Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 38

September 16, 2013

Volume 52, Issue 38

Pages 9861–10123

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: A Suite of Solid-State NMR Experiments for RNA Intranucleotide Resonance Assignment in a 21 kDa Protein–RNA Complex (Angew. Chem. Int. Ed. 38/2013) (page 9861)

      Dr. Alexander Marchanka, Dr. Bernd Simon and Dr. Teresa Carlomagno

      Article first published online: 22 AUG 2013 | DOI: 10.1002/anie.201306359

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      Resonance assignment is the first step of RNA structure determination by NMR spectroscopy. In their Communication on page 9996 ff., T. Carlomagno and co-workers present a suite of solid-state NMR experiments for RNA intranucleotide resonance assignment. These experiments open the way to structural studies of RNA by solid-state NMR spectroscopy.

    2. You have free access to this content
      Inside Cover: Simultaneous Self-Assembly of a [2]Catenane, a Trefoil Knot, and a Solomon Link from a Simple Pair of Ligands (Angew. Chem. Int. Ed. 38/2013) (page 9862)

      Dr. Thirumurugan Prakasam, Dr. Matteo Lusi, Dr. Mourad Elhabiri, Dr. Carlos Platas-Iglesias, Prof. John-Carl Olsen, Dr. Zouhair Asfari, Dr. Sarah Cianférani-Sanglier, Dr. François Debaene, Dr. Loïc J. Charbonnière and Prof. Ali Trabolsi

      Article first published online: 2 AUG 2013 | DOI: 10.1002/anie.201306198

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      Three molecular links were prepared in one pot from a single pair of chelating ligands. In their Communication on page 9956 ff., L. J. Charbonnière, A. Trabolsi et al. describe the self-assembly of a [2]catenane, a trefoil knot, and a Solomon link through combined metal templation, dynamic covalent-bond formation, and noncovalent interactions. During the reaction, product evolution was monitored by mass spectrometry, which provided evidence for the mechanistic routes to all three products.

    3. You have free access to this content
      Inside Back Cover: Catalysis with Anion–π Interactions (Angew. Chem. Int. Ed. 38/2013) (page 10125)

      Dr. Yingjie Zhao, Dr. Yuya Domoto, Dr. Edvinas Orentas, Dr. César Beuchat, Dr. Daniel Emery, Dr. Jiri Mareda, Dr. Naomi Sakai and Prof. Stefan Matile

      Article first published online: 26 AUG 2013 | DOI: 10.1002/anie.201306453

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      The increasing stabilization of an anionic transition state with the increasing π acidity of newly made catalysts provides unprecedented experimental evidence that anion–π interactions can contribute to catalysis. In their Communication on page 9940 ff., S. Matile et al. further disclose theoretical simulations of anion–π catalysis that illustrate how the negative charge slides over the π-acidic surface of the naphthalenediimide catalyst.

    4. You have free access to this content
      Back Cover: Dynamic Single Crystals: Kinematic Analysis of Photoinduced Crystal Jumping (The Photosalient Effect) (Angew. Chem. Int. Ed. 38/2013) (page 10126)

      Prof. Panče Naumov, Dr. Subash Chandra Sahoo, Dr. Boris A. Zakharov and Prof. Elena V. Boldyreva

      Article first published online: 19 AUG 2013 | DOI: 10.1002/anie.201306441

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      When subjected to a light stimulus crystals of certain materials can suddenly hop and leap over distances 102–105 times their own size to release the strain that accumulates in their interior as a result of a photochemical reaction. This photosalient effect is an impressive demonstration of the rapid conversion of light into mechanical motion on a macroscopic scale. In their Communication on page 9990 ff., P. Naumov, E. V. Boldyreva, and co-workers analyze the kinematic motion patterns. Picture design by Bailey Curzadd.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. You have free access to this content
      Editorial: Probes, Sensors, and Labels: Why is Real Progress Slow? (pages 9864–9865)

      Prof. Otto S. Wolfbeis

      Article first published online: 28 AUG 2013 | DOI: 10.1002/anie.201305915

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  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
  4. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Bernhard Breit (pages 9888–9889)

      Article first published online: 22 APR 2013 | DOI: 10.1002/anie.201302473

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      “My motto is ‘simple things first’. My favorite composer is Johann Sebastian Bach. …” This and more about Bernhard Breit can be found on page 9888.

  6. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Design and Applications of Single-Site Heterogeneous Catalysts. Contributions to Green Chemistry, Clean Technology and Sustainability. By John Meurig Thomas. (pages 9892–9893)

      Javier Pérez-Ramírez

      Article first published online: 21 AUG 2013 | DOI: 10.1002/anie.201306646

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      Imperial College Press, London, 2012. 324 pp., hardcover, £ 79.00.—ISBN 978-1848169104

  8. Highlight

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. C[BOND]H Activation

      8-Aminoquinoline: A Powerful Directing Group in Metal-Catalyzed Direct Functionalization of C[BOND]H Bonds (pages 9896–9898)

      Dr. Matthieu Corbet and Dr. Floryan De Campo

      Article first published online: 12 AUG 2013 | DOI: 10.1002/anie.201303556

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      Chelate me if you can: Over the last decade, strategies for the functionalization of both Cinline image[BOND]H and Cinline image[BOND]H bonds have witnessed an increasing use of a simple, yet powerful directing group, 8-aminoquinoline (in blue). This auxiliary is very efficient in a wide range of metal-mediated reactions, and can be readily removed to afford the desired carboxylic acids or corresponding derivatives.

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Aromatic Dehydrogenation

      Comparison of Oxidative Aromatic Coupling and the Scholl Reaction (pages 9900–9930)

      Marek Grzybowski, Kamil Skonieczny, Prof. Dr. Holger Butenschön and Prof. Dr. Daniel T. Gryko

      Article first published online: 14 JUL 2013 | DOI: 10.1002/anie.201210238

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      Where is the oxidant? Although the coupling of arenes in the presence of Lewis acids has been known for some time, the differentiation between reactions in the presence of a non-oxidizing Lewis acid (Scholl reaction) and in the presence of an oxidizing Lewis acid has been lost over the years. This Review highlights the similarities and differences between these reactions, which most probably proceed by two different mechanisms.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Nanoscale Polymetallic Assemblies

      You have full text access to this OnlineOpen article
      A Ring of Rings and Other Multicomponent Assemblies of Cages (pages 9932–9935)

      George F. S. Whitehead, Dr. Fabrizio Moro, Dr. Grigore A. Timco, Dr. Wolfgang Wernsdorfer, Dr. Simon J. Teat and Prof. Dr. Richard E. P. Winpenny

      Article first published online: 31 JUL 2013 | DOI: 10.1002/anie.201304817

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      Ring a ring of roses: Spectacular nanoscale molecular assemblies have been created by design of individual polymetallic components that are then linked together through simple reactions. These include an assembly where six octametallic rings surround a dodecametallic central ring.

    2. Fluorescent Probes

      Lipid Pools As Photolabile “Protecting Groups”: Design of Light-Activatable Bioagents (pages 9936–9939)

      Luong T. Nguyen, Nathan P. Oien, Prof. Nancy L. Allbritton and Prof. David S. Lawrence

      Article first published online: 31 JUL 2013 | DOI: 10.1002/anie.201305510

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      Inactive in the membrane: Lipidated light-responsive constructs that sequester bioagents (R, see scheme) to the membranes of organelles and cells have been constructed. When membrane-bound, the bioagent is not susceptible to processing by its biological target. Photolysis releases the bioagent from its membrane anchor and thereby renders it biologically active.

    3. Anion–π Interactions

      Catalysis with Anion–π Interactions (pages 9940–9943)

      Dr. Yingjie Zhao, Dr. Yuya Domoto, Dr. Edvinas Orentas, Dr. César Beuchat, Dr. Daniel Emery, Dr. Jiri Mareda, Dr. Naomi Sakai and Prof. Stefan Matile

      Article first published online: 14 AUG 2013 | DOI: 10.1002/anie.201305356

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      The conclusion is inevitable: Increasing stabilization of an anionic transition state with increasing π-acidity of the catalyst is observed; thus, anion–π interactions can contribute to catalysis.

    4. Thiodepsipeptides

      A High-Resolution Structure that Provides Insight into Coiled-Coil Thiodepsipeptide Dynamic Chemistry (pages 9944–9947)

      Zehavit Dadon, Dr. Manickasundaram Samiappan, Dr. Anat Shahar, Dr. Raz Zarivach and Prof. Gonen Ashkenasy

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201303900

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      Stable and reactive: A crystal structure at 1.35 Å of a thioester coiled-coil protein reveals high similarity to all-peptide-bond proteins. In these assemblies, the thioester bonds are kept reactive towards thiol molecules in the mixture. This enables efficient domain exchange between proteins in response to changes in folding conditions or introduction of external templates.

    5. Shape Transformation

      Polymeric Microtubules That Breathe: CO2-Driven Polymer Controlled-Self-Assembly and Shape Transformation (pages 9948–9951)

      Dr. Qiang Yan and Prof. Dr. Yue Zhao

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201303984

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      Tubular breathing motion: Polymer tubules self-assembled from a gas-sensitive triblock copolymer can undergo shape evolution. A sequence from microtubes through submicroscopic vesicles to nanosized spherical micelles is modulated by CO2 stimulation levels.

    6. Au Nanosheets

      Self-Assembly of Au15 into Single-Cluster-Thick Sheets at the Interface of Two Miscible High-Boiling Solvents (pages 9952–9955)

      Zhennan Wu, Chunwei Dong, Yanchun Li, Hongxia Hao, Prof. Hao Zhang, Prof. Zhongyuan Lu and Prof. Bai Yang

      Article first published online: 27 AUG 2013 | DOI: 10.1002/anie.201304122

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      Wet (nano)blanket: The self-assembly of Au nanoclusters into single-cluster-thick nanosheets is performed in two miscible high-boiling solvents with a slight polarity difference, which generates microphase separation and acts as a soft template to direct the self-assembly in a two-dimensional orientation.

    7. Molecular Knots

      Simultaneous Self-Assembly of a [2]Catenane, a Trefoil Knot, and a Solomon Link from a Simple Pair of Ligands (pages 9956–9960)

      Dr. Thirumurugan Prakasam, Dr. Matteo Lusi, Dr. Mourad Elhabiri, Dr. Carlos Platas-Iglesias, Prof. John-Carl Olsen, Dr. Zouhair Asfari, Dr. Sarah Cianférani-Sanglier, Dr. François Debaene, Dr. Loïc J. Charbonnière and Prof. Ali Trabolsi

      Article first published online: 5 JUL 2013 | DOI: 10.1002/anie.201302425

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      A topological triptych: Three molecular links, a [2]catenane, a trefoil knot, and a Solomon link, were obtained in one pot through the self-assembly of two simple ligands in the presence of ZnII (see picture). The approach relied on dynamic covalent chemistry and metal templation.

    8. Photonic Hydrogels

      Polymerized Microgel Colloidal Crystals: Photonic Hydrogels with Tunable Band Gaps and Fast Response Rates (pages 9961–9965)

      Mao Chen, Lin Zhou, Prof. Dr. Ying Guan and Prof. Dr. Yongjun Zhang

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201302466

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      Into and out of the blue: The highly ordered structure of a PNIPAM microgel colloidal crystal (MCC) is stabilized by photopolymerization of its surface-bound vinyl groups. The resulting polymerized MCCs can respond reversibly and quickly to external stimuli, including temperature and ionic strength of the surrounding media, allowing the color (see picture) and band gap to be finely tuned in the whole visible range.

    9. B,N Heterocycles

      BN-Dibenzo[a,o]picenes: Analogues of an Unknown Polycyclic Aromatic Hydrocarbon (pages 9966–9969)

      Dr. Benedikt Neue, Juan F. Araneda, Prof. Warren E. Piers and Masood Parvez

      Article first published online: 29 JUL 2013 | DOI: 10.1002/anie.201302911

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      Reflecting on synthetic pinnacles: Whereas the parent hydrocarbon is not readily accessible, several examples of BN substituted-dibenzo[a,o]picenes can be prepared in two steps from known starting materials. These non-linear heptacene analogues are water-stable materials. Their preparation utilizes a potentially general method for preparing extended BN analogues of difficult-to-synthesize polycyclic aromatic hydrocarbon frameworks.

    10. Helical Structures

      Rapid Access to Dibenzohelicenes and their Functionalized Derivatives (pages 9970–9975)

      Andrej Jančařík, Dr. Jiří Rybáček, Kevin Cocq, Dr. Jana Vacek Chocholoušová, Dr. Jaroslav Vacek, Dr. Radek Pohl, Dr. Lucie Bednárová, Dr. Pavel Fiedler, Dr. Ivana Císařová, Dr. Irena G. Stará and Dr. Ivo Starý

      Article first published online: 9 AUG 2013 | DOI: 10.1002/anie.201301739

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      Spiraling up: Easy access to dibenzo[5]-, dibenzo[6]-, and dibenzo[7]helicenes (see picture) as well as their functionalized derivatives includes Sonogashira and Suzuki–Miyaura couplings, desilylation, and [2+2+2] alkyne cycloisomerization. The simplicity of this non-photochemical approach combined with the potential for helicity control favors dibenzohelicenes over the parent helicenes for practical applications.

    11. Synthetic Riboswitches

      A Synthetic Riboswitch that Operates using a Rationally Designed Ligand–RNA Pair (pages 9976–9979)

      Dr. Chikara Dohno, Izumi Kohyama, Maki Kimura, Dr. Masaki Hagihara and Prof. Kazuhiko Nakatani

      Article first published online: 3 SEP 2013 | DOI: 10.1002/anie.201303370

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      The construction of an artificial riboswitch is based on a ligand–RNA pair without any molecular biology-based selection processes. The ligand selectively and significantly stabilized an RNA duplex containing an r(XGG)/r(XGG) sequence (X=U, A, G). The integration of the ligand-binding sequences into the 5′-untranslated region of mRNA provided an artificial riboswitch that was responsive to Z-NCTS.

    12. Alkaloid Biosynthesis

      Discovery of McbB, an Enzyme Catalyzing the β-Carboline Skeleton Construction in the Marinacarboline Biosynthetic Pathway (pages 9980–9984)

      Qi Chen, Changtao Ji, Dr. Yongxiang Song, Dr. Hongbo Huang, Dr. Junying Ma, Dr. Xinpeng Tian and Prof. Dr. Jianhua Ju

      Article first published online: 1 AUG 2013 | DOI: 10.1002/anie.201303449

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      Three genes, mcbABC, that drive the biosynthesis of marinacarbolines, have been elucidated through genome mining, gene inactivation, heterologous expression, feeding, and site-directed mutagenesis experiments. McbB is highlighted as a novel enzyme for the β-carboline core construction, which involves a Pictet–Spengler cyclization process and requiring E97 for biochemical activity.

    13. Zeolite Catalysis

      A Common Intermediate for N2 Formation in Enzymes and Zeolites: Side-On Cu–Nitrosyl Complexes (pages 9985–9989)

      Ja Hun Kwak, Jong H. Lee, Sarah D. Burton, Andrew S. Lipton, Charles H. F. Peden and János Szanyi

      Article first published online: 12 AUG 2013 | DOI: 10.1002/anie.201303498

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      Side on! Combined FTIR and NMR studies revealed the presence of a side-on nitrosyl species in the zeolite Cu-SSZ-13. This intermediate is very similar to those found in nitrite reductase enzyme systems. The identification of this intermediate led to the proposal of a reaction mechanism that is fully consistent with the results of both kinetic and spectroscopic studies.

    14. Actuators

      Dynamic Single Crystals: Kinematic Analysis of Photoinduced Crystal Jumping (The Photosalient Effect) (pages 9990–9995)

      Prof. Panče Naumov, Dr. Subash Chandra Sahoo, Dr. Boris A. Zakharov and Prof. Elena V. Boldyreva

      Article first published online: 19 JUL 2013 | DOI: 10.1002/anie.201303757

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      Crystals on the move: If they are subjected to a strong light stimulus, crystals of the cobalt coordination compound [Co(NH3)5(NO2)]Cl(NO3) undergo sudden jumps and leap over distances 102–105 times their own size to release the strain that accumulates in their interior. The first quantitative kinematic analysis of this phenomenon is reported. The observed effect could be employed for actuation on the macroscopic scale.

    15. Protein–RNA Complexes

      A Suite of Solid-State NMR Experiments for RNA Intranucleotide Resonance Assignment in a 21 kDa Protein–RNA Complex (pages 9996–10001)

      Dr. Alexander Marchanka, Dr. Bernd Simon and Dr. Teresa Carlomagno

      Article first published online: 26 JUL 2013 | DOI: 10.1002/anie.201304779

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      Intranucleotide resonance of the 26mer box C/D RNA in complex with the L7Ae protein were assigned by solid-state NMR (ssNMR; see picture) spectroscopy. This investigation opens the way for studying RNA in large protein–RNA complexes by ssNMR spectroscopy.

    16. NMR Spectroscopy

      Molecular Mechanism of Prion Protein Oligomerization at Atomic Resolution (pages 10002–10005)

      Dr. Kai Schlepckow and Prof. Dr. Harald Schwalbe

      Article first published online: 9 AUG 2013 | DOI: 10.1002/anie.201305184

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      Prion protein oligomerization: Despite the crucial role of oligomers during prion protein (PrP) pathogenesis the molecular mechanism of their formation has remained largely elusive. A 2D time-resolved NMR study which made it possible to characterize the oligomerization kinetics with unprecedented site-specificity is reported (see picture).

    17. Drug Discovery

      Steering Target Selectivity and Potency by Fragment-Based De Novo Drug Design (pages 10006–10009)

      Dr. Tiago Rodrigues, Prof. Dr. Takayuki Kudoh, Filip Roudnicky, Yi Fan Lim, Yen-Chu Lin, Dr. Christian P. Koch, Prof. Dr. Masaharu Seno, Prof. Dr. Michael Detmar and Prof. Dr. Gisbert Schneider

      Article first published online: 26 AUG 2013 | DOI: 10.1002/anie.201304847

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      Kinase inhibitors: Ligand-based de novo design is validated as a viable technology for rapidly generating innovative compounds possessing the desired biochemical profile. The study discloses the discovery of the most selective vascular endothelial growth factor receptor-2 (VEGFR-2) kinase inhibitor (right in scheme) known to date as prime lead for antiangiogenic drug development.

    18. RNA Targeting

      Covalent Small-Molecule–RNA Complex Formation Enables Cellular Profiling of Small-Molecule–RNA Interactions (pages 10010–10013)

      Dr. Lirui Guan and Prof. Dr. Matthew D. Disney

      Article first published online: 1 AUG 2013 | DOI: 10.1002/anie.201301639

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      Won't let you go! A strategy is described to design small molecules that react with their cellular RNA targets. This approach not only improves the activity of compounds targeting RNA in cell culture by a factor of about 2500 but also enables cell-wide profiling of its RNA targets.

    19. Nanoparticles

      Capping with Multivalent Surfactants for Zeolite Nanocrystal Synthesis (pages 10014–10017)

      Changbum Jo, Jinhwan Jung, Hye Sun Shin, Jaeheon Kim and Prof. Ryong Ryoo

      Article first published online: 1 AUG 2013 | DOI: 10.1002/anie.201303088

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      Multiammonium surfactants exhibited a remarkable capping effect for zeolite synthesis in the forms of nanoparticles, nanorods, and nanosponges in cases where common monovalent surfactants failed. A nanorod-shaped mordenite zeolite synthesized in this manner showed significantly enhanced catalytic lifetimes in acid-catalyzed cumene synthesis reactions.

    20. Fluorescent Probes

      A Unique Family of Rigid Analogues of the GFP Chromophore with Tunable Two-Photon Action Cross-Sections for Biological Imaging (pages 10018–10022)

      Lin Yuan, Prof. Weiying Lin, Hua Chen, Sasa Zhu and Longwei He

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201303179

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      Conformationally restricted analogues of the GFP chromophore have been synthesized. The spectroscopic properties of GCTPOC, a unique family with tunable two-photon action cross-sections, were investigated. GCTPOC could be used as a robust two-photon platform for development of a two-photon fluorescent thiol sensor, which could stain endogenous thiols both in vitro and in vivo.

    21. Synthetic Methods

      Rhodium-Catalyzed Oxygenative Addition to Terminal Alkynes for the Synthesis of Esters, Amides, and Carboxylic Acids (pages 10023–10026)

      Insu Kim and Prof. Chulbom Lee

      Article first published online: 12 AUG 2013 | DOI: 10.1002/anie.201303669

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      A gem of a couple: The title reaction of terminal alkynes with O and N nucleophiles proceeds in the presence of [{Rh(cod)Cl}2], P(4-FC6H4)3, and 4-picoline N-oxide. Alcohols, amines, and water add to the terminal alkynes to give esters, amides, and carboxylic acids, respectively. The reaction involves formation of a rhodium vinylidene, oxidation to a ketene by oxygen transfer, and nucleophilic addition.

    22. Polymerization

      Visible-Light Hypervalent Iodide Carboxylate Photo(trifluoro)methylations and Controlled Radical Polymerization of Fluorinated Alkenes (pages 10027–10030)

      Prof. Alexandru D. Asandei, Olumide I. Adebolu, Christopher P. Simpson and Joon-Sung Kim

      Article first published online: 12 AUG 2013 | DOI: 10.1002/anie.201303826

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      IFAB-ulous trifluoromethylation: (CX3COO)2IIIIPh (X=F, H) and (CH3COO)3IV(C6H4COO) are introduced as CX3./CX3I precursors for metal-free, visible-light, radical (trifluoro)(iodo)methylations of alkenes, illustrated by their use as photoinitiators for the controlled radical polymerization of vinylidene fluoride with external (I(CF2)6I) and in situ generated (CF3I) iodine chain transfer agents, and for block copolymer synthesis.

    23. Organoaluminum Compounds

      Syntheses and Structures of an “Alumole” and Its Dianion (pages 10031–10034)

      Dr. Tomohiro Agou, Tatsuya Wasano, Dr. Peng Jin, Prof. Dr. Shigeru Nagase and Prof. Dr. Norihiro Tokitoh

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201304143

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      Base free: An alumole was synthesized and treatment with lithium afforded the lithium salt of the alumole dianion. The structures of these two molecules were then investigated. The C[BOND]C bond lengths of the AlC4 ring in the dianion are nearly equal. DFT calculations revealed that the 3p(Al)–π* conjugation lowers the LUMO level of the alumole and that coordination of two lithium cations to the alumole dianion results in a planar AlC4 ring.

    24. Cross-Coupling

      A General, Practical Palladium-Catalyzed Cyanation of (Hetero)Aryl Chlorides and Bromides (pages 10035–10039)

      Dr. Todd D. Senecal, Dr. Wei Shu and Prof. Dr. Stephen L. Buchwald

      Article first published online: 9 AUG 2013 | DOI: 10.1002/anie.201304188

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      Playing it safe: The nontoxic cyanide source K4[Fe(CN)6]⋅3 H2O can be used for the cyanation of (hetero)aryl halides. The application of palladacycle catalysts prevents poisoning during catalyst formation, thereby allowing for low catalyst loadings, fast reaction times, and wide heterocyclic substrate scope.

    25. Synthetic Methods

      Transition-Metal-Free Multicomponent Reactions Involving Arynes, N-Heterocycles, and Isatins (pages 10040–10043)

      Anup Bhunia, Tony Roy, Pradip Pachfule, Dr. Pattuparambil R. Rajamohanan and Dr. Akkattu T. Biju

      Article first published online: 1 AUG 2013 | DOI: 10.1002/anie.201304278

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      Mix and match: With isoquinoline as the nucleophilic trigger, multicomponent reactions afforded spirooxazino isoquinoline derivatives, proceeding through 1,4-dipolar intermediates. The use of pyridine as a nucleophile furnished indolin-2-one derivatives, with the reaction likely proceeding through a pyridylidene intermediate.

    26. Asymmetric Catalysis

      Rhodium-Catalyzed Tandem Cyclopropanation/Cope Rearrangement of 4-Alkenyl-1-sulfonyl-1,2,3-triazoles with Dienes (pages 10044–10047)

      Brendan T. Parr and Prof. Huw M. L. Davies

      Article first published online: 1 AUG 2013 | DOI: 10.1002/anie.201304310

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      Take your pick… A practical method for the synthesis of structurally diverse rhodium vinylcarbenes from stable 1-sulfonyl-1,2,3-triazole precursors has been developed. The reaction is general for a broad range of 4-alkenyl triazoles and dienes, enabling the stereoselective synthesis of a variety of polycyclic imines, which are readily converted into amines or aldehydes in a one-pot process.

    27. C[BOND]H Activation

      C[BOND]H Alkenylation of Azoles with Enols and Esters by Nickel Catalysis (pages 10048–10051)

      Lingkui Meng, Yuko Kamada, Kei Muto, Prof. Dr. Junichiro Yamaguchi and Prof. Dr. Kenichiro Itami

      Article first published online: 19 JUL 2013 | DOI: 10.1002/anie.201304492

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      Rather u(Ni)que: Two new C[BOND]H alkenylation reactions, that is C[BOND]H/C[BOND]O alkenylation and decarbonylative C[BOND]H alkenylation, of azoles are uniquely catalyzed by Ni/dcype. These azole alkenylation reactions are successfully applied to the convergent formal synthesis of siphonazole B.

    28. Natural Product Synthesis

      A Synthesis of the Chlorosulfolipid Mytilipin A via a Longest Linear Sequence of Seven Steps (pages 10052–10055)

      Dr. Won-jin Chung, Joseph S. Carlson, Dr. D. Karl Bedke and Prof. Christopher D. Vanderwal

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201304565

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      Magnificent seven: The chlorosulfolipid mytilipin A was synthesized in racemic form in seven steps and in enantioenriched form in eight steps. Key transformations include a highly diastereoselective bromoallylation of a sensitive α,β-dichloroaldehyde, a kinetic resolution of a vinyl epoxide, a convergent and highly Z-selective alkene cross-metathesis, and a chemoselective and diastereoselective dichlorination of a complex diene.

    29. Asymmetric Catalysis

      Palladium-Catalyzed Intermolecular Asymmetric Allylic Dearomatization Reaction of Naphthol Derivatives (pages 10056–10059)

      Chun-Xiang Zhuo and Prof. Dr. Shu-Li You

      Article first published online: 9 AUG 2013 | DOI: 10.1002/anie.201304591

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      Baring all: The title reaction provides β-naphthalenones bearing an all-carbon quaternary center in good to excellent yields, as well as excellent chemo- and enantioselectivity (see scheme).

    30. Synthetic Methods

      You have full text access to this OnlineOpen article
      A Rapid Route to Aminocyclopropanes via Carbamatoorganozinc Carbenoids (pages 10060–10063)

      Dr. Shingo Ishikawa, Dr. Tom D. Sheppard, Jarryl M. D'Oyley, Prof. Akio Kamimura and Prof. William B. Motherwell

      Article first published online: 1 AUG 2013 | DOI: 10.1002/anie.201304720

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      Easy as 1,2,3: Reaction of methyl carbamate, triethyl orthoformate, and readily available alkenes provides a highly practical preparation of protected aminocyclopropanes. The reaction proceeds with preferential cis addition to alkenes, and cleavage of the methyl carbamate gives the free aminocyclopropanes as their HI salts (see scheme).

    31. Organophosphorus Compounds

      The 2-Phosphaethynolate Anion: A Convenient Synthesis and [2+2] Cycloaddition Chemistry (pages 10064–10067)

      Andrew R. Jupp and Dr. Jose M. Goicoechea

      Article first published online: 1 AUG 2013 | DOI: 10.1002/anie.201305235

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      Hip to be square: Direct carbonylation of solutions of the heptaphosphide trianion (P73−) afforded the phosphaethynolate anion in moderate yields. This species undergoes [2+2] cycloaddition reactions with diphenylketene and bis(2,6-diisopropylphenyl)carbodiimide to yield the anionic four-membered heterocycles P[C(O)]2C(C6H5)2 and PC(O)(CNDipp)NDipp.

    32. Metallabenzenes

      Building a Parent Iridabenzene Structure from Acetylene and Dichloromethane on an Iridium Center (pages 10068–10071)

      Ángela Vivancos, Prof. Dr. Margarita Paneque, Prof. Dr. Manuel L. Poveda and Dr. Eleuterio Álvarez

      Article first published online: 9 AUG 2013 | DOI: 10.1002/anie.201305319

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      Parenthood: The reaction of [TpIr(C2H4)2] (1) (Tp=hydrotris(pyrazolyl)borate) with acetylene in CH2Cl2 affords a 1:1 mixture of the “parent” metallabenzene 2 (that is, all the ring carbon centers are CH units) and the β-Cl substituted vinyl species 3. Generation of 2 is by the coupling of an iridacyclopentadiene (formed from two acetylene molecules at the Ir center) with the dichloromethane-derived chlorocarbene “:C(H)Cl” and a subsequent α-Cl elimination event.

    33. Natural Products

      Total Syntheses of Amphidinolides T1, T3, and T4 (pages 10072–10075)

      Prof. Dr. J. Stephen Clark and Filippo Romiti

      Article first published online: 29 JUL 2013 | DOI: 10.1002/anie.201305467

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      Concise and high-yielding total syntheses of amphidinolides T1, T3, and T4 have been completed using an alkynyl macrolactone as a common late-stage intermediate. The required α-hydroxy ketone motif was installed by sequential alkyne hydrosilylation, epoxidation, and Fleming–Tamao oxidation. An oxonium ylide rearrangement formed the trisubstituted tetrahydrofuran core found in the natural products.

    34. Partial Reduction

      Catalytic 1,4-Selective Hydrosilylation of Pyridines and Benzannulated Congeners (pages 10076–10079)

      Dipl.-Chem. C. David F. Königs, Dr. Hendrik F. T. Klare and Prof. Dr. Martin Oestreich

      Article first published online: 1 AUG 2013 | DOI: 10.1002/anie.201305028

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      Radically different! The hydrosilylation of pyridines and quinolines is strictly 1,4-selective and likely involves an ionic one-step rather than the established radical two-step hydride transfer from a ruthenium(II) hydride complex onto the respective pyridinium and quinolinium ion intermediates (see scheme; ArF=3,5-(CF3)2C6H3). Even 4-substituted substrates react highly regioselectively. Isoquinolines yield the 1,2-reduced heterocycles.

    35. Abnormal N-Heterocyclic Carbenes

      Synthesis of an Imidazolium Phosphanide Zwitterion and Its Conversion into Anionic Imidazol-2-ylidene Derivatives (pages 10080–10083)

      Paresh K. Majhi, Dr. Gregor Schnakenburg, Zsolt Kelemen, Prof. Dr. Laszlo Nyulaszi, Prof. Dr. Derek P. Gates and Prof. Dr. Rainer Streubel

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201304431

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      Matter of opinion: The novel zwitterion 1 has been synthesized and studied theoretically and also converted into anionic NHCs 2. The former can also be described as a phosphinidene adduct of an abnormal N-heterocyclic carbene (1′) and, in the same vein, the latter represents a phosphinidene adduct of an anionic N-heterocyclic dicarbene (2′).

    36. Azaindole Synthesis

      Preparation of Functionalized Indoles and Azaindoles by the Intramolecular Copper-Mediated Carbomagnesiation of Ynamides (pages 10084–10088)

      M. Sc. Annette Frischmuth and Prof. Dr. Paul Knochel

      Article first published online: 9 AUG 2013 | DOI: 10.1002/anie.201304380

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      Variations on a theme: A mild and general intramolecular copper-mediated carbomagnesiation procedure for the synthesis of functionalized indoles as well as 4-, 5-, 6-, and 7-azaindoles starts from readily available ynamides. Subsequent reactions with various electrophiles provides polyfunctional N-heterocycles in good yields.

    37. Glycosidation

      Cooperative Catalysis in Glycosidation Reactions with O-Glycosyl Trichloroacetimidates as Glycosyl Donors (pages 10089–10092)

      Dr. Yiqun Geng, Dr. Amit Kumar, Prof. Dr. Hassan M. Faidallah, Prof. Dr. Hassan A. Albar, Dr. Ibrahim A. Mhkalid and Prof. Dr. Richard R. Schmidt

      Article first published online: 26 JUL 2013 | DOI: 10.1002/anie.201302158

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      Thiourea mediates cooperative glycosidation through hydrogen bonding. N,N′-Diarylthiourea as cocatalyst enforces an SN2-type acid-catalyzed glycosidation even at room temperature (see scheme; Bn=benzyl). From O-(α-glycosyl) trichloroacetimidates as glycosyl donors and various acceptors, β-glycosides are preferentially or exclusively obtained.

    38. Synthetic Methods

      Full Functionalization of the 7-Azaindole Scaffold by Selective Metalation and Sulfoxide/Magnesium Exchange (pages 10093–10096)

      M. Sc. Nadja M. Barl, Dr. Elodie Sansiaume-Dagousset, Prof. Dr. Konstantin Karaghiosoff and Prof. Dr. Paul Knochel

      Article first published online: 29 JUL 2013 | DOI: 10.1002/anie.201303490

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      Filling positions: 7-Azaindoles are important targets in the pharmaceutical industry. All five carbon positions of the azaindole ring system can be functionalized in a predictable manner starting from the appropriately substituted azaindole 1 by directed metalation and halogen/magnesium and sulfoxide/magnesium exchange. The products are fully substituted azaindoles of type 2.

    39. Self-Assembly

      pH-Switchable Ampholytic Supramolecular Copolymers (pages 10097–10101)

      Hendrik Frisch, Jan Patrick Unsleber, David Lüdeker, Dr. Martin Peterlechner, Priv.-Doz. Dr. Gunther Brunklaus, Dr. Mark Waller and Dr. Pol Besenius

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201303810

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      β-sheet-encoded anionic and cationic dendritic peptide amphiphiles form supramolecular copolymers when self-assembled in a 1:1 feed ratio of the monomers. These ampholytic materials have been designed for on-off polymerization in response to pH triggers. The cooperative supramolecular self-assembly process is switched on at a physiologically relevant pH value and can be switched off by increasing or decreasing the pH value.

    40. Coordination Cages

      Assembly and Stepwise Oxidation of Interpenetrated Coordination Cages Based on Phenothiazine (pages 10102–10106)

      Marina Frank, Jakob Hey, Ilker Balcioglu, Dr. Yu-Sheng Chen, Prof. Dr. Dietmar Stalke, Prof. Dr. Tomoyoshi Suenobu, Prof. Dr. Shunichi Fukuzumi, Dr. Holm Frauendorf and Prof. Dr. Guido H. Clever

      Article first published online: 23 JUL 2013 | DOI: 10.1002/anie.201302536

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      A breath of fresh air is sufficient for the eightfold S-monooxygenation of an interpenetrated double cage based on eight phenothiazine ligands and four square-planar-coordinated PdII cations. Besides these two cages, which were both characterized by X-ray crystallography, an eightfold S-dioxygenated double-cage was obtained under harsher oxidation conditions.

    41. Hybrid Materials

      Well-Defined Nanofibers with Tunable Morphology from Spherical Colloidal Building Blocks (pages 10107–10111)

      Markus B. Bannwarth, Samuel W. Kazer, Sebastian Ulrich, Gunnar Glasser, Dr. Daniel Crespy and Prof. Dr. Katharina Landfester

      Article first published online: 23 JUL 2013 | DOI: 10.1002/anie.201302133

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      From particles to fibers: Nanofibers with different morphologies and periodicities can be fabricated by supraparticular assembly of magnetic spherical nanoparticles. A linear sintering process is used to merge the assembled colloids together. The structure of the obtained fibers is controlled by the process parameters and the morphology of the spherical colloidal building blocks.

    42. Structural Biology

      The Role of Water and Sodium Ions in the Activation of the μ-Opioid Receptor (pages 10112–10115)

      Dr. Shuguang Yuan, Prof. Horst Vogel and Prof. Slawomir Filipek

      Article first published online: 31 JUL 2013 | DOI: 10.1002/anie.201302244

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      Dual effect of sodium ions: The activation of G-protein-coupled receptors depends on the presence of water molecules inside the receptor and also on allosteric interactions. The binding of sodium ions to the allosteric site of the μ opioid receptor was studied by microsecond molecular dynamics simulations and their seemingly contradictory roles in preventing ligand binding and facilitating receptor activation were explained.

    43. Nitrogen Fixation

      Analysis of the Magnetic Properties of Nitrogenase FeMo Cofactor by Single-Crystal EPR Spectroscopy (pages 10116–10119)

      Dr. Thomas Spatzal, Prof. Oliver Einsle and Prof. Susana L. A. Andrade

      Article first published online: 8 AUG 2013 | DOI: 10.1002/anie.201303000

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      The catalytic center of nitrogenase, the [Mo:7Fe:9S:C]:homocitrate FeMo cofactor, is a S=3/2 system with a rhombic magnetic g tensor. Single-crystal EPR spectroscopy in combination with X-ray diffraction were used to determine the relative orientation of the g tensor with respect to the cluster structure. The protein environment influences the electronic structure of the FeMo cofactor, dictating preferred orientations of possible functional relevance.

    44. Borylene Reduction

      Reductive Borylene–CO Coupling with a Bulky Arylborylene Complex (pages 10120–10123)

      Prof. Dr. Holger Braunschweig, Dr. Rian D. Dewhurst, Dipl.-Chem. Christian Hörl, Dr. Krzysztof Radacki, Dr. Christopher W. Tate, Dr. Alfredo Vargas and Dr. Qing Ye

      Article first published online: 25 JUL 2013 | DOI: 10.1002/anie.201303798

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      Partial metal–boron bond cleavage and coupling of a borylene with two CO ligands was observed upon reduction of a new bulky arylborylene complex. Both the borylene precursor and dianionic product were structurally and spectroscopically characterized. In contrast, reduction of an aminoborylene complex led to complete loss of the borylene ligand and classical Hieber reduction. A rationale for these differences based on DFT methods is presented.

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