing Ma, Kim Truc Nguyen, Prof. Dr. Vladimir Korzh and Prof. Dr. Yanli Zhao

      Article first published online: 6 JUL 2012 | DOI: 10.1002/anie.201203993

      Thumbnail image of graphical abstract

      Release me! A new class of photothermal-responsive [2]rotaxane-appended mesoporous silica nanoparticles (MSNPs) was developed. Remote-controlled movement of the α-cyclodextrin ring (green) upon transcis isomerization of the azobenzene axle (red) enables the loading and release of drugs on demand (see scheme). Curcumin-loaded MSNPs were shown to release curcumin into zebrafish larvae upon treatment with visible light or heat.

    39. Gold Catalysis

      Gold–Gold Cooperation in the Addition of Methanol to Alkynes (pages 8378–8382)

      Prof. Jana Roithová, Dr. Štěpánka Janková, Lucie Jašíková, Dr. Jiří Váňa and Dr. Simona Hybelbauerová

      Article first published online: 10 JUL 2012 | DOI: 10.1002/anie.201204003

      Thumbnail image of graphical abstract

      The gold(I)-mediated reaction between an internal alkyne and methanol proceeds by a dual activation mechanism, which directly results in formation of gem-diaurated intermediates. Reaction intermediates were investigated by IR multiphoton dissociation spectroscopy, kinetics by NMR spectroscopy, and the mechanism by DFT calculations.

    40. Protein NMR Spectroscopy

      M2 Proton Channel Structural Validation from Full-Length Protein Samples in Synthetic Bilayers and E. coli Membranes (pages 8383–8386)

      Yimin Miao, Huajun Qin, Dr. Riqiang Fu, Dr. Mukesh Sharma, Thach V. Can, Dr. Ivan Hung, Dr. Sorin Luca, Peter L. Gor'kov, Dr. William W. Brey and Dr. Timothy A. Cross

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201204666

      Thumbnail image of graphical abstract

      Validation: Membrane protein structures are sensitive to the environment used for structural characterization. NMR spectra of the full-length M2 proton channel from influenza A were measured directly in E. coli membranes and compared to spectra of the protein in synthetic lipid bilayers. The results demonstrate that these bilayers provide a native-like membrane environment.

  12. And Finally

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Meeting Review
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. And Finally
    1. Absolute Configuration

      Is Enantiomer Assignment Possible by NMR Spectroscopy Using Residual Dipolar Couplings from Chiral Nonracemic Alignment Media?—A Critical Assessment (pages 8388–8391)

      Prof. Dr. Robert Berger, Prof. Dr. Jacques Courtieu, Prof. Dr. Roberto R. Gil, Prof. Dr. Christian Griesinger, Prof. Dr. Matthias Köck, Prof. Dr. Philippe Lesot, Prof. Dr. Burkhard Luy, Prof. Dr. Denis Merlet, Dr. Armando Navarro-Vázquez, Prof. Dr. Michael Reggelin, Prof. Dr. Uwe M. Reinscheid, Prof. Dr. Christina M. Thiele and Prof. Dr. Markus Zweckstetter

      Article first published online: 10 JUL 2012 | DOI: 10.1002/anie.201107626

      Thumbnail image of graphical abstract

      Insensitive towards inversion: Can residual dipolar couplings (RDCs) and other anisotropic NMR observables be used to determine absolute configuration? A critical assessment of recent approaches is provided to determine the absolute configuration from RDCs.

SEARCH

SEARCH BY CITATION