Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 16

April 14, 2014

Volume 53, Issue 16

Pages 4009–4248

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Organocatalytic Asymmetric Formation of Steroids (Angew. Chem. Int. Ed. 16/2014) (page 4009)

      Kim Søholm Halskov, Bjarke S. Donslund, Dr. Sebastian Barfüsser and Prof. Karl Anker Jørgensen

      Article first published online: 18 MAR 2014 | DOI: 10.1002/anie.201401114

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      Inspired by “Mountain View”, a painting by Paul Klee, K. A. Jørgensen and co-workers present the organocatalytic asymmetric formation of steroids in their Communication on page 4137 ff. The picture applies mosaic shapes in analogy with the artistic elements of Paul Klee to illustrate the organocatalytic asymmetric formation of steroids. The A and B ring in the steroid (to the left) and the D ring (to the right) are merged by the green organocatalyst in the middle towards the blue sky.

    2. You have free access to this content
      Inside Cover: Copper-Catalyzed Coupling of Oxime Acetates with Sodium Sulfinates: An Efficient Synthesis of Sulfone Derivatives (Angew. Chem. Int. Ed. 16/2014) (page 4010)

      Xiaodong Tang, Liangbin Huang, Yanli Xu, Jidan Yang, Dr. Wanqing Wu and Prof. Dr. Huanfeng Jiang

      Article first published online: 2 APR 2014 | DOI: 10.1002/anie.201401135

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      Upon treatment with a Cu catalyst oxime acetates can be converted into sulfonylvinylamine products, which will further transform into useful β-ketosulfones upon hydrolysis with H2O. H. Jiang et al. describe in their Communication on page 4205 ff. how the oxime acetates act as both the substrate and oxidant, thus giving the process an environmentally friendly character. The background shows the ancient Chinese symbol “The Eight Trigrams” to indicate the harmony between humans and nature, which is also the purpose of green chemistry.

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      Inside Back Cover: The Formazanate Ligand as an Electron Reservoir: Bis(Formazanate) Zinc Complexes Isolated in Three Redox States (Angew. Chem. Int. Ed. 16/2014) (page 4249)

      Mu-Chieh Chang, Thomas Dann, Dr. David P. Day, Dr. Martin Lutz, Dr. Gregory G. Wildgoose and Dr. Edwin Otten

      Article first published online: 9 APR 2014 | DOI: 10.1002/anie.201401122

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      Formazans have been known since about 1900 for their intense color, and they find applications as dyestuffs and analytical reagents. In their Communication on page 4118 ff., E. Otten et al. describe formazanate anions as unique ligands in coordination chemistry. The facile and reversible redox chemistry accessible for these ligands allows the full characterization of bis(formazanate) zinc complexes in three oxidation states. Cover image courtesy of Hsin-Wei Lin.

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      Back Cover: The Bioinorganic Chemistry of Apoptosis: Potential Inhibitory Zinc Binding Sites in Caspase-3 (Angew. Chem. Int. Ed. 16/2014) (page 4250)

      A. Gerard Daniel, Erica J. Peterson and Dr. Nicholas P. Farrell

      Article first published online: 19 MAR 2014 | DOI: 10.1002/anie.201401105

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      Zinc ions and copper ions are known to play important and contrasting roles in apoptosis, with zinc inhibiting the pro-apoptotic protein caspase-3. In their Communication on page 4098 ff., N. P. Farrell and co-workers present evidence that zinc inhibits caspase-3 through interacting with the active-site histidine residue rather than with the catalytic dyad as had previously been assumed.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Frontispiece: Rhodium Enalcarbenoids: Direct Synthesis of Indoles by Rhodium(II)-Catalyzed [4+2] Benzannulation of Pyrroles

      Sudam Ganpat Dawande, Vinaykumar Kanchupalli, Jagadeesh Kalepu, Haribabu Chennamsetti, Bapurao Sudam Lad and Dr. Sreenivas Katukojvala

      Article first published online: 14 APR 2014 | DOI: 10.1002/anie.201481671

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      S. Katukojvala et al. describe in their Communication on page 4076 ff. the direct [4+2] benzannulation of pyrroles to indoles by using a rhodium enalcarbenoid generated by rhodium(II)-catalyzed decomposition of enaldiazo compounds.

  3. Graphical Abstract

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
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    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 16/2014 (pages 4013–4025)

      Article first published online: 14 APR 2014 | DOI: 10.1002/anie.201490014

  4. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Corrigendum: Rare-Earth-Metal Methylidene Complexes (page 4025)

      Dr. Jochen Kratsch and Prof. Dr. Peter W. Roesky

      Article first published online: 14 APR 2014 | DOI: 10.1002/anie.201401112

      This article corrects:

      Rare-Earth-Metal Methylidene Complexes

      Vol. 53, Issue 2, 376–383, Article first published online: 7 NOV 2013

  5. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Masaya Sawamura (page 4032)

      Article first published online: 11 DEC 2013 | DOI: 10.1002/anie.201309698

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      “My biggest inspiration is the Pacific Ocean. I advise my students to refresh their brains on Sundays …“ This and more about Masaya Sawamura can be found on page 4032.

  7. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Photochemically-Generated Intermediates in Synthesis. By Angelo Albini and Maurizio Fagnoni. (pages 4034–4035)

      Axel G. Griesbeck

      Article first published online: 5 MAR 2014 | DOI: 10.1002/anie.201400117

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      John Wiley and Sons, Hoboken, 2013. 380 pp., hardcover, € 132.00.—ISBN 978-0470915349

  9. Highlights

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

      Metal-Containing Carbonyl Ylides: Versatile Reactants in Catalytic Enantioselective Cascade Reactions (pages 4038–4040)

      Prof. Dr. Jia-Rong Chen, Xiao-Qiang Hu and Prof. Dr. Wen-Jing Xiao

      Article first published online: 5 MAR 2014 | DOI: 10.1002/anie.201400018

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      New players in town: In situ generated transition-metal-containing carbonyl ylides are a unique class of reagents which have found wide applications in catalytic asymmetric cascade reactions. Recent advances in reaction design are likely to lead to more novel developments with these reactive species.

    2. Natural Products

      Total Syntheses of (±)-Aspidophylline A (pages 4041–4042)

      Dr. Eric Doris

      Article first published online: 5 MAR 2014 | DOI: 10.1002/anie.201400720

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      Yes they can! The groups of Zhu and Ma recently reinvestigated the synthetic route to aspidophilline A. These approaches are discussed in the context of the first total synthesis of the title alkaloid that was reported by Garg and co-workers in 2011.

  10. Minireview

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Iron Catalysis

      Iron Cyclopentadienone Complexes: Discovery, Properties, and Catalytic Reactivity (pages 4044–4055)

      Dr. Adrien Quintard and Prof. Jean Rodriguez

      Article first published online: 18 MAR 2014 | DOI: 10.1002/anie.201310788

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      The new iron age? Iron cyclopentadienone complexes are easily synthesized from simple and cheap materials, are stable, and through the presence of a non-innocent ligand, have unique catalytic features. The properties of such complexes and their applications in original redox-neutral transformations in both racemic and enantioselective reactions are reviewed.

  11. Review

    1. Top of page
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    11. Minireview
    12. Review
    13. Communications
    1. Drug Discovery

      Heart Regeneration: Opportunities and Challenges for Drug Discovery with Novel Chemical and Therapeutic Methods or Agents (pages 4056–4075)

      Dr. Alleyn T. Plowright, Dr. Ola Engkvist, Dr. Adrian Gill, Dr. Laurent Knerr and Dr. Qing-Dong Wang

      Article first published online: 27 JAN 2014 | DOI: 10.1002/anie.201307034

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      Small molecules, RNA approaches, modified peptides, and proteins are promising candidates for the regeneration of heart tissue through differentiation of stem cells, proliferation of existing cardiomyocytes and cardiac progenitor cells, and cell reprogramming to cardiomyocytes. Recent advances, including novel screening strategies, and the upcoming challenges and opportunities to develop these hits into pharmaceuticals are summarized.

  12. Communications

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Heterocycle Synthesis

      Rhodium Enalcarbenoids: Direct Synthesis of Indoles by Rhodium(II)-Catalyzed [4+2] Benzannulation of Pyrroles (pages 4076–4080)

      Sudam Ganpat Dawande, Vinaykumar Kanchupalli, Jagadeesh Kalepu, Haribabu Chennamsetti, Bapurao Sudam Lad and Dr. Sreenivas Katukojvala

      Article first published online: 3 MAR 2014 | DOI: 10.1002/anie.201400161

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      Fat cat: A new class of enaldiazo compounds resulted in the first transition-metal-catalyzed [4+2] benzannulation of pyrroles to deliver indoles. The benzannulation is proposed to involve an unprecedented diacceptor rhodium enalcarbenoid. The reaction was used in the highly efficient synthesis of the natural product leiocarpone and a potent adipocyte fatty-acid binding protein inhibitor.

    2. Enzyme Models

      You have full text access to this OnlineOpen article
      Aerobic Damage to [FeFe]-Hydrogenases: Activation Barriers for the Chemical Attachment of O2 (pages 4081–4084)

      Dr. Adam Kubas, Dr. David De Sancho, Dr. Robert B. Best and Dr. Jochen Blumberger

      Article first published online: 11 MAR 2014 | DOI: 10.1002/anie.201400534

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      Clearing the air: The free energy profiles for the chemical attachment of O2 to the active sites of [FeFe]-hydrogenases from Clostridium pasteurianum and Desulfovibrio desulfuricans were investigated. Based on the results, possible target sites for future mutation studies were suggested that may reduce oxygen binding and thus the oxygen sensitivity of these enzymes.

    3. Hole Transport

      A Simple 3,4-Ethylenedioxythiophene Based Hole-Transporting Material for Perovskite Solar Cells (pages 4085–4088)

      Dr. Hairong Li, Kunwu Fu, Prof. Anders Hagfeldt, Prof. Michael Grätzel, Prof. Subodh G. Mhaisalkar and Prof. Andrew C. Grimsdale

      Article first published online: 14 MAR 2014 | DOI: 10.1002/anie.201310877

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      Heterocycle power! A power-conversion efficiency of 13.8 % under AM 1.5G illumination was achieved in a perovskite-based solar cell with a new hole-transporting material based on 3,4-ethylenedioxythiophene (H101). This is the first heterocycle-containing material with >10 % efficiency in such devices, and has great potential to replace the more expensive spiro-OMeTAD, given its much simpler and less expensive synthesis.

    4. Reactive Intermediates

      Gas-Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes (pages 4089–4092)

      Dr. Caroline C. Womack, Dr. Kyle N. Crabtree, Laura McCaslin, Dr. Oscar Martinez Jr., Prof. Robert W. Field, Prof. John F. Stanton and Dr. Michael C. McCarthy

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201311082

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      A small stable singlet carbene: The geometric structure of dihydroxycarbene (HO[BOND]equation image[BOND]OH) is experimentally determined using Fourier transform microwave spectroscopy. This carbene, a structural isomer of the simplest Criegee intermediate (CH2OO) and formic acid (HCOOH), is found to be long-lived in the dilute gas phase because of the stabilizing effect of the two electron-donating hydroxy groups.

    5. Molecular Switches

      Frontier Orbital Control of Molecular Conductance and its Switching (pages 4093–4097)

      Dr. Yuta Tsuji and Prof. Dr. Roald Hoffmann

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201311134

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      The phase and amplitude of the frontier molecular orbitals at the sites that are connected to electrodes play an essential role in determining transmission of electrons through a π system. When applied to two diarylethene switches, theory then predicts that for some specified sites the switching behavior will be inverted; that is, the “open” molecular form of the switch will be more conductive.

    6. Enzyme Inhibition

      The Bioinorganic Chemistry of Apoptosis: Potential Inhibitory Zinc Binding Sites in Caspase-3 (pages 4098–4101)

      A. Gerard Daniel, Erica J. Peterson and Dr. Nicholas P. Farrell

      Article first published online: 18 MAR 2014 | DOI: 10.1002/anie.201311114

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      Zinc site insight: Zinc inhibition of caspase-3 is largely uncompetitive. Substrate binding was shown to be unaffected by Zn2+ in the sub-micromolar range where most inhibition occurs. This rules out zinc binding to the catalytic dyad, the generally assumed inhibitory site. Based on a hypothesis that zinc inhibition occurs through interaction with the catalytic His residue, a new inhibitory zinc site was proposed and was shown to better fit the experimental observations.

    7. Electrocatalysts

      Carbon Nanotubes/Heteroatom-Doped Carbon Core–Sheath Nanostructures as Highly Active, Metal-Free Oxygen Reduction Electrocatalysts for Alkaline Fuel Cells (pages 4102–4106)

      Young Jin Sa, Dr. Chiyoung Park, Dr. Hu Young Jeong, Dr. Seok-Hee Park, Prof. Zonghoon Lee, Prof. Kyoung Taek Kim, Dr. Gu-Gon Park and Prof. Sang Hoon Joo

      Article first published online: 19 FEB 2014 | DOI: 10.1002/anie.201307203

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      A facile, scalable route for the synthesis of new nanocomposites that are based on carbon nanotubes/heteroatom-doped carbon (CNT/HDC) core–sheath nanostructures has been developed. The CNT/HDC nanostructures exhibit excellent electrocatalytic activity, kinetics, and durability for the oxygen reduction reaction, and they also performed well as the cathode catalysts in alkaline fuel cells.

    8. Single-Molecule Studies

      Direct and Single-Molecule Visualization of the Solution-State Structures of G-Hairpin and G-Triplex Intermediates (pages 4107–4112)

      Dr. Arivazhagan Rajendran, Prof. Dr. Masayuki Endo, Kumi Hidaka and Prof. Dr. Hiroshi Sugiyama

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201308903

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      Back to the fold: Using a DNA origami frame as a nanoscaffold for the structural control, the unprecedented solution-state structures of a tetramolecular antiparallel and (3+1)-type G-quadruplex intermediates in the G-quadruplex folding, such as G-hairpin and G-triplex, can be visualized directly at the single-molecule level with nanometer resolution by AFM.

    9. Protein Chemistry

      Click-Tag and Amine-Tag: Chemical Tag Approaches for Efficient Protein Labeling In Vitro and on Live Cells using the Naturally Split Npu DnaE Intein (pages 4113–4117)

      Dr. Vivien Schütz and Prof. Dr. Henning D. Mootz

      Article first published online: 11 MAR 2014 | DOI: 10.1002/anie.201309396

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      Click and splice: Short tags of only a few amino acids fused to a recombinantly produced split intein fragment were modified with synthetic moieties and then transferred to a protein of interest by protein trans-splicing. These two-step procedures circumvent exposure of the protein of interest to copper ions for click chemistry and undesired modification of lysines, even though standard bioconjugation reagents are used.

    10. Redox-Non-Innocent Ligands

      The Formazanate Ligand as an Electron Reservoir: Bis(Formazanate) Zinc Complexes Isolated in Three Redox States (pages 4118–4122)

      Mu-Chieh Chang, Thomas Dann, Dr. David P. Day, Dr. Martin Lutz, Dr. Gregory G. Wildgoose and Dr. Edwin Otten

      Article first published online: 24 FEB 2014 | DOI: 10.1002/anie.201309948

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      N is better than C: Bis(formazanate) zinc complexes (see picture; Zn yellow, N blue, O red, Na green) show sequential and reversible redox chemistry in which the formazanate ligands are reduced to metallaverdazyl radicals. These ligands are very similar to β-diketiminates, but the nitrogen-rich NNCNN backbone of formazanates opens the door to redox chemistry that is otherwise difficult to access.

    11. Supramolecular Chemistry

      Hydrophobic Self-Assembly Affords Robust Noncovalent Polymer Isomers (pages 4123–4126)

      Dr. Jonathan Baram, Dr. Haim Weissman, Dr. Yaron Tidhar, Dr. Iddo Pinkas and Prof. Boris Rybtchinski

      Article first published online: 18 MAR 2014 | DOI: 10.1002/anie.201310571

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      A strong hold: Strong hydrophobic interactions result in stable noncovalent polymer isomers derived from a single covalent unit. These isomers have different electronic and photonic properties and are stable in water, even upon prolonged heating to 100 °C.

    12. Biomineralization

      Functionalizing Single Crystals: Incorporation of Nanoparticles Inside Gel-Grown Calcite Crystals (pages 4127–4131)

      Yujing Liu, Wentao Yuan, Ye Shi, Xiaoqiang Chen, Prof. Yong Wang, Prof. Hongzheng Chen and Prof. Hanying Li

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310712

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      Functionalization of crystals: Biogenic single crystals incorporate biomacromolecules and form single-crystal composites. The abnormal composite structure led to the idea to obtain synthetic crystals with nonintrinsic properties by modifing their internal structure. Intrinsically colorless and diamagnetic calcite single crystals are turned into colored and paramagnetic solids through incorporation of gold and ferroferric oxide nanoparticles.

    13. Surface Chemistry

      Spatial and Directional Control over Self-Assembly Using Catalytic Micropatterned Surfaces (pages 4132–4136)

      Dr. Alexandre G. L. Olive, Nor Hakimin Abdullah, Dr. Iwona Ziemecka, Dr. Eduardo Mendes, Dr. Rienk Eelkema and Prof. Dr. Jan H. van Esch

      Article first published online: 11 MAR 2014 | DOI: 10.1002/anie.201310776

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      Following a pattern: Catalyst-assisted self-assembly is widespread in nature to achieve spatial control over structure formation. Reported herein is the formation of hydrogel micropatterns on catalytic surfaces. A unique mechanism of fiber formation for a synthetic system, using building blocks added at the interface, leads to orientated structures. Therefore organization is attained at the micro- and nanoscale.

    14. Synthetic Methods

      Organocatalytic Asymmetric Formation of Steroids (pages 4137–4141)

      Kim Søholm Halskov, Bjarke S. Donslund, Dr. Sebastian Barfüsser and Prof. Karl Anker Jørgensen

      Article first published online: 19 FEB 2014 | DOI: 10.1002/anie.201400203

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      Organocatalysis made it possible: The reported methodology gives 14 β-steroids, displaying a broad generality, in one step, and includes various substituents on the A ring, variations of the B ring, hydroxy or alkyl substituents in the 12-position of the C ring, and different substituents in the angular position at C13. Furthermore, the developed reaction concept includes reactions with quinones to form D-homosteroids in excellent yields and stereoselectivities.

    15. Nanoparticle Catalysis

      The Origin of Shape Sensitivity in Palladium-Catalyzed Suzuki–Miyaura Cross Coupling Reactions (pages 4142–4145)

      Dr. Gillian Collins, Michael Schmidt, Dr. Colm O'Dwyer, Prof. Justin D. Holmes and Dr. Gerard P. McGlacken

      Article first published online: 11 MAR 2014 | DOI: 10.1002/anie.201400483

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      Tracking catalysis: The shape sensitivity of cubic, cuboctahedral, and octahedral Pd nanoparticle catalysts in Suzuki–Miyaura coupling reactions was studied. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals.

    16. Nanoporous Carbon

      Visible-Light Photochemical Activity of Nanoporous Carbons under Monochromatic Light (pages 4146–4148)

      Dr. Leticia F. Velasco, Dr. Joao C. Lima and Dr. Conchi Ania

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201400887

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      Scratching the surface: The ability of semiconductor-free nanoporous carbons to absorb low-energy photons from visible light and convert them into chemical reactions (i.e., phenol photooxidation) is demonstrated by using monochromatic light. Data showed the strong dependence of the photochemical activity on the wavelength of the irradiation source and the chemical composition of the nanoporous carbon.

    17. α-Amination

      Merging Aerobic Oxidation and Enamine Catalysis in the Asymmetric α-Amination of β-Ketocarbonyls Using N-Hydroxycarbamates as Nitrogen Sources (pages 4149–4153)

      Changming Xu, Dr. Long Zhang and Prof. Dr. Sanzhong Luo

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201400776

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      Merging O and N: Enantioselective α-amination of β-ketocarbonyl compounds has been achieved by merging enamine catalysis and CuI-catalyzed aerobic oxidation of hydroxycarbamates. Excellent chemoselectivity and enantioselectivity are obtained with the aid of a simple primary/tertiary diamine catalyst. This presents a facile route for the asymmetric synthesis of unnatural amino acids.

    18. Synthetic Methods

      Copper(II)-Catalyzed Silylation of Activated Alkynes in Water: Diastereodivergent Access to E- or Z-β-Silyl-α,β-Unsaturated Carbonyl and Carboxyl Compounds (pages 4154–4158)

      Joseph A. Calderone and Prof. Dr. Webster L. Santos

      Article first published online: 14 FEB 2014 | DOI: 10.1002/anie.201310695

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      Dial a diastereomer: The title reaction proceeds through the activation of Me2PhSiBpin in water at room temperature and open atmosphere to produce high yields of vinylsilanes conjugated to carbonyl groups. A surprising diastereodivergent access to olefin geometry was discovered using this silyl conjugate addition strategy: aldehydes were Z selective while esters and amides exclusively delivered the E-configured products.

    19. Green Chemistry

      Stereoselective Silylcupration of Conjugated Alkynes in Water at Room Temperature (pages 4159–4163)

      Roscoe T. H. Linstadt, Carl A. Peterson, Daniel J. Lippincott, Carina I. Jette and Prof. Bruce H. Lipshutz

      Article first published online: 18 MAR 2014 | DOI: 10.1002/anie.201311035

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      Fast, cheap, and green: Micellar catalysis enables the selective construction of a variety β-silyl-substituted carbonyl derivatives under mild aqueous conditions. The reaction is catalyzed by low levels of CuI, is compatible with numerous electron-withdrawing groups, affords high yields, and provides opportunities for scale-up and recycling of the reaction medium. The environmental impact, as measured by E Factors, is very low.

    20. Natural Product Synthesis

      Total Synthesis of (±)-Clavilactones A, B, and Proposed D through Iron-Catalyzed Carbonylation–Peroxidation of Olefin (pages 4164–4167)

      Leiyang Lv, Prof. Dr. Baojian Shen and Prof. Dr. Zhiping Li

      Article first published online: 11 MAR 2014 | DOI: 10.1002/anie.201400326

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      A general, concise, and efficient approach for synthesis of clavilactones A, B, and D has been established. Three steps from aldehydes, 1,5-dienes, and tBuOOH build up α,β-epoxy-γ-butyrolactones (see scheme, left) as the key building blocks for synthesis of clavilactone family and its derivatives. From these results, the previously proposed clavilactone D structure requires revision.

    21. Cumulene Structures

      C4 Cumulene and the Corresponding Air-Stable Radical Cation and Dication (pages 4168–4172)

      Yan Li, Dr. Kartik Chandra Mondal, Dr. Prinson P. Samuel, Prof. Dr. Hongping Zhu, Claudia M. Orben, Dr. Saravanan Panneerselvam, Priv.-Doz. Dr. Birger Dittrich, Dr. Brigitte Schwederski, Prof. Dr. Wolfgang Kaim, Totan Mondal, Dr. Debasis Koley and Prof. Dr. Herbert W. Roesky

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310975

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      Carbons get excited! Commercially available CBr4 is utilized as a source of dicarbon for the preparation of the C4 cumulene that contains a cyclic alkyl(amino) carbene (cAAC). Lithium or potassium is used as a reducing agent. The corresponding air-stable radical cation and dication of the C4 cumulene were also synthesized and their interconversion was studied by cyclic voltammetry.

    22. Functional Materials

      Phosphoryl-Rich Flame-Retardant Ions (FRIONs): Towards Safer Lithium-Ion Batteries (pages 4173–4176)

      Michael F. Rectenwald, Joshua R. Gaffen, Prof. Arnold L. Rheingold, Dr. Alexander B. Morgan and Prof. John D. Protasiewicz

      Article first published online: 11 MAR 2014 | DOI: 10.1002/anie.201310867

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      Playing with fire: A series of borate and phosphate anions (flame-retardant ions; FRIONs) have been produced in high yields and purity using a readily accessible diphosphinatocatechol. The phosphoryl-rich character of the anions imparts flame-retardant qualities and offers potential utility as lithium salts for safer lithium-ion batteries.

    23. Synthetic Methods

      Metal-Triflate-Catalyzed Synthesis of Polycyclic Tertiary Alcohols by Cyclization of γ-Allenic Ketones (pages 4177–4180)

      Ilhem Diaf, Dr. Gilles Lemière and Dr. Elisabet Duñach

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310724

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      Simply complex: The described catalytic carbonyl-ene reaction is efficiently performed under mild reaction conditions by using only 1 mol % of bismuth(III) triflate, thus affording functionalized molecular scaffolds. Complex polycyclic structures with a defined stereochemistry have been synthesized by using the carbonyl-ene products in a subsequent hydroxy-directed Diels–Alder reaction.

    24. Homogeneous Catalysis

      cis-Specific Hydrofluorination of Alkenylarenes under Palladium Catalysis through an Ionic Pathway (pages 4181–4185)

      Dr. Enrico Emer, Lukas Pfeifer, Dr. John M. Brown and Prof. Véronique Gouverneur

      Article first published online: 18 MAR 2014 | DOI: 10.1002/anie.201310056

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      See attached PdF: A series of benzylic fluorides was prepared by hydrofluorination which proceeds through a PdII/IV catalytic manifold. The method is mechanistically distinct from previously reported radical hydrofluorination, and is characterized by its clean regioselectivity and unique cis stereospecificity. The first example of enantioselective net HF addition onto 2-vinylnaphthalene is also disclosed.

    25. Asymmetric Catalysis

      Enantioselective Synthesis of Allylboronates and Allylic Alcohols by Copper-Catalyzed 1,6-Boration (pages 4186–4190)

      Dr. Yunfei Luo, Iain D. Roy, Amaël G. E. Madec and Prof. Hon Wai Lam

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310380

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      1,6-Borations of electron-deficient dienes with bis(pinacolato)diboron using copper catalyst loadings as low as 0.0049 mol % provided chiral allylboronates that, after oxidation, result in allylic alcohols in high enantioselectivities and 1,6:1,4 ratios. The allylboronates can also be used in stereoselective allylations of aldehydes. This process was applied to a concise synthesis of atorvastatin.

    26. Homogeneous Catalysis

      Rhodium(III)-Catalyzed Alkenylation Reactions of 8-Methylquinolines with Alkynes by C(sp3)[BOND]H Activation (pages 4191–4195)

      Bingxian Liu, Tao Zhou, Prof. Dr. Bin Li, Prof. Shansheng Xu, Prof. Dr. Haibin Song and Prof. Dr. Baiquan Wang

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310711

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      Highly regio- and stereoselective alkenylation reactions of 8-methylquinolines with alkynes give 8-allylquinolines in good yields. These reactions are catalyzed by [{Cp*RhCl2}2] (Cp*=C5Me5) and proceed by C(sp3)[BOND]H bond activation.

    27. Heterocycles

      Hexafluoroantimonic Acid Catalysis: Formal [3+2+2] Cycloaddition of Aziridines with Two Alkynes (pages 4196–4199)

      Ming-Bo Zhou, Ren-Jie Song and Prof. Dr. Jin-Heng Li

      Article first published online: 11 MAR 2014 | DOI: 10.1002/anie.201310944

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      Superacid powers: The title reaction of unactivated aziridines with two of the same or different terminal alkyne components has been developed, thus opening a new access to seven-membered heterocyclic ring systems. This transformation is experimentally simple while furnishing azepine derivatives in good yields (up to 78%) with good levels of chemo- and regioselectivity. Ts= 4-toluenesulfonyl.

    28. Sustainable Chemistry

      Highly Efficient Chemical Process To Convert Mucic Acid into Adipic Acid and DFT Studies of the Mechanism of the Rhenium-Catalyzed Deoxydehydration (pages 4200–4204)

      Dr. Xiukai Li, Di Wu, Dr. Ting Lu, Dr. Guangshun Yi, Prof. Haibin Su and Dr. Yugen Zhang

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310991

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      Taking a dip: A highly efficient synthetic protocol has been developed for the conversion of mucic acid into adipic acid by the oxorhenium-complex-catalyzed deoxydehydration reaction and subsequent Pt/C-catalyzed transfer hydrogenation. Quantitative yields were achieved for the conversion of mucic acid into muconic acid and adipic acid esters either through separate sequences or through a one-pot process.

    29. Synthetic Methods

      Copper-Catalyzed Coupling of Oxime Acetates with Sodium Sulfinates: An Efficient Synthesis of Sulfone Derivatives (pages 4205–4208)

      Xiaodong Tang, Liangbin Huang, Yanli Xu, Jidan Yang, Dr. Wanqing Wu and Prof. Dr. Huanfeng Jiang

      Article first published online: 20 FEB 2014 | DOI: 10.1002/anie.201311217

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      Copper brings us together: The title reaction involves copper-catalyzed N[BOND]O bond cleavage, activation of a vinyl sp2 C[BOND]H bond and C[BOND]S bond formation; it uses simple oxime acetates and sodium sulfinates to synthesize sulfonylvinylamine products without the need for additional oxidants or additives. Upon hydrolysis, useful β-ketosulfones are obtained.

    30. C[BOND]H Activation

      You have full text access to this OnlineOpen article
      Diastereoselective Carbocyclization of 1,6-Heptadienes Triggered by Rhodium-Catalyzed Activation of an Olefinic C[BOND]H Bond (pages 4209–4212)

      Dr. Christophe Aïssa, Kelvin Y. T. Ho, Dr. Daniel J. Tetlow and María Pin-Nó

      Article first published online: 14 MAR 2014 | DOI: 10.1002/anie.201400080

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      Folding alkenes: Described is the first example of a rhodium(I)-catalyzed functionalization of an olefinic C[BOND]H bond with a 1,6-heptadiene reagent. This carbocyclization is completely diastereoselective and creates at least three stereogenic centers from simple prochiral substrates. The directing group can easily be converted into other functional groups.

    31. Naturstoffe

      Total Synthesis of the Antibiotic Kendomycin: A Macrocyclization Using the Tsuji–Trost Etherification (pages 4213–4216)

      Dr. Tetsuya Sengoku, Dr. Shu Xu, Kenji Ogura, Yoshinori Emori, Kenji Kitada, Prof. Dr. Daisuke Uemura and Prof. Dr. Hirokazu Arimoto

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201400305

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      A new construct: The asymmetric total synthesis of the antibiotic kendomycin was accomplished by using a highly stereocontrolled convergent route. The key feature of the synthetic strategy is the construction of an 18-membered carbocycle based on an intramolecular Tsuji–Trost etherification/transannular Claisen rearrangement sequence. TBS=tert-butyldimethylsilyl.

    32. Total Synthesis

      Catalysis-Based Total Synthesis of Putative Mandelalide A (pages 4217–4221)

      Dipl.-Chem. Jens Willwacher and Prof. Alois Fürstner

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201400605

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      Bitter and sweet: The synthesis of the proposed structure of the cytotoxic macrolide mandelalide A reiterates the notion that structure elucidation of architecturally complex natural products is not always reliable. From the chemical viewpoint, the chosen route attests to the power of (transition) metals as catalysts for stereoselective synthesis. Most notable is the first application of terminal-acetylene metathesis to natural product chemistry.

    33. Chemical DNA Ligation

      DNA with 3′-5′-Disulfide Links—Rapid Chemical Ligation through Isosteric Replacement (pages 4222–4226)

      Dr. Volker Patzke, Prof. Dr. John S. McCaskill and Prof. Dr. Günter von Kiedrowski

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310644

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      Thiolated oligonucleotides show unprecedented high reaction rates in chemical ligation experiments. The influence of temperature on the templated reaction is shown with a system designed for fluorescence monitoring. Side reactions and the nontemplated ligation reactions are efficiently suppressed by the choice of DNA modification and the activation site.

    34. Protein Aggregation

      Sequestration of a β-Hairpin for Control of α-Synuclein Aggregation (pages 4227–4230)

      Dr. Ewa A. Mirecka, Hamed Shaykhalishahi, Aziz Gauhar, Şerife Akgül, Dr. Justin Lecher, Prof. Dr. Dieter Willbold, Dr. Matthias Stoldt and Dr. Wolfgang Hoyer

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201309001

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      Wrapping the hairpin: NMR spectroscopy identifies a β-hairpin conformation of α-synuclein in complex with an engineered β-wrapin. The β-wrapin inhibits α-synuclein aggregation and toxicity at substoichiometric concentration. Sequestration of a β-hairpin is a novel approach to interfere with the initial steps of the aggregation reaction.

    35. Cancer Therapy

      A Small-Molecule Drug Conjugate for the Treatment of Carbonic Anhydrase IX Expressing Tumors (pages 4231–4235)

      Nikolaus Krall, Francesca Pretto, Willy Decurtins, Dr. Gonçalo J. L. Bernardes, Prof. Claudiu T. Supuran and Prof. Dario Neri

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310709

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      Size advantage: Antibodies are currently the most widely used vehicles for drug-delivery applications. Small-molecule ligands, however, may have improved pharmacokinetics and better tissue penetration. Targeted small-molecule drug conjugates directed against the tumor marker carbonic anhydrase IX were synthesized, characterized in vitro, and tested in vivo.

    36. Bionanotechnology

      Hydrophobic Actuation of a DNA Origami Bilayer Structure (pages 4236–4239)

      Dipl.-Phys. Jonathan List, Michael Weber and Prof. Dr. Friedrich C. Simmel

      Article first published online: 11 MAR 2014 | DOI: 10.1002/anie.201310259

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      Hydrophobic interactions within cholesterol-modified DNA origami structures can induce large conformational changes, which can be used as the basis of a novel molecular switching mechanism. Intramolecularly folded DNA bilayer sheets are shown to unfold in the presence of surfactants and lipid membranes. Hydrophobic switching can be combined with a DNA-based lock and key mechanism, resulting in the conditional opening of the DNA bilayer structures.

    37. Borylene Exchange

      Metal-Only Lewis Pairs by Reversible Insertion of Ruthenium and Osmium Fragments into Metal–Boron Double Bonds (pages 4240–4243)

      Dipl.-Chem. Stefanie Bertsch, Dr. Rüdiger Bertermann, Prof. Dr. Holger Braunschweig, Dr. Alexander Damme, Dr. Rian D. Dewhurst, Dr. Ashwini K. Phukan, Christian Saalfrank, Dr. Alfredo Vargas, Benedikt Wennemann and Dr. Qing Ye

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310520

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      Separation anxiety: The insertion of a zerovalent ruthenium or osmium complex into the chromium–boron double bond of a borylene complex leads to new metal-only Lewis pairs (MOLPs: Ru[RIGHTWARDS ARROW]Cr and Os[RIGHTWARDS ARROW]Cr). The reaction creates new borylene complexes and is crystallization-controlled. A mechanism is proposed based on DFT calculations, along with a computational study of the unusual MOLPs.

    38. Combinatorial Chemistry

      Multi-Objective Molecular De Novo Design by Adaptive Fragment Prioritization (pages 4244–4248)

      Michael Reutlinger, Dr. Tiago Rodrigues, Dr. Petra Schneider and Prof. Dr. Gisbert Schneider

      Article first published online: 12 MAR 2014 | DOI: 10.1002/anie.201310864

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      Finding the best way: A molecular design method inspired by ant colony optimization generated novel, highly potent, druglike ligands for the sigma-1 and dopamine D4 receptors. The computational approach is readily applicable to combinatorial chemistry and delivers focused compound libraries profiled for desired target-panel activities.

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