Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 22

May 27, 2013

Volume 52, Issue 22

Pages 5651–5884

  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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: A Facile Strategy for Selective Incorporation of Phosphoserine into Histones (Angew. Chem. Int. Ed. 22/2013) (page 5651)

      Sangsik Lee, Seunghee Oh, Aerin Yang, Jihyo Kim, Prof. Dieter Söll, Prof. Daeyoup Lee and Prof. Hee-Sung Park

      Version of Record online: 2 MAY 2013 | DOI: 10.1002/anie.201303269

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      Selective phosphoserine incorporation is described by H.-S. Park et al. in their Communication on page 5771 ff. A general strategy for producing recombinant histones with site-specific serine phosphorylation has been developed by engineering phosphoseryl-tRNA synthethase (SepRS) and elongation factor Tu (EF-Tu). This method should facilitate the study of histone phosphorylation and cross-regulatory mechanisms.

    2. You have free access to this content
      Inside Cover: Polycyclooctadiene Complexes of Rhodium(I): Direct Access to Organometallic Nanoparticles (Angew. Chem. Int. Ed. 22/2013) (page 5652)

      Dr. Sudheendran Mavila, Dr. Charles E. Diesendruck, Sivan Linde, Liron Amir, Dr. Rafi Shikler and Prof. Dr. N. Gabriel Lemcoff

      Version of Record online: 2 MAY 2013 | DOI: 10.1002/anie.201303263

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      Organometallic nanoparticles can be prepared by intramolecular cross-linking of polycyclooctadiene with [{RhCl(C2H4)2}2]. In their Communication on page 5767 ff., N. G. Lemcoff et al. describe the controllability of the nanoparticle size through the amount of rhodium added. Furthermore, the parent polymer can be regenerated through the addition of a phosphine aldehyde derivative, thus proving the accessibility and reactivity of the imbedded metal.

    3. You have free access to this content
      Inside Back Cover: General and Efficient Synthesis of Indoles through Triazene-Directed C–H Annulation (Angew. Chem. Int. Ed. 22/2013) (page 5885)

      Chengming Wang, Huan Sun, Yan Fang and Prof. Dr. Yong Huang

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201303274

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      Directed C[BOND]H annulation reactions provide a straightforward solution to the synthesis of substituted indoles. In their Communication on page 5795 ff., Y. Huang and co-workers describe a general protocol for the synthesis of unprotected indoles. By using a cleavable triazene as the directing group, C[BOND]H annulation with a wide scope of alkynes was accomplished with excellent regioselectivity for both aryl,alkyl and alkyl,alkyl disubstituted acetylenes.

    4. You have free access to this content
      Back Cover: A Programmable Sensor to Probe the Internalization of Proteins and Nanoparticles in Live Cells (Angew. Chem. Int. Ed. 22/2013) (page 5886)

      Haiyin Liu and Dr. Angus P. R. Johnston

      Version of Record online: 2 MAY 2013 | DOI: 10.1002/anie.201303271

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      The internalization of proteins and nanoparticles in living cells can be quantified by using a new DNA nanosensor, as described by A. P. R. Johnston and H. Liu in their Communication on page 5744 ff. The material of interest is labeled with a fluorescent DNA probe, and the fluorescence of any material that remains on the surface of the cell is quenched upon the addition of a quencher probe. The fluorescence of internalized material and other fluorophores is unaffected. This technique enables multi-color assays and studies in primary cells without compromising sensitivity or quantification.

  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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. You have free access to this content
      Intellectual Freedom in Academic Scientific Research under Threat (pages 5654–5655)

      Prof. Sir John Meurig Thomas

      Version of Record online: 29 APR 2013 | DOI: 10.1002/anie.201302192

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      “… In Great Britain and most probably also in other countries, a restoration of the proven qualities of intellectual freedom is mandatory. It has contributed so much to the culture, and facilitated the economic growth and the communal well-being, of the nation …” Read more in the Editorial by Sir John Meurig Thomas.

  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. Highlight
    11. Essay
    12. Review
    13. 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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. You have free access to this content
  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. Highlight
    11. Essay
    12. Review
    13. 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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Hisashi Yamamoto (pages 5678–5679)

      Version of Record online: 5 FEB 2013 | DOI: 10.1002/anie.201209483

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      “I chose chemistry as a career because it is so beautiful and yet still mysterious. I decided to be a chemist when I was 10 years old and I have never to this day regretted that rather early decision. I would not want to use whatever luck I might have for the lottery but rather would like to use it for my work in chemistry …” This and more about Hisashi Yamamoto can be found on page 5678.

  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. Highlight
    11. Essay
    12. Review
    13. 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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Prize Fight. The Race and the Rivalry to be the First in Science. By Morton A. Myers. (pages 5681–5682)

      Jay Labinger

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301713

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      Palgrave Macmillan, New York, 2012. 272 pp., hardcover, $ 27.00.—ISBN 978-0230338906

  9. Highlight

    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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Synthetic Methods

      Transition-Metal-Free Amination of Aryl boronic Acids and Their Derivatives (pages 5684–5686)

      Dr. Vincent Coeffard, Dr. Xavier Moreau, Dr. Christine Thomassigny and Prof. Christine Greck

      Version of Record online: 19 APR 2013 | DOI: 10.1002/anie.201300382

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      Free rein: Advances in transition-metal-free direct amination of aryl boronic acids and their derivatives have been recently described (see scheme). These reactions are based on the use of hydroxylamine or azide derivatives and offer great potential for further applications.

  10. 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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Programmable Atom Equivalents

      Nucleic Acid-Modified Nanostructures as Programmable Atom Equivalents: Forging a New “Table of Elements” (pages 5688–5698)

      Robert J. Macfarlane, Matthew N. O'Brien, Dr. Sarah Hurst Petrosko and Prof. Chad A. Mirkin

      Version of Record online: 2 MAY 2013 | DOI: 10.1002/anie.201209336

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      A nanoparticle-based analogue to the Periodic Table of the elements, where rather than arranging entries by electronic configuration, they are arranged by nanoscale architectural feature (e.g., composition, size, shape, and surface functionality). Using this table as a guide, the design considerations associated with using nucleic acids to assemble these nanoparticle-based programmable atom equivalents (PAEs) into superlattices is discussed.

  11. 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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Enzyme Design

      Computational Enzyme Design (pages 5700–5725)

      Dr. Gert Kiss, Dr. Nihan Çelebi-Ölçüm, Dr. Rocco Moretti, Prof. Dr. David Baker and Prof. Dr. Dr. K. N. Houk

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201204077

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      The “inside-out” approach to computer-based enzyme design unites the newest developments in the areas of computational chemistry and biology. This has enabled the design of proteins that catalyze reactions not accelerated in nature. The achievements and limitations of the current technology are highlighted and compared to other methods.

  12. 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. Highlight
    11. Essay
    12. Review
    13. Communications
    1. Natural Products

      Enzyme-Labile Protecting Groups for the Synthesis of Natural Products: Solid-Phase Synthesis of Thiocoraline (pages 5726–5730)

      Dr. Judit Tulla-Puche, Dr. Miriam Góngora-Benítez, Dr. Núria Bayó-Puxan, Dr. Andrés M. Francesch, Dr. Carmen Cuevas and Prof. Fernando Albericio

      Version of Record online: 25 APR 2013 | DOI: 10.1002/anie.201301708

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      Another (orthogonal) dimension: The solid-phase synthesis of thiocoraline was accomplished for the first time by a combined approach involving chemical and enzymatic methods. One-pot cleavage of the phenylacetamidomethyl protecting group using immobilized penicillin G acylase enzyme (see picture) and disulfide formation are the key steps of the synthetic strategy.

    2. Redox-Responsive Actuators

      Redox-Generated Mechanical Motion of a Supramolecular Polymeric Actuator Based on Host–Guest Interactions (pages 5731–5735)

      Masaki Nakahata, Dr. Yoshinori Takashima, Dr. Akihito Hashidzume and Prof. Dr. Akira Harada

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201300862

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      A supramolecular hydrogel is formed by a water-soluble polymer cross-linked with host–guest inclusion complexes between cyclodextrin and ferrocene. Dissociation and re-formation of inclusion complexes by redox stimuli lead to macroscale expansion and contraction of the hydrogel. The gel is utilized as a redox-responsive actuator and the mechanical work done is evaluated.

    3. Biradicals

      Unusual Inorganic Biradicals: A Theoretical Analysis (pages 5736–5739)

      Dr. Evangelos Miliordos, Prof. Klaus Ruedenberg and Dr. Sotiris S. Xantheas

      Version of Record online: 19 APR 2013 | DOI: 10.1002/anie.201300654

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      The biradical character β (1 for an ideal biradical) is determined from multi-reference configuration interaction (MRCI) wavefunctions. Triatomics in the series FX2+ (X=O, S, Se, Te, Po) exhibit unusually high biradical characters for X=Te, Po (0.76<β<0.92), the largest among the homologous 18 valence electron molecules CX22−, NX2, X3, and OX2. On the same scale, the biradical character of O3 is just 0.19, whereas that of C(CH2)3 is 0.97.

    4. Cyclophanes

      Synthesis of Highly Distorted π-Extended [2.2]Metacyclophanes by Intermolecular Double Oxidative Coupling (pages 5740–5743)

      Yutaro Koyama, Dr. Satoru Hiroto and Prof. Dr. Hiroshi Shinokubo

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301180

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      A strained relationship: Oxidation of dihydroxy-substituted acenes provides face-to-face [2.2]metacyclophane-like dimers (see scheme; O red, Si of iPr3Si groups blue). The products exhibited highly distorted structures caused by steric repulsion. UV/Vis and electrochemical analysis revealed that the HOMO–LUMO gap was decreased upon dimerization.

    5. Internalization Sensor

      A Programmable Sensor to Probe the Internalization of Proteins and Nanoparticles in Live Cells (pages 5744–5748)

      Haiyin Liu and Dr. Angus P. R. Johnston

      Version of Record online: 19 APR 2013 | DOI: 10.1002/anie.201301243

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      A molecular sensor has been developed to probe the internalization of proteins and nanoparticles into live cells. This simple, high-throughput technique is compatible with cell phenotyping and is independent of the cellular fate of the material.

    6. Complex Catenanes

      You have full text access to this OnlineOpen article
      Generation of a Dynamic System of Three-Dimensional Tetrahedral Polycatenanes (pages 5749–5752)

      Samuel P. Black, Dr. Artur R. Stefankiewicz, Dr. Maarten M. J. Smulders, Dominik Sattler, Prof. Christoph A. Schalley, Dr. Jonathan R. Nitschke and Prof. Jeremy K. M. Sanders

      Version of Record online: 18 APR 2013 | DOI: 10.1002/anie.201209708

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      Seven of the best: A dynamic combinatorial library of polycatenated tetrahedra was prepared by complexation between a dynamic Fe4L6 tetrahedral cage, constructed from ligands containing an electron-deficient naphthalenediimide core, and an electron-rich aromatic crown ether, 1,5-dinaphtho[38]crown-10. The highest order species in the library is the tetrahedral [7]catenane.

    7. Solvent Adsorption on LiCoO2

      Preferential Adsorption of Solvents on the Cathode Surface of Lithium Ion Batteries (pages 5753–5756)

      Dr. Le Yu, Dr. Huijin Liu, Yan Wang, Dr. Naoaki Kuwata, Prof. Masatoshi Osawa, Prof. Junichi Kawamura and Prof. Shen Ye

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201209976

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      The adsorption structures of solvents on the surface of LiCoO2, which is the most widely used cathode material for Li-ion batteries, in contact with nonaqueous electrolyte solutions of carbonate esters have been characterized by in situ sum frequency generation (SFG) spectroscopy. The cyclic carbonate of ethylene carbonate (EC) is preferentially adsorbed on the LiCoO2 surface, in contrast to linear carbonates, such as dimethyl carbonate (DMC).

    8. Oral Delivery of siRNA

      Supramolecular Self-Assembled Nanoparticles Mediate Oral Delivery of Therapeutic TNF-α siRNA against Systemic Inflammation (pages 5757–5761)

      Dr. Lichen Yin, Ziyuan Song, Dr. Qiuhao Qu, Kyung Hoon Kim, Nan Zheng, Catherine Yao, Isthier Chaudhury, Dr. Haoyu Tang, Dr. Nathan P. Gabrielson, Prof. Dr. Fatih M. Uckun and Prof. Dr. Jianjun Cheng

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201209991

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      A functional package: Multifunctional supramolecular self-assembled nanoparticles (SSNPs) consist of a set of rationally designed components that collectively facilitate efficient intestinal absorption of siRNA and induce potent TNF-α silencing in macrophages. Single gavage of SSNPs in mice depletes systemic TNF-α production at an siRNA dose as low as 50 μg kg−1, and thus protects mice from lipopolysaccharide-induced hepatic injury.

    9. Biomineralization

      Multiphase Intrafibrillar Mineralization of Collagen (pages 5762–5766)

      Dr. Li-na Niu, Dr. Kai Jiao, Dr. Heonjune Ryou, Dr. Cynthia K. Y. Yiu, Dr. Ji-hua Chen, Dr. Lorenzo Breschi, Dr. Dwayne D. Arola, Dr. David H. Pashley and Dr. Franklin R. Tay

      Version of Record online: 18 APR 2013 | DOI: 10.1002/anie.201210259

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      Why waste space? In the first stage of the multiphase biomineralization of collagen, silicic acid precursors (purple) infiltrated the collagen fibril (yellow) and condensed into amorphous silica to give a hierarchical composite. Amorphous calcium phosphate precursors (red) then filled the intrafibrillar spaces of the silicified collagen, where the precipitation and maturation of apatite crystallites (blue) occurred to complete the process.

    10. Organometallic Nanoparticles

      Polycyclooctadiene Complexes of Rhodium(I): Direct Access to Organometallic Nanoparticles (pages 5767–5770)

      Dr. Sudheendran Mavila, Dr. Charles E. Diesendruck, Sivan Linde, Liron Amir, Dr. Rafi Shikler and Prof. Dr. N. Gabriel Lemcoff

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300362

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      Content matters: The reaction of polycyclooctadiene (Poly(COD)) and [{RhCl(C2H4)2}2] produced well-defined π-bound hybrid polymers, the size of which depended on rhodium content (see picture). The reaction of these polymers with a phosphine aldehyde led to the regeneration of the original polymers, thus proving the accessibility of the metal.

    11. Protein Modifications

      A Facile Strategy for Selective Incorporation of Phosphoserine into Histones (pages 5771–5775)

      Sangsik Lee, Seunghee Oh, Aerin Yang, Jihyo Kim, Prof. Dieter Söll, Prof. Daeyoup Lee and Prof. Hee-Sung Park

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201300531

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      Phosphoserine incorporation: A general strategy for producing recombinant histones with site-specific serine phosphorylation is developed by engineering phosphoseryl-tRNA synthetase (SepRS) and elongation factor Tu (EF-Tu; see picture). Serine-phosphorylated nucleosomes provide direct evidence for crosstalk between phosphorylation and acetylation in histones.

    12. Heterogeneous Catalysis

      Photocatalytic Conversion of Carbon Dioxide with Water into Methane: Platinum and Copper(I) Oxide Co-catalysts with a Core–Shell Structure (pages 5776–5779)

      Qingge Zhai, Shunji Xie, Wenqing Fan, Prof. Dr. Qinghong Zhang, Yu Wang, Dr. Weiping Deng and Prof. Dr. Ye Wang

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301473

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      Binary co-catalysts of Pt and Cu2O with a core–shell structure significantly enhance the photocatalytic reduction of CO2 with H2O to CH4 and CO. The Cu2O shell provides sites for the preferential activation and conversion of CO2, whereas the Pt core extracts the photogenerated electrons from TiO2. The deposition of Cu2O shell on Pt nanoparticles markedly suppresses the reduction of H2O to H2 (see picture).

    13. Selective Alcohol Oxidation

      Molecular Understanding of Reactivity and Selectivity for Methanol Oxidation at the Au/TiO2 Interface (pages 5780–5784)

      Dr. Matteo Farnesi Camellone, Dr. Jianli Zhao, Lanying Jin, Dr. Yuemin Wang, Prof. Dr. Martin Muhler and Prof. Dr. Dominik Marx

      Version of Record online: 15 APR 2013 | DOI: 10.1002/anie.201301868

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      Gold catalysis: Experimental and theoretical data demonstrated consistently that the interfacial sites on a Au/TiO2 catalyst show both high reactivity and selectivity for low-temperature methanol oxidation with O2 to give formaldehyde. The microscopic mechanism of this complex reaction has been unraveled in full molecular detail (see picture, gold cluster on TiO2 surface).

    14. Tetronate Antibiotics

      Unusual Acetylation–Elimination in the Formation of Tetronate Antibiotics (pages 5785–5788)

      Chompoonik Kanchanabanca, Dr. Weixin Tao, Dr. Hui Hong, Yajing Liu, Dr. Frank Hahn, Dr. Markiyan Samborskyy, Prof. Dr. Zixin Deng, Prof. Dr. Yuhui Sun and Prof. Dr. Peter F. Leadlay

      Version of Record online: 18 APR 2013 | DOI: 10.1002/anie.201301680

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      The identity and reactivity of the intermediates in agglomerin biosynthesis were established and the respective roles of the acetyltransferase Agg4 and the eliminating enzyme Agg5 identified (see scheme). It is proposed that enzymes homologous to Agg4 and Agg5 carry out the dehydration steps in all spirotetronate biosynthetic pathways. If this proves correct, it may assist engineering of these pathways.

    15. Cooperative Catalysis

      An Efficient Approach to the Securinega Alkaloids Empowered by Cooperative N-Heterocyclic Carbene/Lewis Acid Catalysis (pages 5789–5794)

      Dr. Adel M. ElSohly, Dr. Daniel A. Wespe, Tyler J. Poore and Prof. Dr. Scott A. Snyder

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301849

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      Folding it all together: Most of the syntheses developed for the securinega alkaloid class require lengthy sequences to create their bridging butenolide domains. A novel approach uses N-heterocyclic carbenes (NHCs) and Lewis acids to forge the entire domain in a single step from appropriate precursors, showing that ynal-derived homoenolates can participate as nucleophiles in intramolecular settings (see scheme).

    16. Synthetic Methods

      General and Efficient Synthesis of Indoles through Triazene-Directed C–H Annulation (pages 5795–5798)

      Chengming Wang, Huan Sun, Yan Fang and Prof. Dr. Yong Huang

      Version of Record online: 19 APR 2013 | DOI: 10.1002/anie.201301742

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      Unprotected indoles are prepared with the title method, which has a wide scope for alkynes. Excellent regioselectivity was accomplished for aryl–alkyl and alkyl–alkyl disubstituted acetylenes. This reaction features an unusual 1,2 rhodium migration and ring-contraction-triggered N[BOND]N bond cleavage. It allows rapid conversion of the reaction products into several functional molecules.

    17. Copper Catalysis

      Copper-Catalyzed Arylative Meyer–Schuster Rearrangement of Propargylic Alcohols to Complex Enones Using Diaryliodonium Salts (pages 5799–5802)

      Beatrice S. L. Collins, Dr. Marcos G. Suero and Prof. Matthew J. Gaunt

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301529

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      Free choice: A copper-catalyzed arylative Meyer–Schuster rearrangement is described. The reaction is compatible with a range of substituted propargylic alcohols and diaryliodonium salts and delivers complex trisubstituted enone products selectively as the E isomers.

    18. Organocatalysis

      Enantioselective N-Heterocyclic Carbene Catalyzed Aza-Benzoin Reaction of Enals with Activated Ketimines (pages 5803–5806)

      Li-Hui Sun, Zhi-Qin Liang, Wen-Qiang Jia and Prof. Dr. Song Ye

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301304

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      α-Amino ketones, which are versatile building blocks for organic synthesis, were obtained with the title reaction. A free hydroxy group on the NHC catalyst was found to be crucial for the reaction, and the possible competing reaction through a homoenolate or enolate was not observed with this catalyst (see scheme).

    19. Cross-Coupling

      Weak Arene C[BOND]H⋅⋅⋅O Hydrogen Bonding in Palladium-Catalyzed Arylation and Vinylation of Lactones (pages 5807–5812)

      Dr. Zhiyan Huang, Dr. Zuliang Chen, Li Hui Lim, Gia Chuong Phan Quang, Prof. Dr. Hajime Hirao and Prof. Dr. Jianrong (Steve) Zhou

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201300481

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      Weak force in action: In the title reaction, the palladium catalyst (see figure, left) uses weak CH⋅⋅⋅O hydrogen bonding to control the absolute configuration of the new stereocenter. A similar palladium catalyst (right) used conventional NH⋅⋅⋅O hydrogen bonding to guide stereoselection.

    20. Catalytic C[BOND]F Activation

      Palladium-Catalyzed Ortho-Selective C[BOND]F Activation of Polyfluoroarenes with Triethylsilane: A Facile Access to Partially Fluorinated Aromatics (pages 5813–5817)

      Zhao Chen, Chun-Yang He, Zengsheng Yin, Liye Chen, Yi He and Prof. Dr. Xingang Zhang

      Version of Record online: 19 APR 2013 | DOI: 10.1002/anie.201300400

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      PdF: A simple catalytic system, broad substrate scope, and high versatility provide a useful and facile access to partially fluorinated aromatics (see scheme). Tuning the reaction conditions enables a diverse range of product structures to be prepared.

    21. Heterogeneous Catalysis

      Highly Stereoselective Cyclopropanation of α,β-Unsaturated Carbonyl Compounds with Methyl (Diazoacetoxy)acetate Catalyzed by a Chiral Ruthenium(II) Complex (pages 5818–5821)

      Soda Chanthamath, Suguru Takaki, Prof. Dr. Kazutaka Shibatomi and Prof. Dr. Seiji Iwasa

      Version of Record online: 16 APR 2013 | DOI: 10.1002/anie.201300468

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      Tantalizing triangles: The title reaction gives bicarbonyl cyclopropane products that can lead to versatile intermediates with high yields and stereoselectivities. This system was also applied to the enantioselective total synthesis of spiro cyclopropane oxindole, an HIV-1 nonnucleoside reverse transcriptase inhibitor.

    22. Catalyst Activation

      The Impact of Palladium(II) Reduction Pathways on the Structure and Activity of Palladium(0) Catalysts (pages 5822–5826)

      Carolyn S. Wei, Geraint H. M. Davies, Omid Soltani, Jacob Albrecht, Qi Gao, Charles Pathirana, Yi Hsiao, Srinivas Tummala and Martin D. Eastgate

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201210252

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      Two roads diverged: The mechanism of in situ PdII catalyst activation to generate an active {LnPd0} catalyst from an air-stable PdII precursor was examined using the standard conditions of a Miyaura borylation reaction. Two pathways for catalyst activation exist under these conditions, producing two structurally and chemically distinct {LnPd0} complexes (see scheme).

    23. C[BOND]H Activation

      PdCl2 and N-Hydroxyphthalimide Co-catalyzed C sp 2[BOND]H Hydroxylation by Dioxygen Activation (pages 5827–5831)

      Yuepeng Yan, Peng Feng, Qing-Zhong Zheng, Yu-Feng Liang, Jing-Fen Lu, Yuxin Cui and Ning Jiao

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201300957

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      Rad transition: The combination of transition-metal-catalyzed C[BOND]H activation and a NHPI-initiated radical process is essential for the title transformation. The neutral conditions and the ideal oxidant, molecular oxygen, make this hydroxylation environmentally friendly and practical. NHPI=N-hydroxyphthalimide.

    24. Hydrogen storage

      Metal-Free Catalysis of Ammonia–Borane Dehydrogenation/Regeneration for a Highly Efficient and Facilely Recyclable Hydrogen-Storage Material (pages 5832–5835)

      Ziwei Tang, Xiaowei Chen, Hao Chen, Prof. Limin Wu and Prof. Xuebin Yu

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301049

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      As easy as ABC: Mesoporous graphitic carbon nitride (MGCN; g-C3N4) is utilized to support ammonia borane (AB) on the basis of its accessible nanoporous structure and basic properties. A high loading of uniformly dispersed AB nanoparticles into the MGCN is possible giving greatly enhanced H2 generation from AB, and facile regeneration cycles by a hydrazine hydrogenation process, even at room temperature.

    25. Heterocycles

      Unveiling Latent α-Iminocarbene Reactivity for Intermolecular Cascade Reactions through Alkyne Oxidative Amination (pages 5836–5839)

      Nina Mace, Aaron R. Thornton and Prof. Dr. Simon B. Blakey

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301087

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      Setting a trap: Described is the development of a metallonitrene-initiated alkyne oxidation cascade with intermolecular trapping of the reactive intermediate with a variety of allyl ethers to provide α-oxyimine products in which new C[DOUBLE BOND]N, C[BOND]O, and C[BOND]C bonds have all been generated (see Scheme; tfacam=trifluoroacetamide).

    26. Modified Nucleic Acids

      Base-Pairing Properties of a Structural Isomer of Glycerol Nucleic Acid (pages 5840–5844)

      Dr. Phaneendrasai Karri, Dr. Venkateshwarlu Punna, Dr. Keunsoo Kim and Prof. Dr. Ramanarayanan Krishnamurthy

      Version of Record online: 18 APR 2013 | DOI: 10.1002/anie.201300795

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      Know your limit! IsoGNA (a structural isomer of GNA) was found—in sharp contrast to GNA—to be highly restricted in its ability to base-pair with itself and other nucleic acids. While homogeneous sequences (e.g. isoGNA(A)16) formed duplexes, the heterogeneous sequences showed no base-pairing. This exemplifies the limitations of canonical nucleobases as the recognition elements in simpler, more primitive phosphate backbones.

    27. Prebiotic Systems Chemistry

      You have full text access to this OnlineOpen article
      Synthesis of Aldehydic Ribonucleotide and Amino Acid Precursors by Photoredox Chemistry (pages 5845–5847)

      Dr. Dougal J. Ritson and Prof. Dr. John D. Sutherland

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201300321

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      Light work: UV irradiation of a system formed by adding copper(I) cyanide to an aqueous solution of glycolonitrile, sodium phosphate, and hydrogen sulfide efficiently generates aldehyde precursors to the building blocks of RNA and proteins.

    28. Gold Catalysis

      Copper Salts as Additives in Gold(I)-Catalyzed Reactions (pages 5848–5852)

      Dr. Amandine Guérinot, Weizhen Fang, Dr. Marie Sircoglou, Dr. Christophe Bour, Dr. Sophie Bezzenine-Lafollée and Prof. Dr. Vincent Gandon

      Version of Record online: 19 APR 2013 | DOI: 10.1002/anie.201300600

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      The right combination: CuI and CuII salts can advantageously replace silver additives in AuI-catalyzed reactions. On the basis of reactivity studies and NMR experiments, it is believed that anion metathesis between CuYn (Y=OTf, BF4, PF6, SbF6) and [R3PAuCl] takes place to give [R3PAu]Y. As this process is slow, there is no fast decay of the active species, thus allowing large-scale reactions, even at high temperatures, with low loadings of the gold complex.

    29. Zinc Catalysis

      Zinc-Catalyzed Synthesis of Functionalized Furans and Triarylmethanes from Enynones and Alcohols or Azoles: Dual X[BOND]H Bond Activation by Zinc (pages 5853–5857)

      Jesús González, Dr. Javier González, Carmela Pérez-Calleja, Dr. Luis A. López and Dr. Rubén Vicente

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301625

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      Ba'zinc'ga! A zinc-catalyzed sequence involving a cyclization with a subsequent C[BOND]O, C[BOND]N, or C[BOND]C bond formation enables the preparation of a variety of valuable furfuryl ethers (with alcohols) and unsymmetrically substituted triarylmethane derivatives (with azoles or arenes). ZnCl2 serves as the catalyst.

    30. Carbohydrate Synthesis (1)

      Automated Solid-Phase Synthesis of Chondroitin Sulfate Glycosaminoglycans (pages 5858–5861)

      Dr. Steffen Eller, Dr. Mayeul Collot, Dr. Jian Yin, Heung Sik Hahm and Prof. Dr. Peter H. Seeberger

      Version of Record online: 15 APR 2013 | DOI: 10.1002/anie.201210132

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      Glycosaminoglycans (GAGs) are important sulfated carbohydrates prevalent in the extracellular matrix. The synthesis of structurally defined GAGs requires laborious procedures, and incorporating defined sulfation patterns is challenging. The automated synthesis of defined sulfated chondroitin hexasaccharides on solid support has been achieved using a photolabile linker that is efficiently cleaved in a continuous-flow photoreactor.

    31. Carbohydrate Synthesis (2)

      Automated Polysaccharide Synthesis: Assembly of a 30mer Mannoside (pages 5862–5865)

      Oliviana Calin, Dr. Steffen Eller and Prof. Dr. Peter H. Seeberger

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201210176

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      Automated carbohydrate synthesis breaks new grounds: The longest sugar chemically synthesized to date (a 30 mer) has been accessed. Key to the process is the use of a catch–release technique, which labels the saccharide, thus allowing it to be separated later through temporary attachement to magnetic particles.

    32. Total Synthesis

      Total Synthesis of the Tubulin Inhibitor WF-1360F Based on Macrocycle Formation through Ring-Closing Alkyne Metathesis (pages 5866–5870)

      M. Sc. Christian M. Neuhaus, M. Sc. Marc Liniger, Dr. Martin Stieger and Prof. Dr. Karl-Heinz Altmann

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201300576

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      Key steps in this total synthesis of the antimitotic natural product WF-1360F (3) include the formation of the macrocycle through ring-closing alkyne metathesis and the subsequent conversion of the ensuing alkyne moiety into an E-configured double bond. As illustrated by the synthesis of 4, the macrocyclic vinyl iodide 2 can also serve as a common precursor for the synthesis of side-chain-modified rhizoxin analogues (see scheme; TIPS=triisopropylsilyl).

    33. Natural Product Synthesis

      Total Synthesis of the Antifungal Agent Echinocandin C (pages 5871–5875)

      Frauke Messik and Dr. Markus Oberthür

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201301262

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      Reliably stable: A dipeptide building block with fully elaborated N-acyl hemiaminal proved to be a versatile precursor for echinocandin C, a prototypical member of the echinocandin group of antimycotic drugs. This first total synthesis of an N-acyl hemiaminal-containing echinocandin is concise and highly convergent, thereby making additional derivatives easily accessible. PG=protecting group.

    34. Frustrated Lewis Pairs

      Functional-Group Tolerance in Frustrated Lewis Pairs: Hydrogenation of Nitroolefins and Acrylates (pages 5876–5879)

      Dipl.-Chem. Lutz Greb, Dr. Constantin-Gabriel Daniliuc, Dr. Klaus Bergander and Priv.-Doz. Dr. Jan Paradies

      Version of Record online: 22 APR 2013 | DOI: 10.1002/anie.201210175

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      Weak Lewis acid for high nucleophilicity: Hydridoborate derived from B(2,6-F2C6H3)3 shows significant hydride character. Solid-state and solution structure analysis revealed a dihydrogen-bonded aggregate. The new frustrated Lewis pair was applied in the hydrogenation of nitroolefins and acrylates (see scheme; EWG=electron-withdrawing group). The decreased Lewis acidity provides higher reactivity and functional-group tolerance.

    35. Gold Carbenoids

      Gold Catalysis: Highly Functionalized Cyclopentadienes Prepared by Intermolecular Cyclization of Ynamides and Propargylic Carboxylates (pages 5880–5884)

      Dipl.-Chem. Eva Rettenmeier, Dr. Andreas M. Schuster, Dr. Matthias Rudolph, Dr. Frank Rominger, Christoph A. Gade and Prof. Dr. A. Stephen K. Hashmi

      Version of Record online: 24 APR 2013 | DOI: 10.1002/anie.201301382

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      When an ynamide meets a gold carbenoid: Highly electrophilic gold carbenoids available from propargylic esters by means of 1,2-acyloxy migration open up new reaction pathways for ynamide gold chemistry. In this way highly functionalized cyclopentadiene derivatives become accessible (see scheme; EWG=electron-withdrawing group).

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