Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 52

December 21, 2012

Volume 51, Issue 52

Pages 12899–13177

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. You have free access to this content
      Cover Picture: One Hundred Years of Vitamins—A Success Story of the Natural Sciences (Angew. Chem. Int. Ed. 52/2012) (page 12899)

      Dr. Manfred Eggersdorfer, Dr. Dietmar Laudert, Dr. Ulla Létinois, Dr. Tom McClymont, Dr. Jonathan Medlock, Dr. Thomas Netscher and Priv.-Doz. Dr. Werner Bonrath

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/anie.201209488

      Thumbnail image of graphical abstract

      In 1912, the name vitamins was coined by Casimir Funk to describe essential bioactive substances contained in food. The use of vitamins has since resulted in an enormous improvement in human health. Their structures provided challenging synthetic problems for chemists in academia and industry. In the Review on page 12960 ff., W. Bonrath et al. present 100 years of achievement in vitamin preparation, from the first synthesis to manufacture on an industrial scale.

    2. You have free access to this content
      Inside Cover: Efficient Metathesis of Terminal Alkynes (Angew. Chem. Int. Ed. 52/2012) (page 12900)

      Dipl.-Chem. Birte Haberlag, Dr. Matthias Freytag, Dr. Constantin G. Daniliuc, Prof. Dr. Peter G. Jones and Prof. Dr. Matthias Tamm

      Version of Record online: 28 NOV 2012 | DOI: 10.1002/anie.201208969

      Thumbnail image of graphical abstract

      The curtain rises for a molybdenum alkylidyne complex that efficiently catalyzes the metathesis of internal and terminal alkynes by the breaking and making of C[BOND]C triple bonds. In their Communication on page 13019 ff., M. Tamm et al. describe the synthesis of 2,4,6-trimethylbenzylidyne complexes of molybdenum and tungsten; the Mo complex exhibits high catalytic activity in terminal alkyne metathesis (TAM) and terminal ring-closing metathesis (TRAM).

    3. You have free access to this content
      Inside Back Cover: The Triplet Surface of the Zimmerman Di-π-Methane Rearrangement of Dibenzobarrelene (Angew. Chem. Int. Ed. 52/2012) (page 13179)

      Dr. Ricardo A. Matute and Prof. Dr. Kendall N. Houk

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201209048

      Thumbnail image of graphical abstract

      The di-π-methane rearrangement of dibenzobarrelene, described with a two-step mechanism on the triplet state, was pioneered by Howard Zimmerman (1926–2012). In their Communication on page 13097 ff., R. A. Matute and K. N. Houk give a novel mechanistic insight of competing one-step and two-step pathways on the triplet surface. The picture shows a dromedary and a bactrian camel with the transition states on their humps.

    4. You have free access to this content
      Back Cover: Photocatalytic Overall Water Splitting Promoted by an α–β phase Junction on Ga2O3 (Angew. Chem. Int. Ed. 52/2012) (page 13180)

      Xiang Wang, Dr. Qian Xu, Dr. Mingrun Li, Shuai Shen, Dr. Xiuli Wang, Dr. Yaochuan Wang, Prof. Zhaochi Feng, Dr. Jingying Shi, Prof. Hongxian Han and Prof. Can Li

      Version of Record online: 4 DEC 2012 | DOI: 10.1002/anie.201209123

      Thumbnail image of graphical abstract

      Charge separation is one of the key issues related to the photocatalytic activity of semiconductor-based photocatalysts for overall water splitting. In their Communication on page 13089 ff., C. Li et al. show that the phase junction formed between two phases of Ga2O3 can facilitate charge separation, resulting in high photocatalytic activity for overall water splitting.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. You have free access to this content
  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
  4. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. You have free access to this content
      Corrigendum: Iron-Catalyzed Polymerization of Isoprene and Other 1,3-Dienes (page 12920)

      Dr. Jean Raynaud, Dr. Jessica Y. Wu and Prof. Tobias Ritter

      Version of Record online: 18 DEC 2012 | DOI: 10.1002/anie.201209042

      This article corrects:

      Iron-Catalyzed Polymerization of Isoprene and Other 1,3-Dienes1

      Vol. 51, Issue 47, 11805–11808, Version of Record online: 18 OCT 2012

  5. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
  6. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. Jonathan R. Nitschke (page 12928)

      Version of Record online: 21 AUG 2012 | DOI: 10.1002/anie.201205932

      Thumbnail image of graphical abstract

      “My favorite place on earth is Yosemite National Park. The most significant scientific advance of the last 100 years has been the identification of the Higgs Boson …” This and more about Jonathan R. Nitschke can be found on page 12928.

  7. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
  8. Book Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. NMR in Organometallic Chemistry. By Paul S. Pregosin. (pages 12930–12931)

      Dmitry G. Gusev

      Version of Record online: 3 DEC 2012 | DOI: 10.1002/anie.201208000

      Thumbnail image of graphical abstract

      Wiley-VCH, Weinheim, 2012. 392 pp., softcover, € 59.00.—ISBN 978-3527330133

  9. Highlights

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. Asymmetric Catalysis

      Desymmetrization Catalyzed by Transition-Metal Complexes: Enantioselective Formation of Silicon-Stereogenic Silanes (pages 12932–12934)

      Prof. Dr. Li-Wen Xu

      Version of Record online: 29 NOV 2012 | DOI: 10.1002/anie.201207932

      Thumbnail image of graphical abstract

      Prochiral silanes: Recent work has demonstrated the powerful potential of enantioselective desymmetrization catalyzed by transition-metal complexes in the stereoselective formation of silicon-stereogenic silanes. These methods offer new possibilities for asymmetric synthesis of any functionalized chiral silanes that possess tetraorganosilicon stereocenters.

    2. Gold Hydrides

      Fire and Ice: A Gold(III) Monohydride (pages 12935–12936)

      Prof. Dr.  A. Stephen K. Hashmi

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201208603

      Thumbnail image of graphical abstract

      Good as gold: Gold hydrides were long considered unstable. In the past few years reports have appeared on not only the stable NHC gold(I) monohydride complex 1 (see structure; NHC=N-heterocyclic carbene) but also a dinuclear gold(I) hydride and most recently the gold(III) monohydride complex 2 with a C-N-C pincer ligand. One can expect new and important impulses for inorganic and organometallic chemistry and homogeneous gold catalysis.

  10. Correspondence

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. Oil/Water Interface (1)

      Surface Impurities Are Not Responsible For the Charge on the Oil/Water Interface: A Comment (pages 12938–12940)

      Dr. Kailash C. Jena, Rüdiger Scheu and Prof. Dr. Sylvie Roke

      Version of Record online: 23 NOV 2012 | DOI: 10.1002/anie.201204662

      Thumbnail image of graphical abstract

      The origin of the charge on oil/water interfaces that can be found from electrokinetic mobility measurements is a long-standing issue that has invoked different explanations. Sum frequency scattering (SFS) shows that impurities are likely not a general cause for the charge (see picture).

    2. Oil/Water Interface (2)

      Oil/Water Interface Charged by Hydroxide Ions and Deprotonated Fatty Acids: A Comment (pages 12941–12942)

      James K. Beattie and Angus Gray-Weale

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201205927

      Thumbnail image of graphical abstract

      The effect of fatty acid impurities on the electrophoretic mobility of hexadecane in water emulsions is reinterpreted, occasioned by an error in the surface charge attributed to the fatty acids. The results are consistent with a surface charge contributed by both hydroxide ions and deprotonated fatty acids (see picture).

    3. Oil/Water Interface (3)

      Uncontaminated Hydrophobic/Water Interfaces Are Uncharged: A Reply (pages 12943–12945)

      Kevin Roger and Dr. Bernard Cabane

      Version of Record online: 6 DEC 2012 | DOI: 10.1002/anie.201207114

      Thumbnail image of graphical abstract

      Pure is uncharged: Uncontaminated hydrophobic interfaces, such as PMMA-H/water interfaces, are uncharged. If the macromolecules have instead ionizable carboxylic acid endgroups, such as PMMA-COOH, a surface charge similar to the contaminated oil/water interface is obtained.

  11. Essay

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. William Lawrence Bragg

      William Lawrence Bragg: The Pioneer of X-ray Crystallography and His Pervasive Influence (pages 12946–12958)

      Prof. Sir John Meurig Thomas

      Version of Record online: 4 DEC 2012 | DOI: 10.1002/anie.201206509

      Thumbnail image of graphical abstract

      A new age dawned when 22-year-old William Lawrence Bragg (see picture) realized that the observations of X-ray diffraction by a crystal can be interpreted very simply as arising from the reflection of the X-rays by planes of atoms in the crystal. In the 100 years since this insight X-ray diffraction has transformed chemistry, mineralogy, metallurgy, and, most recently, biology.

  12. Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. Vitamins

      One Hundred Years of Vitamins—A Success Story of the Natural Sciences (pages 12960–12990)

      Dr. Manfred Eggersdorfer, Dr. Dietmar Laudert, Dr. Ulla Létinois, Dr. Tom McClymont, Dr. Jonathan Medlock, Dr. Thomas Netscher and Priv.-Doz. Dr. Werner Bonrath

      Version of Record online: 3 DEC 2012 | DOI: 10.1002/anie.201205886

      Thumbnail image of graphical abstract

      Essential: The discovery of vitamins was a scientific breakthrough that changed the world! The synthesis of vitamins on a commercial scale and their application in diets had a dramatically positive impact on human and animal health as well as economic development. The key achievements in research of vitamins are highlighted in this Review, starting from the first industrial synthesis of L-ascorbic acid up to modern catalytic methods.

  13. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Correspondence
    12. Essay
    13. Review
    14. Communications
    1. Protein Mass Spectrometry

      Exploring an Orbitrap Analyzer for the Characterization of Intact Antibodies by Native Mass Spectrometry (pages 12992–12996)

      Sara Rosati, Dr. Rebecca J. Rose, Dr. Natalie J. Thompson, Dr. Esther van Duijn, Dr. Eugen Damoc, Dr. Eduard Denisov, Dr. Alexander Makarov and Prof. Albert J. R. Heck

      Version of Record online: 22 NOV 2012 | DOI: 10.1002/anie.201206745

      Thumbnail image of graphical abstract

      Antibody profiling: Native mass spectrometry analysis of intact antibodies can be achieved with improved speed, sensitivity, and mass resolution by using a modified orbitrap instrument. Complex mixtures of monoclonal antibodies can be resolved and their glycan “fingerprints” can be profiled (see picture). Noncovalent interactions are maintained, thus allowing antibody–antigen binding to be measured.

    2. Reduction of Oxygen

      Why is Gold such a Good Catalyst for Oxygen Reduction in Alkaline Media? (pages 12997–13000)

      Dr. P. Quaino, Dr. N. B. Luque, Prof. Dr. R. Nazmutdinov, Dr. E. Santos and Prof. Dr. Wolfgang Schmickler

      Version of Record online: 21 NOV 2012 | DOI: 10.1002/anie.201205902

      Thumbnail image of graphical abstract

      The two faces of gold: The reduction of oxygen on gold electrodes in alkaline solutions has been investigated theoretically. The most favorable reaction leads directly to adsorbed O2, but the activation energy for a two-step pathway, in which the first step is an outer-sphere electron transfer to give solvated O2, is only slightly higher. d-band catalysis, which dominates oxygen reduction in acid media, plays no role. The reason why the reaction is slow in acid media is also explained.

    3. Double C[BOND]H Activation

      Rhodium(III) and Hexabromobenzene—A Catalyst System for the Cross-Dehydrogenative Coupling of Simple Arenes and Heterocycles with Arenes Bearing Directing Groups (pages 13001–13005)

      Dr. Joanna Wencel-Delord, Corinna Nimphius, Dr. Honggen Wang and Prof. Dr. Frank Glorius

      Version of Record online: 19 OCT 2012 | DOI: 10.1002/anie.201205734

      Thumbnail image of graphical abstract

      C6Brsix & drugs! C6Br6 can be used as the cooxidant/catalyst modifier for the [RhIIICp*]-catalyzed (Cp*=C5Me5) dehydrogenative cross-coupling of benzamides with simple benzene derivatives (see scheme, DG=directing group). Similarly, heterocycles can be coupled and druglike structures formed. Mechanistic studies suggest a unique and multiple role of the Cu(OAc)2/C6Br6 system and a nonchelate-assisted C[BOND]H activation as the rate-determing step.

    4. Acetylide Chemistry

      Evidence of Solubility of the Acetylide Ion C22−: Syntheses and Crystal Structures of K2C2⋅2 NH3, Rb2C2⋅2 NH3, and Cs2C2⋅7 NH3 (pages 13006–13010)

      Markus Hamberger, Stefan Liebig, Ute Friedrich, Prof. Dr. Nikolaus Korber and Prof. Dr. Uwe Ruschewitz

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201206349

      Thumbnail image of graphical abstract

      Carbon anions in solution: C22− dumbbells are well-known in solid-state compounds. The crystallization of the title compounds now shows that acetylide ions are existent in solution and therefore chemistry with small dissolved carbon anions may be within reach.

    5. Organobismuth Chemistry

      The Bis(allyl)bismuth Cation: A Reagent for Direct Allyl Transfer by Lewis Acid Activation and Controlled Radical Polymerization (pages 13011–13015)

      Crispin Lichtenberg, Fangfang Pan, Dr. Thomas P. Spaniol, Prof. Dr. Ulli Englert and Prof. Dr. Jun Okuda

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201206782

      Thumbnail image of graphical abstract

      A positive effect: The bis(allyl)bismuth cation (see picture) in [Bi(C3H5)2(thf)2][B(C6H3Cl2)4] is superior to neutral tris(allyl)bismuth in the additive-free allylation of unsaturated C-heteroatom functionalities and the controlled living radical polymerization of activated olefins.

    6. Enzyme Catalysis

      Enzymatic Amine Acyl Exchange in Peptides on Gold Surfaces (pages 13016–13018)

      Roberto Castangia, Dr. Martina Austeri and Prof. Sabine L. Flitsch

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201205404

      Thumbnail image of graphical abstract

      Reversible as well as stereo- and chemoselective: Various proteases such as thermolysin and chymotrypsin catalyze amine acyl exchange in peptides. This acyl exchange can be used to modify amino-functionalized surfaces under physiological reaction conditions and provides an alternative mechanism for posttranslational transpeptidation reactions such as peptide-splicing reactions in the proteasome.

    7. Alkyne Metathesis

      Efficient Metathesis of Terminal Alkynes (pages 13019–13022)

      Dipl.-Chem. Birte Haberlag, Dr. Matthias Freytag, Dr. Constantin G. Daniliuc, Prof. Dr. Peter G. Jones and Prof. Dr. Matthias Tamm

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201207772

      Thumbnail image of graphical abstract

      Now even terminal: The 2,4,6-trimethylbenzylidyne complexes [MesC[TRIPLE BOND]M{OC(CF3)2Me}3] (M=Mo, W) were synthesized from [Mo(CO)6] and [W(CO)6], respectively. The molybdenum complex is an efficient catalyst for the metathesis of internal and terminal alkynes and also for the ring-closing metathesis of internal and terminal α,ω-diynes at room temperature and low catalyst concentrations.

    8. Chiral Resolution

      Total Spontaneous Resolution by Deracemization of Isoindolinones (pages 13023–13025)

      Fumitoshi Yagishita, Hiroki Ishikawa, Tatsuo Onuki, Shoko Hachiya, Prof. Takashi Mino and Prof. Masami Sakamoto

      Version of Record online: 13 NOV 2012 | DOI: 10.1002/anie.201205097

      Thumbnail image of graphical abstract

      Separated: 3-Hydroxy-3-phenylisoindolin-1-ones have been resolved by dynamic preferential crystallization. The compounds were effectively racemized through ring-opening and ring-closing reactions via achiral intermediates under basic conditions. Crystallization from a toluene solution containing 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with stirring and evaporation of the solvent gave optically active crystals quantitatively with high ee values.

    9. Phosphanide Ligands

      Accessing the Coordination Chemistry of Phosphorus(I) Zwitterions (pages 13026–13030)

      Jonathan W. Dube, Prof. Charles L. B. Macdonald and Prof. Paul J. Ragogna

      Version of Record online: 12 NOV 2012 | DOI: 10.1002/anie.201205744

      Thumbnail image of graphical abstract

      Go for the gold! Incorporating a borate anion into the backbone of a triphosphenium cation produces a unique zwitterionic phosphanide that can coordinate to one or two {AuCl} fragments depending on the steric bulk of the ligand (see picture; Au yellow, P purple, Cl green). Computational investigations show that in this μ-type ligand, the phosphorus atom behaves only as a σ,π donor.

    10. Asymmetric Catalysis

      Rhodium-Catalyzed Regio-, Diastereo-, and Enantioselective [2+2+2] Cycloaddition of 1,6-Enynes with Acrylamides (pages 13031–13035)

      Koji Masutomi, Norifumi Sakiyama, Prof. Dr. Keiichi Noguchi and Prof. Dr. Ken Tanaka

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201206122

      Thumbnail image of graphical abstract

      Ring ring: Annulated cyclohexenes were synthesized by using the title reaction with the cationic rhodium(I)/(R)-H8-binap complex as a catalyst. In this catalysis, regioselective insertion of the acrylamide into a rhodacyclopentene intermediate and the coordination of the carbonyl group of the acrylamide to the cationic rhodium center suppress the undesired β-hydride elimination.

    11. Structure Elucidation

      Versatile Bottom-up Approach to Stapled π-Conjugated Helical Scaffolds: Synthesis and Chiroptical Properties of Cyclic o-Phenylene Ethynylene Oligomers (pages 13036–13040)

      Dr. Noelia Fuentes, Ana Martin-Lasanta, Dr. Luis Alvarez de Cienfuegos, Prof. Dr. Rafael Robles, Dr. Duane Choquesillo-Lazarte, Prof. Dr. Juan M. García-Ruiz, Lara Martínez-Fernández, Dr. Inés Corral, Dr. María Ribagorda, Dr. Antonio J. Mota, Prof. Dr. Diego J. Cárdenas, Prof. Dr. M. Carmen Carreño and Dr. Juan M. Cuerva

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201206259

      Thumbnail image of graphical abstract

      Spring loaded: The smallest members of a family of carbon nanocoils (CNCs), adopting a fixed helical structure, have been synthesized by introduction of one or two staples in o-phenylene ethynylene oligomers. The chiroptical responses of the systems having enantiopure L-tartrate-derived staples confirmed the induced helicity. Theoretical studies suggest that these CNCs are pseudoelastic.

    12. Homogeneous Catalysis

      Catalytic Hydrogenation of Cyclic Carbonates: A Practical Approach from CO2 and Epoxides to Methanol and Diols (pages 13041–13045)

      Dr. Zhaobin Han, Liangce Rong, Jiang Wu, Dr. Lei Zhang, Dr. Zheng Wang and Prof. Dr. Kuiling Ding

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201207781

      Thumbnail image of graphical abstract

      Two birds with one stone: The simultaneous production of two important bulk chemicals, methanol and ethylene glycol, from CO2 and ethylene oxide has been achieved under mild conditions by the highly efficient homogeneous catalytic hydrogenation of ethylene carbonate in the presence of a (PNP)RuII catalyst (see scheme).

    13. Fullerene Complexes

      [(μ-H)3Re3(CO)9222-Sc2C2@C3v(8)-C82)]: Face-Capping Cluster Complex of an Endohedral Fullerene (pages 13046–13049)

      Dr. Chia-Hsiang Chen, Dr. Wen-Yann Yeh, Yi-Hung Liu and Dr. Gene-Hsiang Lee

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201207261

      Thumbnail image of graphical abstract

      Like a miniature trophy, the complex pictured was obtained as the sole product from the reaction of Sc2C2@C3v(8)-C82 and [(μ-H)3Re3(CO)11(NCMe)] and characterized by IR, visible/near-infrared, and NMR spectroscopy, mass spectrometry, and X-ray diffraction. Coordination of the Re3 cluster to the unique hexagon oriented perpendicular to the C3 axis of the fullerene core altered the geometry and electronic properties of Sc2C2@C3v(8)-C82.

    14. Allylboration

      You have full text access to this OnlineOpen article
      Palladium-Catalyzed Synthesis and Isolation of Functionalized Allylboronic Acids: Selective, Direct Allylboration of Ketones (pages 13050–13053)

      Dr. Mihai Raducan, Rauful Alam and Prof. Kálmán J. Szabó

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207951

      Thumbnail image of graphical abstract

      Textbook revision: Allylboronic acids, which are easily prepared from allylic alcohols, react readily and selectively with ketones without Lewis acid catalysts.

    15. Rhodium(II) Catalysis

      Ring Expansion and Rearrangements of Rhodium(II) Azavinyl Carbenes (pages 13054–13057)

      Dr. Nicklas Selander, Brady T. Worrell and Dr. Valery V. Fokin

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207820

      Thumbnail image of graphical abstract

      Room for expansion: An efficient, regioselective, and convergent method for the ring expansion and rearrangement of 1-sulfonyl-1,2,3-triazoles under rhodium(II)-catalyzed conditions is described. These denitrogenative reactions form substituted enaminone and olefin-based products (see scheme). The enaminone products can be further functionalized to give various heterocycles and ketone derivatives, thus rendering the sulfonyl triazole traceless.

    16. Homogeneous Catalysis

      Sustainable Synthesis of Diverse Privileged Heterocycles by Palladium-Catalyzed Aerobic Oxidative Isocyanide Insertion (pages 13058–13061)

      Tjøstil Vlaar, Razvan C. Cioc, Pieter Mampuys, Prof. Dr. Bert U. W. Maes, Prof. Dr. Romano V. A. Orru and Dr. Eelco Ruijter

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201207410

      Thumbnail image of graphical abstract

      O2 in, H2O out: Various diamines and related bisnucleophiles readily undergo oxidative isocyanide insertion with Pd(OAc)2 (1 mol %) as the catalyst and O2 as the terminal oxidant to give a diverse array of medicinally relevant N heterocycles. The utility of this highly sustainable method is demonstrated by a formal synthesis of the antihistamines astemizole and norastemizole.

    17. Natural Product Synthesis

      Total Synthesis of (−)-Acetylaranotin (pages 13062–13065)

      Dr. Hideto Fujiwara, Taichi Kurogi, Shun Okaya, Dr. Kentaro Okano and Prof. Dr. Hidetoshi Tokuyama

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207307

      Thumbnail image of graphical abstract

      The key step in this total synthesis of (−)-acetylaranotin is the efficient formation of the characteristic dihydrooxepine ring from cyclohexenone through an unusual vinylogous Rubottom oxidation and a regioselective Baeyer–Villiger oxidation. (−)-Acetylaranotin is obtained in 22 steps from commercially available L-Cbz-tyrosine (Cbz=benzyloxycarbonyl).

    18. Total Synthesis and Stereochemical Revision of the Chlorinated Sesquiterpene (±)-Gomerone C (pages 13066–13069)

      Nikolas Huwyler and Prof. Dr. Erick M. Carreira

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201207203

      Thumbnail image of graphical abstract

      Revised: The total synthesis of gomerone C results in revision of the stereochemical assignment at C3 (see scheme). The synthetic strategy relies on a late-stage Conia-ene reaction, which efficiently forms the bicyclo[3.2.1]octane containing the bridgehead chloride and generates an exocyclic olefin, which can be used as a flexible handle for further elaboration. The two contiguous quaternary centers are installed by means of a Diels–Alder reaction.

    19. Catalytic Hydroxylation

      Pd-Catalyzed C[BOND]H Oxygenation with TFA/TFAA: Expedient Access to Oxygen-Containing Heterocycles and Late-Stage Drug Modification (pages 13070–13074)

      Gang Shan, Xinglin Yang, Linlin Ma and Prof. Dr. Yu Rao

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207458

      Thumbnail image of graphical abstract

      Acid brings the oxygen: A general method for palladium-catalyzed C[BOND]H oxygenation has been developed for the facile synthesis of a wide range of functionalized phenols with readily available aryl ketones, benzoates, benzamides, acetanilides, and sulfonamides. A trifluoroacetic acid/trifluoroacetic acid anhydride solvent system serves as the oxygen source and is the critical factor for C[BOND]H activation.

    20. C[BOND]H Activation

      Synthesis of ortho-Acylphenols through the Palladium-Catalyzed Ketone-Directed Hydroxylation of Arenes (pages 13075–13079)

      Dr. Fanyang Mo, Louis J. Trzepkowski and Prof. Dr. Guangbin Dong

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207479

      Thumbnail image of graphical abstract

      Ketone in charge: A formal ketone-directed palladium-catalyzed ortho-hydroxylation of arenes has been developed as an effective approach to access o-acylphenols from simple arylketones. A Pd-catalyzed oxidative ortho-carbonylation reaction using ketone directing groups to access a ketal–lactone motif is also demonstrated. The ubiquity and versatile nature of ketones make these methods attractive. BTI=PhI(TFA)2; DCE=1,2-dichloroethane.

      Corrected by:

      Corrigendum: Corrigendum: Synthesis of ortho-Acylphenols through the Palladium-Catalyzed Ketone-Directed Hydroxylation of Arenes

      Vol. 52, Issue 21, 5425, Version of Record online: 10 MAY 2013

    21. RNA Labeling

      You have full text access to this OnlineOpen article
      2′-SCF3 Uridine—A Powerful Label for Probing Structure and Function of RNA by 19F NMR Spectroscopy (pages 13080–13084)

      M. Sc. Katja Fauster, Dr. Christoph Kreutz and Prof. Dr. Ronald Micura

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207128

      Thumbnail image of graphical abstract

      Fluorishing: The Togni reagent allows efficient synthetic access to fluorine-labeled RNA molecules (see picture). These are in turn highly useful for NMR spectroscopic analyses of secondary and tertiary structures, RNA–protein interactions, and functionality of riboswitch modules.

    22. Thiol-Ene Polymerization

      Nonenzymatic Polymerization of Ubiquitin: Single-Step Synthesis and Isolation of Discrete Ubiquitin Oligomers (pages 13085–13088)

      Vivian H. Trang, Ellen M. Valkevich, Shoko Minami, Yi-Chen Chen, Prof. Ying Ge and Prof. Eric R. Strieter

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207171

      Thumbnail image of graphical abstract

      Linked: A method based on thiol-ene chemistry enables the synthesis and purification of ubiquitin oligomers with ≥4 units. This approach, which employs free-radical polymerization, can be applied towards the synthesis of homogeneous Lys6-linked ubiquitin oligomers currently inaccessible by enzymatic methods. By using these chains, one can study their roles in the ubiquitin proteasome system and the DNA damage response pathway.

    23. Photocatalysis

      Photocatalytic Overall Water Splitting Promoted by an α–β phase Junction on Ga2O3 (pages 13089–13092)

      Xiang Wang, Dr. Qian Xu, Dr. Mingrun Li, Shuai Shen, Dr. Xiuli Wang, Dr. Yaochuan Wang, Prof. Zhaochi Feng, Dr. Jingying Shi, Prof. Hongxian Han and Prof. Can Li

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207554

      Thumbnail image of graphical abstract

      When Alpha met Beta: A tuneable α—β surface phase junction on Ga2O3 can significantly improve photocatalytic overall water splitting into H2 and O2 over individual α-Ga2O3 or β-Ga2O3 surface phases. This enhanced photocatalytic performance is mainly attributed to the efficient charge separation and transfer across the α–β phase junction.

    24. Fluxional Intermediates

      Gold for the Generation and Control of Fluxional Barbaralyl Cations (pages 13093–13096)

      Dr. Paul R. McGonigal, Claudia de León, Yahui Wang, Anna Homs, César R. Solorio-Alvarado and Prof. Antonio M. Echavarren

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207682

      Thumbnail image of graphical abstract

      The frog prince with his two identities pales in comparison with the shape-shifting barbaralyl cation, which exists as a mixture of 181 400 degenerate forms. Gold-catalyzed cycloisomerizations of 7-alkynyl cyclohepta-1,3,5-trienes were found to proceed via fluxional barbaralyl intermediates (see scheme). The evolution of the intermediates into 1- or 2-substituted indenes could be controlled by the choice of gold complex.

    25. Photorearrangements

      The Triplet Surface of the Zimmerman Di-π-Methane Rearrangement of Dibenzobarrelene (pages 13097–13100)

      Dr. Ricardo A. Matute and Prof. Dr. Kendall N. Houk

      Version of Record online: 26 NOV 2012 | DOI: 10.1002/anie.201208002

      Thumbnail image of graphical abstract

      High-level calculations: The Zimmerman di-π-methane rearrangement of dibenzobarrelene occurs via a triplet state to form dibenzosemibullvalene, overcoming two barriers connecting two biradicals. The shape of the triplet potential-energy surface shows that the rearrangement involves two transition states. The first triplet diradical intermediate may bypass in the passive of the alkene triplet to the final intermediate (see picture).

    26. Polydopamine

      Electrochemically Driven, Electrode-Addressable Formation of Functionalized Polydopamine Films for Neural Interfaces (pages 13101–13104)

      Kyungtae Kang, Seokyoung Lee, Raeyoung Kim, Prof. Dr. Insung S. Choi and Prof. Dr. Yoonkey Nam

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201207129

      Thumbnail image of graphical abstract

      The electrode-specific formation of polydopamine films is achieved by applying positive voltage to the target electrodes at pH 6.0. The functionalization of the films is simultaneously carried out by co-depositing dopamine with molecules of interest onto the electrode.

    27. Antiaromaticity

      A Möbius Antiaromatic Complex as a Kinetically Controlled Product in Phosphorus Insertion to a [32]Heptaphyrin (pages 13105–13108)

      Tomohiro Higashino, Byung Sun Lee, Jong Min Lim, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201208147

      Thumbnail image of graphical abstract

      Singly twisted Möbius antiaromatic [34]heptaphyrin A and doubly twisted Hückel aromatic [34]heptaphyrin B were formed by a phosphorus insertion reaction. A rearranges thermally to give the more stable B with P[DOUBLE BOND]O migration from NNN to NNC, and thus A is a rare case of a kinetically controlled Möbius antiaromatic molecule.

    28. Asymmetric Catalysis

      Dienamine-Mediated Inverse-Electron-Demand Hetero-Diels–Alder Reaction by Using an Enantioselective H-Bond-Directing Strategy (pages 13109–13113)

      Dr. Łukasz Albrecht, Dr. Gustav Dickmeiss, Dr. Christian F. Weise, Dr. Carles Rodríguez-Escrich and Prof. Dr. Karl Anker Jørgensen

      Version of Record online: 12 NOV 2012 | DOI: 10.1002/anie.201207122

      Thumbnail image of graphical abstract

      Giving directions: Optically active dihydropyrans bearing three contiguous stereogenic centers can be efficiently prepared by the title reaction. High stereo- and regiocontrol can be achieved by employing a bifunctional H-bond-directing aminocatalyst.

    29. Nanocluster Structure

      Total Structure and Electronic Properties of the Gold Nanocrystal Au36(SR)24 (pages 13114–13118)

      Chenjie Zeng, Dr. Huifeng Qian, Tao Li, Dr. Gao Li, Prof. Nathaniel L. Rosi, Dr. Bokwon Yoon, Dr. Robert N. Barnett, Prof. Robert L. Whetten, Prof. Uzi Landman and Prof. Rongchao Jin

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201207098

      Thumbnail image of graphical abstract

      A golden opportunity: The total structure of a Au36(SR)24 nanocluster (see figure) reveals an unexpected face-centered-cubic tetrahedral Au28 kernel (magenta). The protecting layer exhibits an intriguing combination of binding modes, consisting of four regular arch-like staples and the unprecedented appearance of twelve bridging thiolates (yellow). This unique protecting network and superatom electronic shell structure confer extreme stability and robustness.

    30. Self-Assembly

      Facile Route to an All-Organic, Triply Threaded, Interlocked Structure by Templated Dynamic Clipping (pages 13119–13122)

      Andrew Pun, David A. Hanifi, Gavin Kiel, Evan O'Brien and Dr. Yi Liu

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201207048

      Thumbnail image of graphical abstract

      Encaged! Three-terminal interlocked molecular species were obtained by dynamic (2+3) assembly of a cagelike macro-bicycle around a trifurcated trispyridinium π guest. The complex is stabilized by π–π interactions and multiple [C[BOND]H⋅⋅⋅O] and [C[BOND]H⋅⋅⋅N] interactions. Uncomplexed guest molecules cocrystallize alongside the threaded complexes in the solid state, thus giving extended π-stacked columns.

    31. Metallo-Foldamers

      Metallo-Foldamers with Backbone-Coordinative Oxime Peptides: Control of Secondary Structures (pages 13123–13127)

      Dr. Shohei Tashiro, Koji Matsuoka, Ai Minoda and Prof. Dr. Mitsuhiko Shionoya

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201206968

      Thumbnail image of graphical abstract

      Metal-mediated secondary structures of peptide-based foldamers were constructed using artificial backbone-coordinative oxime peptides. Complexation of the peptides with PdII afforded several mononuclear and dinuclear secondary structures such as helices and hairpins as confirmed by single-crystal XRD and NMR analyses (see picture).

    32. Imaging Agents

      Intrinsically Copper-64-Labeled Organic Nanoparticles as Radiotracers (pages 13128–13131)

      Tracy W. Liu, Thomas D. MacDonald, Dr. Jiyun Shi, Prof.Dr. Brian C. Wilson and Prof.Dr. Gang Zheng

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201206939

      Thumbnail image of graphical abstract

      PET friendly: Labels for PET imaging are incorporated into completely organic porphysomes by using a fast (30 min), one-pot, high-yielding (>95 %) procedure to produce highly stable (>48 h) radiolabeled nanoparticles that show the highest specific activity ever reported for a 64Cu-labeled nanoparticle. These 64Cu-porphysomes can be accurately and noninvasively tracked in vivo.

    33. Biomaterials

      Fibrous Nanostructures from the Self-Assembly of Designed Repeat Protein Modules (pages 13132–13135)

      Dr. Jonathan J. Phillips, Charlotte Millership and Dr. Ewan R. G. Main

      Version of Record online: 13 NOV 2012 | DOI: 10.1002/anie.201203795

      Thumbnail image of graphical abstract

      Single-protein-chain superhelical filaments are obtained from monomeric repeat proteins by controlling the chemistry and solvent exposure at their terminal interfaces. The assembly was achieved in aqueous solution, at neutral pH value, and at room temperature. The building block was a recombinantly engineered designed tetratricopeptide repeat protein. Directed head-to-tail self-assembly was driven by genetically encoded orthogonal native chemical ligation.

    34. Peptide Design

      Combination of Phage Display and Molecular Grafting Generates Highly Specific Tumor-Targeting Miniproteins (pages 13136–13139)

      Dr. Frederic Zoller, Dr. Annette Markert, Dr. Philippe Barthe, Wenye Zhao, Prof. Dr. Wilko Weichert, Dr. Vasileios Askoxylakis, Dr. Annette Altmann, Dr. Walter Mier and Prof. Dr. Uwe Haberkorn

      Version of Record online: 13 NOV 2012 | DOI: 10.1002/anie.201203857

      Thumbnail image of graphical abstract

      Frankenstein′s peptide: The grafting of the binding domain from miniprotein Min-23 into the sunflower trypsin inhibitor (SFTI-I) peptide scaffold (see scheme) preserved its in vitro and in vivo binding specificity and proteolytic stability. The combination of these peptides was shown to be tumor-specific with a good binding affinity for delta-like ligand 4 (Dll4) protein. The use of SFTI-I as a peptide scaffold is ideal for hit-to-lead development.

    35. Amyloid β-Peptides

      You have full text access to this OnlineOpen article
      Site-Specific Identification of an Aβ Fibril–Heparin Interaction Site by Using Solid-State NMR Spectroscopy (pages 13140–13143)

      Dr. Jillian Madine, Dr. Maya J. Pandya, Dr. Matthew R. Hicks, Prof. Alison Rodger, Dr. Edwin A. Yates, Prof. Sheena E. Radford and Prof. David A. Middleton

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201204459

      Thumbnail image of graphical abstract

      At the surface of Aβ1-40 amyloid fibrils that have a threefold molecular symmetry (green in the left picture) a site of interaction of the glycosaminoglycan analogue heparin (blue) was identified. The binding site consists of residues at the N terminus and the turn regions defining the apices of the triangular geometry. Heparin has a lower affinity for Aβ1-40 fibrils having twofold molecular symmetry, thus revealing a remarkable morphological selectivity.

    36. Reaction Mechanisms

      Dihydrooxazine Oxides as Key Intermediates in Organocatalytic Michael Additions of Aldehydes to Nitroalkenes (pages 13144–13148)

      Dr. Gokarneswar Sahoo, Dr. Hasibur Rahaman, Dr. Ádám Madarász, Dr. Imre Pápai, Mikko Melarto, Dr. Arto Valkonen and Prof. Dr. Petri M. Pihko

      Version of Record online: 13 NOV 2012 | DOI: 10.1002/anie.201204833

      Thumbnail image of graphical abstract

      Pause and play: Dihydrooxazine oxides are stable intermediates that are protonated directly, without the intermediacy of the zwitterions, in organocatalytic Michael additions of aldehydes and nitroalkenes (see scheme, R=alkyl). Protonation of these species explains both the role of the acid co-catalyst in these reactions, and the observed stereochemistry when the reaction is conducted with α-alkylnitroalkenes.

    37. Lithium Batteries

      High-Voltage Pyrophosphate Cathode: Insights into Local Structure and Lithium-Diffusion Pathways (pages 13149–13153)

      John M. Clark, Dr. Shin-ichi Nishimura, Prof. Atsuo Yamada and Prof. M. Saiful Islam

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201205997

      Thumbnail image of graphical abstract

      Ion-transport paths: Combined modeling and neutron diffraction studies provide atomic-scale insights into Li2FeP2O7, a material proposed for a new lithium-battery cathode with reversible electrode operation at the highest voltage of all known Fe-based phosphates. The results indicate that Li+ ions are transported rapidly through a 2D network along the paths shown in green in the picture.

    38. Photochromism

      Photoelectrocatalysis to Improve Cycloreversion Quantum Yields of Photochromic Dithienylethene Compounds (pages 13154–13158)

      Sumin Lee, Dr. Youngmin You, Dr. Kei Ohkubo, Prof. Shunichi Fukuzumi and Prof. Wonwoo Nam

      Version of Record online: 13 NOV 2012 | DOI: 10.1002/anie.201206256

      Thumbnail image of graphical abstract

      An open and shut case: Photoirradiation of the 9-mesityl-10-methylacridinium ion, which acts as a photoredox catalyst, evoked catalytic cycloreversion of the photochromic 1,2-dithienylethene (DTE) compounds with one order of magnitude enhancement in quantum yields. Mechanistic studies revealed that the back electron transfer and electron transfer from the neutral closed form of DTE compounds to the open-form radical cation are key steps.

    39. Asymmetric Catalysis

      The Synthesis of Chiral Isotetronic Acids with Amphiphilic Imidazole/Pyrrolidine Catalysts Assembled in Oil-in-Water Emulsion Droplets (pages 13159–13162)

      Boyu Zhang, Dr. Zongxuan Jiang, Dr. Xin Zhou, Dr. Shengmei Lu, Dr. Jun Li, Dr. Yan Liu and Prof. Can Li

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201206438

      Thumbnail image of graphical abstract

      Drop it! A highly enantioselective catalytic cascade reaction of α-ketoacids and aldehydes is achieved using the title catalyst and water as the solvent. Fluorescence imaging shows that the catalyst is mainly distributed on the surface of emulsion droplets. Optically active isotetronic acids can be obtained with this method and the emulsion droplets are responsible for the high reactivity and enantioselectivity.

    40. Surface Chemistry

      Improved Hydrothermal Stability of Mesoporous Oxides for Reactions in the Aqueous Phase (pages 13163–13167)

      Dr. Hien N. Pham, Amanda E. Anderson, Robert L. Johnson, Prof. Klaus Schmidt-Rohr and Prof. Abhaya K. Datye

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201206675

      Thumbnail image of graphical abstract

      A simple and inexpensive approach is used to coat metal oxide surfaces (SBA-15) with thin films of carbon. These carbon films provide improved hydrothermal stability to oxides, such as silica and alumina, which are not otherwise stable at elevated temperatures in the presence of liquid water (see picture). Furthermore, the carbon film changes the surface chemistry of the support.

    41. Chemical Hydrogen Storage

      Reduction of Borazines Mediated by Low-Valent Chromium Species (pages 13168–13172)

      Tyler J. Carter, Dr. Jeff W. Kampf and Prof. Nathaniel K. Szymczak

      Version of Record online: 14 NOV 2012 | DOI: 10.1002/anie.201206668

      Thumbnail image of graphical abstract

      Recharging spent BN fuel: {Cr(CO)3} mediates the reduction of borazines by hydride and methyl nucleophiles to generate anionic complexes of dearomatized hexamethylborazine. Subsequent quenching leads to the release of a substituted cyclotriborazane, successfully demonstrating the stepwise reduction of a B[DOUBLE BOND]N bond.

    42. Natural Products

      Imaging Mass Spectrometry and Genome Mining Reveal Highly Antifungal Virulence Factor of Mushroom Soft Rot Pathogen (pages 13173–13177)

      Katharina Graupner, Dr. Kirstin Scherlach, Tom Bretschneider, Dr. Gerald Lackner, Dr. Martin Roth, Prof. Dr. Harald Gross and Prof. Dr. Christian Hertweck

      Version of Record online: 19 NOV 2012 | DOI: 10.1002/anie.201206658

      Thumbnail image of graphical abstract

      Caught in the act: Imaging mass spectrometry of a button mushroom (see picture) infected with the soft rot pathogen Janthinobacterium agaricidamnosum in conjunction with genome mining revealed jagaricin as a highly antifungal virulence factor that is not produced under standard cultivation conditions. The structure of jagaricin was rigorously elucidated by a combination of physicochemical analyses, chemical derivatization, and bioinformatics.

SEARCH

SEARCH BY CITATION