Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 35

August 26, 2013

Volume 52, Issue 35

Pages 9051–9330

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireviews
    11. Communications
    1. You have free access to this content
      Cover Picture: From Short-Range to Long-Range Intermolecular NOEs in Ionic Liquids: Frequency Does Matter (Angew. Chem. Int. Ed. 35/2013) (page 9051)

      Mag. Sonja Gabl, Prof. Dr. Othmar Steinhauser and Prof. Dr. Hermann Weingärtner

      Version of Record online: 22 JUL 2013 | DOI: 10.1002/anie.201305786

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      The nuclear Overhauser effect … … (NOE) is used for studying the local structures in ionic liquids. In their Communication on page 9242 ff., H. Weingärtner et al. report a new model theory that makes it possible to analyze intermolecular 1H-19F NOE data of 1-butyl-3-methylimidazolium tetrafluoroborate. The arrow in the picture indicates that a H-F NOE at a H–F distance of about 20 Å can be predicted, although it is common knowledge that this effect is only observed for a distance of 5 Å.

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      Inside Cover: Carboxylation of Methyl Acrylate by Carbon Dioxide Radical Anions in Gas-Phase Water Clusters (Angew. Chem. Int. Ed. 35/2013) (page 9052)

      M. Sc. Amou Akhgarnusch, Dr. Robert F. Höckendorf, Dr. Qiang Hao, K. Philip Jäger, Dr. Chi-Kit Siu and Prof. Dr. Martin K. Beyer

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/anie.201305676

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      Electron transfer turns the chemically inert CO2 molecule into a reactive radical anion. In their Communication on page 9327 ff., C.-K. Siu, M. K. Beyer, and co-workers show how CO2.−, stabilized in a water cluster, attacks the C[DOUBLE BOND]C bond of methyl acrylate to form a new covalent bond. Without the hydration shell, however, neutral CO2 is released.

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      Inside Back Cover: Controlled Polymer-Brush Growth from Microliter Volumes using Sacrificial-Anode Atom-Transfer Radical Polymerization (Angew. Chem. Int. Ed. 35/2013) (page 9331)

      Junfeng Yan, Bin Li, Bo Yu, Prof. Wilhelm T. S. Huck, Prof. Weimin Liu and Prof. Feng Zhou

      Version of Record online: 26 JUL 2013 | DOI: 10.1002/anie.201305978

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      Electrochemical potential difference can be used to activate atom-transfer radical polymerization catalysts in a sandwiched metal substrate with microliter volumes. In their Communication on page 9125 ff., W. T. S. Huck, W. Liu, F. Zhou et al. use a single droplet solution (10 μL) to grow polymer brushes in controlled gradients and other complex shapes.

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      Back Cover: Maximum Aromaticity as a Guiding Principle for the Most Suitable Hosting Cages in Endohedral Metallofullerenes (Angew. Chem. Int. Ed. 35/2013) (page 9332)

      Marc Garcia-Borràs, Dr. Sílvia Osuna, Prof. Marcel Swart, Dr. Josep M. Luis and Prof. Miquel Solà

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/anie.201305725

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      The encapsulation of metal clusters in endohedral metallofullerenes takes place in cages that, in most cases, are far from being the most stable isomer among the corresponding hollow fullerenes. In their Communication on page 9275 ff., M. Solà, J. M. Luis et al. demonstrate that, in contrast to previous proposals, their results indicate that it is the maximum aromaticity criterion that determines the most suitable hosting cages.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireviews
    11. Communications
    1. 50 Years Ago ... (page 9068)

      Version of Record online: 22 AUG 2013 | DOI: 10.1002/anie.201306077

      Angewandte Chemie International Edition was first published in 1962, the mother journal first in 1888. In this monthly flashback, we feature some of the articles that appeared 50 years ago. This look back can open our eyes, stimulate discussion, or even raise a smile.

  4. News

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    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireviews
    11. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireviews
    11. Communications
    1. Stefan Grimme (pages 9076–9077)

      Version of Record online: 15 APR 2013 | DOI: 10.1002/anie.201301621

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      “My greatest achievement has been finishing a marathon run in reasonable time. Guaranteed to make me laugh is Loriot (German humorist). …” This and more about Stefan Grimme can be found on page 9074.

  6. News

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    4. Flashback
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    7. News
    8. Book Review
    9. Highlight
    10. Minireviews
    11. Communications
  7. Book Review

    1. Top of page
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    11. Communications
    1. Metal-Catalyzed Reactions in Water. Edited by Pierre H. Dixneuf and Victorio Cadierno. (page 9079)

      Boy Cornils

      Version of Record online: 22 JUL 2013 | DOI: 10.1002/anie.201305528

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      Wiley-VCH, Weinheim, 2013. 408 pp., hardcover, € 139.00.—ISBN 978-3527331888

  8. Highlight

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    4. Flashback
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    7. News
    8. Book Review
    9. Highlight
    10. Minireviews
    11. Communications
    1. Biosynthesis

      Elimination Reactions of Esters in the Biosynthesis of Polyketides and Ribosomal Peptides (pages 9082–9084)

      Dr. Bartlomiej Krawczyk, Eric F. van Herwerden, Prof. Dr. Herman S. Overkleeft and Prof. Dr. Roderich D. Süssmuth

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/anie.201304851

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      Enoyl intermediates are normally obtained through β-elimination of β-hydroxy carbonyl compounds. The OH group is eliminated either directly or is first activated through phosphorylation. Alternative strategies have now been identified: Glutamination or acetylation of a β-hydroxycarbonyl compound followed by β-elimination of an ester was proven to be a key step in the biosynthesis of class I lantipeptide and tetronate antibiotics.

  9. Minireviews

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    4. Flashback
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    11. Communications
    1. Asymmetric Catalysis

      Lewis Base Catalysis of the Mukaiyama Directed Aldol Reaction: 40 Years of Inspiration and Advances (pages 9086–9096)

      Dr. Gregory L. Beutner and Prof. Dr. Scott E. Denmark

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201302084

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      Aldol evergreen: Since the landmark publication of the first directed aldol addition reaction in 1973, the site, diastereo-, and enantioselective reaction has been elevated to the rarefied status of being both a named and a strategy-level reaction. The challenges of merging site, diastereo-, and enantioselectivity with catalysis into a unified reaction manifold have stimulated the development of Lewis base catalyzed aldol addition reactions.

    2. Natural Products

      The Impact of the Mukaiyama Aldol Reaction in Total Synthesis (pages 9097–9108)

      Dr. S. B. Jennifer Kan, Kenneth K.-H. Ng and Prof. Dr. Ian Paterson

      Version of Record online: 26 JUL 2013 | DOI: 10.1002/anie.201303914

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      Four decades since Mukaiyama's first reports on the use of silicon and boron enolates in directed aldol reactions, this highly controlled carbon–carbon bond-forming method has been developed into a powerful tool for natural product synthesis. A number of representative total syntheses that demonstrate the impact of the Mukaiyama aldol reaction are described and the underlying mechanistic rationale that determines the stereochemical outcomes is discussed.

    3. Mukaiyama Aldol Reaction

      The Mukaiyama Aldol Reaction: 40 Years of Continuous Development (pages 9109–9118)

      Dr. Jun-ichi Matsuo and Prof. Dr. Masahiro Murakami

      Version of Record online: 23 JUL 2013 | DOI: 10.1002/anie.201303192

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      The rest is history: Teruaki Mukaiyama developed three directed cross-aldol reactions, which were mediated by silyl enol ethers, boron enolates, and tin(II) enolates. These reactions had an immense impact on the stereoselective construction of acyclic polyoxygenated carbon frameworks. This Minireview provides a look at the history of the three directed cross-aldol reactions and portrays the early stages of their development.

  10. Communications

    1. Top of page
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    4. Flashback
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    11. Communications
    1. Nanocrystals

      Compositionally Tunable Photoluminescence Emission in Cu2ZnSn(S1−xSex)4 Nanocrystals (pages 9120–9124)

      Dr. Ajay Singh, Shalini Singh, Dr. Sergiu Levcenko, Dr. Thomas Unold, Dr. Fathima Laffir and Dr. Kevin M. Ryan

      Version of Record online: 18 JUN 2013 | DOI: 10.1002/anie.201302867

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      Inorganic nanostructures: Alloyed Cu2ZnSn(S1−xSex)4 wurtzite nanocrystals (10 nm in size) with a varying composition (x=0–1) were synthesized using a colloidal hot injection route. A photoluminescence (PL) emission study of these nanocrystals shows a compositionally tunable band-gap ranging between 0.9–1.4 eV that directly correlates to the sulfur-to-selenium ratio (see picture).

    2. Polymer Brushes

      Controlled Polymer-Brush Growth from Microliter Volumes using Sacrificial-Anode Atom-Transfer Radical Polymerization (pages 9125–9129)

      Junfeng Yan, Bin Li, Bo Yu, Prof. Wilhelm T. S. Huck, Prof. Weimin Liu and Prof. Feng Zhou

      Version of Record online: 1 JUL 2013 | DOI: 10.1002/anie.201304449

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      Brushing up on polymers: A difference in electrochemical potential allows surface-initiated atom-transfer radical polymerization on a sandwiched metal substrate using microliter volumes. CuI activators are continuously generated and diffuse to the initiator-modified substrate (see scheme), while CuII deactivators maintain polymerization. Polymer-brush gradients of SPMA and complex shapes were produced using this method.

    3. Magnetic Properties

      Slow Magnetic Relaxation in a CoII–YIII Single-Ion Magnet with Positive Axial Zero-Field Splitting (pages 9130–9134)

      Prof. Enrique Colacio, Dr. José Ruiz, Prof. Eliseo Ruiz, Eduard Cremades, Dr. J. Krzystek, Prof. Stefano Carretta, Dr. Joan Cano, Dr. Tatiana Guidi, Dr. Wolfgang Wernsdorfer and Prof. Euan K. Brechin

      Version of Record online: 14 JUL 2013 | DOI: 10.1002/anie.201304386

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      A magnetic Co-production: The complex [Co(μ-L)(μ-OAc)Y(NO3)2] (see structure O red, N blue, C gray), in which the CoII ion exhibits a D value of approximately +45 cm−1, as determined by magnetic and inelastic neutron scattering experiments, exhibits slow magnetic relaxation and single-ion magnet behavior.

    4. Asymmetric Autocatalysis

      Asymmetric Autocatalysis Induced by Cinnabar: Observation of the Enantioselective Adsorption of a 5-Pyrimidyl Alkanol on the Crystal Surface (pages 9135–9138)

      Prof. Dr. Hitoshi Shindo, Yusuke Shirota, Kaori Niki, Prof. Dr. Tsuneomi Kawasaki, Dr. Kenta Suzuki, Yuko Araki, Dr. Arimasa Matsumoto and Prof. Dr. Kenso Soai

      Version of Record online: 23 JUL 2013 | DOI: 10.1002/anie.201304284

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      A chiral mineral, cinnabar, served as a chiral source of asymmetric autocatalysis to afford enantioenriched 5-pyrimidyl alkanol. The adsorption structures of related compounds were observed with atomic force microscopy. Enantioselective adsorption of the asymmetric autocatalyst was found in microcrystal formations at the chiral surface of cinnabar.

    5. Heterocycles

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      Palladium- and Ruthenium-Catalyzed Cycloisomerization of Enynamides and Enynhydrazides: A Rapid Approach to Diverse Azacyclic Frameworks (pages 9139–9143)

      P. Ross Walker, Dr. Craig D. Campbell, Abid Suleman, Greg Carr and Dr. Edward A. Anderson

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/anie.201304186

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      I want to ride my azacycle: The title reaction of enynamides affords a wide diversity of azacycles. The reactions are high-yielding, highly stereoselective, and proceed rapidly under mild reaction conditions. Equivalent transformations using enynhydrazides offer new routes to pyrazole and indazole scaffolds. Boc=tert-butoxycarbonyl, EWG=electron-withdrawing group, Ns=4-nitrobenzenesulfonyl, Ts=4-toluenesulfonyl.

    6. C[BOND]H Activation

      Phosphoramidate Tantalum Complexes for Room-Temperature C[BOND]H Functionalization: Hydroaminoalkylation Catalysis (pages 9144–9148)

      Dr. Pierre Garcia, Ying Yin Lau, Mitchell R. Perry and Prof. Dr. Laurel L. Schafer

      Version of Record online: 23 JUL 2013 | DOI: 10.1002/anie.201304153

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      A cooled reaction: Phosphoramidate–ClTaMe3 complexes promote the first example of room-temperature hydroaminoalkylation catalysis. This reaction can be realized under solvent-free conditions and with challenging substrates such as styrenes and dialkyl amines. When using a vinylsilane substrate, for the first time the linear regioisomer is obtained preferentially using a Group 5 metal. TBS=tert-butyldimethylsilyl, TMS=trimethylsilyl.

    7. N-Heterocyclic Carbene

      N-tert-Butyl Triazolylidenes: Catalysts for the Enantioselective (3+2) Annulation of α,β-Unsaturated Acyl Azoliums (pages 9149–9152)

      Lisa Candish, Dr. Craig M. Forsyth and Dr. David W. Lupton

      Version of Record online: 14 JUL 2013 | DOI: 10.1002/anie.201304081

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      But(yl) not futile: A range of N-tert-butyl-substituted triazolylidene N-heterocyclic carbenes have been prepared. Of these, the morpholinone-derived catalyst (1) proved best suited to the enantioselective synthesis of cyclopentanes from donor–acceptor cyclopropanes and α,β-unsaturated acyl fluorides. The performance of this catalyst has been correlated to the electronic nature of the catalyst by 13C NMR analysis. M.S.=molecular sieves, TMS=trimethylsilyl.

    8. Cross-Coupling Methods

      Nickel-Catalyzed Enantioselective Arylation of Pyridinium Ions: Harnessing an Iminium Ion Activation Mode (pages 9153–9156)

      Stephen T. Chau, J. Patrick Lutz, Kevin Wu and Prof. Abigail G. Doyle

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201303994

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      A nickel for your thoughts … An enantioselective nickel-catalyzed cross-coupling between N-acylpyridinium salts and organozinc reagents is reported. The catalytic system, which is comprised of an air-stable NiII source and a chiral phosphoramidite ligand, affords 2-substituted-2,3-dihydro-4-pyridones with up to >99 % ee.

    9. Carbohydrate Vaccine

      Synthesis of Neisseria meningitidis Serogroup W135 Capsular Oligosaccharides for Immunogenicity Comparison and Vaccine Development (pages 9157–9161)

      Chia-Hung Wang, Shiou-Ting Li, Tzu-Lung Lin, Yang-Yu Cheng, Dr. Tsung-Hsien Sun, Prof. Jin-Town Wang, Dr. Ting-Jen R. Cheng, Prof. Kwok Kong Tony Mong, Prof. Chi-Huey Wong and Prof. Chung-Yi Wu

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201302540

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      Sweetening the deal: N. meningitidis serogroup W135 capsular oligosaccharides were synthesized in lengths from disaccharides to decasaccharides. Sera from mice immunized with these oligosaccharide–protein conjugates were examined by a glycan microarray (see picture) and bactericidal assay for antibody specificity and the ability to kill bacteria.

    10. Lithium batteries

      Quasi-Solid-State Rechargeable Lithium-Ion Batteries with a Calix[4]quinone Cathode and Gel Polymer Electrolyte (pages 9162–9166)

      Dr. Weiwei Huang, Dr. Zhiqiang Zhu, Dr. Lijiang Wang, Dr. Shiwen Wang, Hao Li, Prof. Dr. Zhanliang Tao, Prof. Dr. Jifu Shi, Prof. Dr. Lunhui Guan and Prof. Dr. Jun Chen

      Version of Record online: 3 JUL 2013 | DOI: 10.1002/anie.201302586

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      Filled to capacity: Calix[4]quinone (C4Q) has eight available carbonyl groups for binding lithium ions (see picture). It can be exploited to prepare quasi-solid-state rechargeable lithium batteries with a poly(methyl acrylate)/poly(ethylene glycol) based gel polymer electrolyte and a LiClO4/DMSO loading. It shows an initial discharge capacity of 422 mA h g−1 and a capacity retention of 379 mA h g−1 after 100 cycles.

    11. Molecular Switches

      A Directly Linked Ferrocene–Naphthalenediimide Conjugate: Precise Control of Stacking Structures of π-Systems by Redox Stimuli (pages 9167–9171)

      Dr. Atsuro Takai, Dr. Takeshi Yasuda, Dr. Tomoya Ishizuka, Prof. Dr. Takahiko Kojima and Prof. Dr. Masayuki Takeuchi

      Version of Record online: 23 JUL 2013 | DOI: 10.1002/anie.201302587

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      A ferrocene derivative having directly connected naphthalenediimide moieties has been synthesized. The stacking–destacking structures of the naphthalenediimides can be switched in response to redox stimuli by associating with the pivoting motion of ferrocene. The conformation and the electronic structure of naphthalenediimides are elucidated quantitatively in each electron-transfer state. The composite exhibited n-type semiconducting behavior.

    12. Zeolite Synthesis

      Solvent-Free Synthesis of Silicoaluminophosphate Zeolites (pages 9172–9175)

      Yinying Jin, Qi Sun, Guodong Qi, Chengguang Yang, Dr. Jun Xu, Fang Chen, Dr. Xiangju Meng, Prof. Feng Deng and Prof. Feng-Shou Xiao

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201302672

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      Solvents, who needs them? Silicoaluminophosphate zeolites with various frameworks have been successfully synthesized by a solvent-free route. Catalytic tests for the conversion of methanol to olefins show that thus obtained SAPO-34 (see picture) exhibited catalytic performance comparable to that of zeolites made by the conventional hydrothermal route.

    13. Palladium Catalysis

      Palladium-Catalyzed Asymmetric Construction of Vicinal All-Carbon Quaternary Stereocenters and its Application to the Synthesis of Cyclotryptamine Alkaloids (pages 9176–9181)

      Prof. Barry M. Trost and Maksim Osipov

      Version of Record online: 3 JUL 2013 | DOI: 10.1002/anie.201302805

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      A twofold Pd-DAAA Pd-catalyzed decarboxylative allylic alkylation (see scheme) was used to construct two vicinal all-carbon quaternary stereocenters (marked in red) in a diastereo- and enantioselective fashion. The products of the Pd-DAAA were further elaborated to complete the formal syntheses of cyclotryptamine alkaloids. The twofold Pd-catalyzed transformation proceeds through an initial matched allylation followed by a second mismatched allylation to deliver the desired product.

    14. Gene Delivery

      Light-Responsive Helical Polypeptides Capable of Reducing Toxicity and Unpacking DNA: Toward Nonviral Gene Delivery (pages 9182–9186)

      Dr. Lichen Yin, Dr. Haoyu Tang, Kyung Hoon Kim, Nan Zheng, Ziyuan Song, Dr. Nathan P. Gabrielson, Dr. Hua Lu and Prof. Dr. Jianjun Cheng

      Version of Record online: 5 JUL 2013 | DOI: 10.1002/anie.201302820

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      Gene delivery vehicles: Helical, cationic polypeptides with light-responsive domains showed potent membrane activity and promoted efficient cellular internalization of DNA (see picture). After transfection, a light trigger induces protecting-group removal to expose anionic carboxylate groups. The reduced cationic charge and helix distortion of the polypeptides result in enhanced DNA unpacking and reduced material toxicity because of the eliminated membrane activity.

    15. Bio-inspired Chemistry

      Poly(norepinephrine): Ultrasmooth Material-Independent Surface Chemistry and Nanodepot for Nitric Oxide (pages 9187–9191)

      Seonki Hong, Jihoon Kim, Yun Suk Na, Junghong Park, Sunjin Kim, Kaushik Singha, Prof. Dr. Gun-Il Im, Dr. Dong-Keun Han, Prof. Dr. Won Jong Kim and Prof. Dr. Haeshin Lee

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201301646

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      Capture and release: The material-independent surface chemistry of a poly(norepinephrine) (pNE) which exhibits perfect smoothness at the nanometer scale is controlled by 3,4-dihydroxybenzaldehyde-norepinephrine (DHBA-NE) conjugates. The pNE layer containing DHBA-NE serves to store and release small therapeutics such as nitric oxide.

    16. NMR Spectroscopy

      Protein Folding Studied by Dissolution Dynamic Nuclear Polarization (pages 9192–9195)

      Hsueh-Ying Chen, Mukundan Ragavan and Prof. Dr. Christian Hilty

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/anie.201301851

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      Folding and hyperpolarization: A method is presented for the measurement of protein folding by nuclear magnetic resonance. Denatured polypeptide is hyperpolarized using dissolution dynamic nuclear polarization, yielding a substantial signal enhancement that allows real-time 13C NMR spectroscopy of the refolding process after a rapid pH jump. The resulting spectra indicate global and site-specific changes in the protein.

    17. Photocatalysis

      Nanoporous Nitrogen-Doped Titanium Dioxide with Excellent Photocatalytic Activity under Visible Light Irradiation Produced by Molecular Layer Deposition (pages 9196–9200)

      Dr. Chaoqiu Chen, Ping Li, Guizhen Wang, Yu Yu, Feifei Duan, Caiying Chen, Prof. Weiguo Song, Prof. Yong Qin and Prof. Mato Knez

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201302329

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      Ultrathin films: A new molecular layer deposition process for the synthesis of nanoporous nitrogen-doped titanium dioxide films is developed. This process is based on a four-step ABCB reaction sequence using TiCl4, ethanolamine, and malonyl chloride as precursors (see picture). The obtained nanoporous N-doped TiO2 exhibits excellent photocatalytic activity upon irradiation with visible light.

    18. Natural Product Synthesis

      Total Synthesis of Indotertine A and Drimentines A, F, and G (pages 9201–9204)

      Yu Sun, Ruofan Li, Wenhao Zhang and Prof. Dr. Ang Li

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/anie.201303334

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      Oh my darling, Drimentine: The first total synthesis of the pyrroloindoline alkaloids drimentines A, F, and G, and their congener, indotertine A, is reported. An intermolecular radical conjugate addition was key in the synthesis of the drimentine alkaloids, and a biologically inspired iminium–olefin cyclization converted drimentine F into indotertine A.

    19. Isotopic Labeling

      N-Terminal Labeling of Peptides by Trypsin-Catalyzed Ligation for Quantitative Proteomics (pages 9205–9209)

      Yanbo Pan, Prof. Dr. Mingliang Ye, Dr. Liang Zhao, Kai Cheng, Mingming Dong, Chunxia Song, Hongqiang Qin, Dr. Fangjun Wang and Prof. Dr. Hanfa Zou

      Version of Record online: 5 JUL 2013 | DOI: 10.1002/anie.201303429

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      Two times an enzyme: Trypsin was first used as a protease to catalyze the digestion of proteins and then as a ligase to catalyze the linking of isotopically labeled amino acids to the N termini of tryptic peptides for quantitative proteomics. Reliable and accurate quantification of proteins was demonstrated for model proteins as well as proteome samples.

    20. Graphene Materials

      3D Honeycomb-Like Structured Graphene and Its High Efficiency as a Counter-Electrode Catalyst for Dye-Sensitized Solar Cells (pages 9210–9214)

      Hui Wang, Dr. Kai Sun, Prof. Franklin Tao, Dr. Dario J. Stacchiola and Prof. Yun Hang Hu

      Version of Record online: 29 JUL 2013 | DOI: 10.1002/anie.201303497

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      A useful Li: A simple reaction between Li2O and CO, gives a new type of three-dimensional graphene sheets—honeycomb-structured graphene. A dye-sensitized solar cell (DSSC) with the new graphene counter electrode has an energy conversion efficiency as high as 7.8 %, which is comparable to that of DSSCs with an expensive Pt counter electrode.

    21. Catalyst Development

      Hydrogen Bonding and Alcohol Effects in Asymmetric Hypervalent Iodine Catalysis: Enantioselective Oxidative Dearomatization of Phenols (pages 9215–9218)

      Prof. Dr. Muhammet Uyanik, Dr. Takeshi Yasui and Prof. Dr. Kazuaki Ishihara

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/anie.201303559

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      Iodine chooses: A conformationally flexible C2-symmetric organoiodine(III) catalyst for the highly enantioselective catalytic oxidative dearomatization of phenols has been developed. Catalysis is controlled by intramolecular hydrogen-bonding interactions and additional achiral alcohols.

    22. DNA Nanostructures

      Self-Assembly of DNA Origami and Single-Stranded Tile Structures at Room Temperature (pages 9219–9223)

      Dr. Zhao Zhang, Jie Song, Prof. Flemming Besenbacher, Dr. Mingdong Dong and Prof. Kurt V. Gothelf

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201303611

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      Efficient self-assembly: Self-assembly of DNA nanostructures at room temperature was achieved by incubating the component strands in the presence of a denaturing agent (30–40% formamide). This isothermal method is efficient for assembly of both DNA origami (purple, see scheme) and single-stranded tile (SST, blue) structures, as well as an SST ribbon growing on an origami template.

    23. Cell Sorting

      Micropatterned Photodegradable Hydrogels for the Sorting of Microbeads and Cells (pages 9224–9228)

      Christian Siltanen, Dr. Dong-Sik Shin, Prof. Julie Sutcliffe and Prof. Alexander Revzin

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/anie.201303965

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      Sorted out: Soft-lithography micropatterning of a photodegradable poly(ethylene glycol) hydrogel was utilized to sort cell-bound microbeads. Biofunctionalized microbeads were patterned, screened for cell binding activity, and isolated from arrays by UV irradiation. The technique is a simple approach for sorting and downstream processing of cultured cells.

    24. Asymmetric Catalysis

      Asymmetric Catalytic 1,6-Conjugate Addition/Aromatization of para-Quinone Methides: Enantioselective Introduction of Functionalized Diarylmethine Stereogenic Centers (pages 9229–9233)

      Wen-Dao Chu, Le-Fen Zhang, Xu Bao, Xian-He Zhao, Chao Zeng, Ji-Yuan Du, Guo-Biao Zhang, Fang-Xin Wang, Xiao-Yan Ma and Prof. Dr. Chun-An Fan

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/anie.201303928

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      It′s just a phase: The title reaction sequence of para-quinone methides (p-QMs) has been developed with malonates under phase-transfer catalysis. The reaction also offers an alternative route to asymmetric construction of diarylmethine stereocenters in excellent enantioselectivities and high yields.

    25. Soft Robotics

      Wavelength-Selective, IR Light-Driven Hinges Based on Liquid Crystalline Elastomer Composites (pages 9234–9237)

      Ryan R. Kohlmeyer and Prof. Jian Chen

      Version of Record online: 8 MAR 2013 | DOI: 10.1002/anie.201210232

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      An uphill climb: The title systems show fast, reversible bending with a large strain. Such hinges can power remote-controlled soft robots, including foldable origami structures, Venus flytrap-inspired grippers that can pick up delicate objects, and inchworm walkers that can crawl up a 50° incline (see picture).

    26. Reactive Intermediates

      Driving Force for Oxygen-Atom Transfer by Heme-Thiolate Enzymes (pages 9238–9241)

      Xiaoshi Wang, Sebastian Peter, Dr. René Ullrich, Prof. Martin Hofrichter and Prof. John T. Groves

      Version of Record online: 3 JUL 2013 | DOI: 10.1002/anie.201302137

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      Absolutely: Redox potentials for three redox couples in AaeAPO-catalyzed reactions have been measured, thus placing these heme-thiolate reactive intermediates on an absolute energy scale for the first time. The importance of the axial thiolate ligand and the basic nature of compound II ferryl oxygen atom are discussed in terms of these redox potentials.

    27. Ionic Liquids

      From Short-Range to Long-Range Intermolecular NOEs in Ionic Liquids: Frequency Does Matter (pages 9242–9246)

      Mag. Sonja Gabl, Prof. Dr. Othmar Steinhauser and Prof. Dr. Hermann Weingärtner

      Version of Record online: 17 JUN 2013 | DOI: 10.1002/anie.201302712

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      Frequency-dependent NOE: A new model theory was used to analyze the spatial range of the intermolecular nuclear Overhauser effect in ionic liquids. The spatial range undergoes a transition from long-range nature at low frequency to a short-range character at high frequencies. The experimentally accessible cross-relaxation rate involves contributions from both regimes, but the long-range component dominates.

    28. Asymmetric Catalysis

      Desymmetrization of meso-2,5-Diallylpyrrolidinyl Ureas through Asymmetric Palladium-Catalyzed Carboamination: Stereocontrolled Synthesis of Bicyclic Ureas (pages 9247–9250)

      Nicholas R. Babij and Prof. John P. Wolfe

      Version of Record online: 3 JUL 2013 | DOI: 10.1002/anie.201302720

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      Lost symmetry: Fused bicyclic ureas are enantioselectively obtained through Pd-catalyzed desymmetrizing carboaminations of meso-2,5-diallylpyrrolidinyl ureas (see scheme). The reactions generate a C[BOND]N and a C[BOND]C bond, and afford products with three stereocenters. One of these products was transformed to a tricyclic guanidine and then to 9-epi-batzelladine K over several steps.

    29. Heterocycles

      Key Intermediates of Iodine-Mediated Electrophilic Cyclization: Isolation and Characterization in an Osmabenzene System (pages 9251–9255)

      Tongdao Wang, Dr. Hong Zhang, Feifei Han, Lipeng Long, Prof. Dr. Zhenyang Lin and Prof. Dr. Haiping Xia

      Version of Record online: 29 JUL 2013 | DOI: 10.1002/anie.201302863

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      Caught in the act: Key intermediates in an iodine-mediated electrophilic cyclization reaction was isolated by introducing metallabenzenes as the starting material. The unique structure of the intermediate should be described as the intimate ion pair form, instead of the widely accepted iodonium ion form.

    30. Anticancer Lead Discovery

      Mycalol: A Natural Lipid with Promising Cytotoxic Properties against Human Anaplastic Thyroid Carcinoma Cells (pages 9256–9260)

      Dr. Adele Cutignano, Dr. Genoveffa Nuzzo, Dr. Daniela D'Angelo, Dr. Eleonora Borbone, Dr. Alfredo Fusco and Dr. Angelo Fontana

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/anie.201303039

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      From Antarctic waters: Human anaplastic thyroid carcinoma (ATC) cells which stably express antisense construct against nuclear high-mobility group A (HMGA) proteins were used in a novel phenotypic assay for screening marine natural extracts. The rational search led to the isolation and identification of a novel polyoxygenated linear lipid (1) that showed important and selective cytotoxicity against ATC-derived tumor cell lines.

    31. Asymmetric Synthesis

      Core-Structure-Motivated Design of Iminium–Enolate Organocascade Reactions: Enantioselective Syntheses of 5,6-Dihydroindolizines (pages 9261–9265)

      Dr. Xianxing Jiang, Bin Tan and Prof. Dr. Carlos F. Barbas III

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201303300

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      Indolizine skeletons: A highly efficient dual iminium–enolate generation/activation process is introduced as a new platform for the design of organocatalytic intermolecular domino reactions for the direct construction of 5,6-dihydroindolizine derivatives. This process provides ready access to indolizine skeletons with high optically purity from simple starting materials (see picture).

    32. Synthetic Methods

      Enantioselective Organocatalytic Fluorination-Induced Wagner–Meerwein Rearrangement (pages 9266–9270)

      Fedor Romanov-Michailidis, Dr. Laure Guénée and Prof. Dr. Alexandre Alexakis

      Version of Record online: 14 JUL 2013 | DOI: 10.1002/anie.201303527

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      Cracked under strain: Strained allylic cyclobutanols and cyclopropanols readily undergo a ring expansion described by the title rearrangement. This reaction is promoted by catalytic amounts of 1 and displays high tolerance with respect to the substrate scope. The corresponding β-fluoro spiroketone products are isolated in high yields and with excellent stereoselectivities. EDG=electron-donating group, EWG=electron-withdrawing group.

    33. Heterocycles

      Facile [7C+1C] Annulation as an Efficient Route to Tricyclic Indolizidine Alkaloids (pages 9271–9274)

      Prof. Dr. Xianxiu Xu, Lingjuan Zhang, Xiqing Liu, Dr. Ling Pan and Prof. Dr. Qun Liu

      Version of Record online: 2 JUL 2013 | DOI: 10.1002/anie.201303604

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      A handle on annulation: The two alkenoyl moieties of the cyclic dithiolane are parallel to each other and enables the [7C+1C] annulation with ethyl isocyanoacetate to occur. As a result, tricyclic indolizidine alkaloids are constructed by a two-step, base-catalyzed [7C+1C] annulation/intramolecular cyclization with subsequent reduction/cyclization.

    34. Computational Chemistry

      Maximum Aromaticity as a Guiding Principle for the Most Suitable Hosting Cages in Endohedral Metallofullerenes (pages 9275–9278)

      Marc Garcia-Borràs, Dr. Sílvia Osuna, Prof. Marcel Swart, Dr. Josep M. Luis and Prof. Miquel Solà

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201303636

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      Encapsulating! The encapsulation of metal clusters in endohedral metallofullerenes takes place in cages that, in most cases, are far from being the most stable isomer in the corresponding hollow fullerenes. In contrast to previous proposals, new results indicate that it is the maximum aromaticity criterion that determines the most suitable hosting cages.

    35. C[BOND]H Activation

      Copper-Catalyzed Dehydrogenative Coupling of Arenes with Alcohols (pages 9279–9283)

      Dr. Sukalyan Bhadra, Christian Matheis, Dr. Dmitry Katayev and Prof. Dr. Lukas J. Gooßen

      Version of Record online: 22 JUL 2013 | DOI: 10.1002/anie.201303702

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      What a couple! Arenes functionalized with donating groups undergo oxidative dehydrogenative coupling with alcohols in the presence of a copper/silver catalyst system. This intermolecular C[BOND]H alkoxylation provides a convenient synthetic route to the important class of aryl ethers. The catalyst system also allows the alkoxylation of benzylic C[BOND]H groups with formation of benzyl alkyl ethers.

    36. Alkene Difunctionalization

      Copper-Catalyzed Intramolecular Electrophilic Carbofunctionalization of Allylic Amides (pages 9284–9288)

      Elise Cahard, Dr. Nadine Bremeyer and Prof. Matthew J. Gaunt

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/anie.201303724

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      An­ endo-selective copper-catalyzed oxyarylation and oxyvinylation of allylic amides was developed. The products are the six-membered ring oxazines and are formed exclusively as the anti isomers. A range of substituted allylic amides and a wide selection of diaryliodonium and vinyl(aryl)iodonium triflates are compatible with this transformation.

    37. Multicomponent Reactions

      Diversity-Oriented Three-Component Reactions of Diazo Compounds with Anilines and 4-Oxo-Enoates (pages 9289–9292)

      Changcheng Jing, Dr. Dong Xing, Yu Qian, Taoda Shi, Yun Zhao and Prof. Dr. Wenhao Hu

      Version of Record online: 3 JUL 2013 | DOI: 10.1002/anie.201303987

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      Choosing a path: The title reaction can proceed through two different reaction pathways, and is controlled by the addition sequence of the substrates. Divergent polyfunctional products, pyrrolidines or linear α-amino ester derivatives, are obtained in good yields and high diastereoselectivities.

    38. Organocatalysis

      Catalytic Asymmetric Benzidine Rearrangement (pages 9293–9295)

      Dr. Chandra Kanta De, Dr. Fabio Pesciaioli and Prof. Dr. Benjamin List

      Version of Record online: 5 JUL 2013 | DOI: 10.1002/anie.201304039

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      A chiral Brønsted acid catalyzes the asymmetric benzidine rearrangement of N,N′-dinaphthylhydrazines. Different electronically and structurally diverse axially chiral 2,2′-binaphthyl diamine (BINAM) derivatives are obtained with high enantioselectivity.

    39. Synthetic Methods

      Metal-Free Intramolecular Carbocyanation of Activated Alkenes: Functionalized Nitriles Bearing β-Quaternary Carbon Centers (pages 9296–9300)

      Jianming Chen, Gongfeng Zou and Prof. Dr. Weiwei Liao

      Version of Record online: 14 JUL 2013 | DOI: 10.1002/anie.201304102

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      The CN shuffle: The described intramolecular alkenyl- and acylcyanation reaction of activated alkenes proceed by cleavage of a C[BOND]N bond. This protocol provides access to functionalized acyclic nitriles with quaternary carbon centers under neutral and mild reaction conditions, demonstrates broad scope, and good functional-group compatibility and versatility. Y=O or CHR4; R1,R4=electron-withdrawing group; TBACN=tetrabutylammonium cyanide.

    40. Radicals

      Direct Detection of a Persistent Carbonyloxyl Radical in the Gas Phase (pages 9301–9304)

      Dr. Berwyck L. J. Poad, Dr. Benjamin B. Kirk, Pramesh I. Hettiarachchi, Dr. Adam J. Trevitt, Prof. Stephen J. Blanksby and Prof. Timothy Clark

      Version of Record online: 14 JUL 2013 | DOI: 10.1002/anie.201304316

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      Long lived: Carbonyloxyl radicals (RCO2.) are reactive intermediates that play key roles in initiating polymerization reactions. This reactivity also makes their direct observation difficult. For the first time a persistent organic RCO2. radical is detected in the gas phase, its extraordinary longevity is attributed to the high barrier towards fragmentation owing to the endothermicity of the decarboxylation products.

    41. Synthetic Methods

      Palladium-Catalyzed Three-Component Reaction of Allenes, Aryl Iodides, and Diazo Compounds: Approach to 1,3-Dienes (pages 9305–9308)

      Qing Xiao, Binglong Wang, Leiming Tian, Yang Yang, Jian Ma, Dr. Yan Zhang, Prof. Dr. Shufeng Chen and Prof. Dr. Jianbo Wang

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/anie.201304327

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      'Diene' to know: The title reaction leads to the formation of 1,3-dienes in high yields (see scheme). The reaction also proceeds with the use of N-tosylhydrazone substrates. Carbopalladation to the allene and palladium carbene migratory insertion are proposed to play the key role in this transformation.

    42. Enzymatic C[BOND]H Amination

      Enantioselective Intramolecular C[BOND]H Amination Catalyzed by Engineered Cytochrome P450 Enzymes In Vitro and In Vivo (pages 9309–9312)

      Dr. John A. McIntosh, Dr. Pedro S. Coelho, Christopher C. Farwell, Dr. Z. Jane Wang, Prof. Dr. Jared C. Lewis, Tristan R. Brown and Prof. Dr. Frances H. Arnold

      Version of Record online: 24 JUL 2013 | DOI: 10.1002/anie.201304401

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      Nitrogen activation: Though P450 enzymes are masters of oxygen activation and insertion into C[BOND]H bonds, their ability to use nitrogen for the same purpose has so far not been explored. Engineered variants of cytochrome P450BM3 have now been found to catalyze intramolecular C[BOND]H aminations in azide substrates. Mutations to two highly conserved residues significantly increased this activity.

    43. Synthetic Methods

      Asymmetric Hydrogenation of tert-Alkyl Ketones: DMSO Effect in Unification of Stereoisomeric Ruthenium Complexes (pages 9313–9315)

      Tomoya Yamamura, Hiroshi Nakatsuka, Shinji Tanaka and Prof. Dr. Masato Kitamura

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201304408

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      Face off: The ruthenium complexes of a new axially chiral PNN ligand (L) are highly efficient in the presence of dimethylsulfoxide (DMSO) for hydrogenation of both functionalized and unfunctionalized tert-alkyl ketones. DMSO is thought to narrow down the many possible complex stereoisomers into a single facial L/Ru complex, thus enhancing the reactivity, selectivity, and productivity.

    44. BN Heterocycles

      Rhodium-Catalyzed Boron Arylation of 1,2-Azaborines (pages 9316–9319)

      Gabriel E. Rudebusch, Dr. Lev N. Zakharov and Prof. Dr. Shih-Yuan Liu

      Version of Record online: 5 JUL 2013 | DOI: 10.1002/anie.201304443

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      A Sn-phony in B! BN isosteres of biphenyl compounds are prepared through Rh-catalyzed cross-coupling between 2-chloro-1,2-azaborines and arylstannanes (see scheme). The synthetic method should enable investigations of structure–activity relationships (SARs) by expanding the chemical space of the pharmaceutically relevant biphenyl structure through BN/CC isosterism.

    45. Photochromic Actuators

      Photoinduced Twisting of a Photochromic Diarylethene Crystal (pages 9320–9322)

      Daichi Kitagawa, Dr. Hiroyasu Nishi and Prof. Dr. Seiya Kobatake

      Version of Record online: 19 JUL 2013 | DOI: 10.1002/anie.201304670

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      Let's do the twist! Molecular crystals of a diarylethene derivative exhibit photoreversible twisting upon irradiation with UV and visible light. The left-handed and right-handed helix formation is ascribed to the contraction of the crystal in a diagonal direction, depending on which face is irradiated with UV light.

    46. Asymmetric Catalysis

      Highly Enantioselective Reduction of α-Methylated Nitroalkenes (pages 9323–9326)

      Dr. Edyta Burda, Tina Reß, Till Winkler, Carolin Giese, Xenia Kostrov, Tobias Huber, Prof. Dr. Werner Hummel and Prof. Dr. Harald Gröger

      Version of Record online: 26 JUL 2013 | DOI: 10.1002/anie.201301814

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      Highly selective: The reduction of α-methyl-substituted nitroalkenes succeeds in a highly enantioselective fashion with an ene reductase from Gluconobacter oxydans. Under optimized reaction conditions the desired nitroalkanes are formed with enantiomeric excesses of up to 95% in these biotransformations.

    47. CO2 Activation

      Carboxylation of Methyl Acrylate by Carbon Dioxide Radical Anions in Gas-Phase Water Clusters (pages 9327–9330)

      M. Sc. Amou Akhgarnusch, Dr. Robert F. Höckendorf, Dr. Qiang Hao, K. Philip Jäger, Dr. Chi-Kit Siu and Prof. Dr. Martin K. Beyer

      Version of Record online: 10 JUL 2013 | DOI: 10.1002/anie.201302827

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      The addition of CO2 to olefins in nanoscale water droplets was studied by mass spectrometry. One electron is enough to turn a CO2 molecule into its bent, reactive radical anionic form (left in scheme), which is stabilized by a hydration shell. This species reacts with methyl acrylate by radical addition to the carbon–carbon double bond. Without the hydration shell, however, neutral carbon dioxide is released.

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