Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 32

August 4, 2014

Volume 53, Issue 32

Pages 8253–8522

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Fast Prediction of Adsorption Properties for Platinum Nanocatalysts with Generalized Coordination Numbers (Angew. Chem. Int. Ed. 32/2014) (page 8253)

      Dr. Federico Calle-Vallejo, Dr. José I. Martínez, Prof. Juan M. García-Lastra, Dr. Philippe Sautet and Dr. David Loffreda

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201405515

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      In heterogeneous catalysis and fuel-cell design, the fast and accurate prediction of chemical reactivity is paramount. Current theoretical models use electronic-structure-based descriptors with known limitations. D. Loffreda et al. demonstrate in their Communication on page 8316 ff. that the adsorption energetics of oxygenated species on various platinum nanoparticles and surfaces are linearly captured by a non-electronic, exact, and powerful descriptor: the generalized coordination number.

    2. You have free access to this content
      Inside Cover: A Protein-Based Pentavalent Inhibitor of the Cholera Toxin B-Subunit (Angew. Chem. Int. Ed. 32/2014) (page 8254)

      Dr. Thomas R. Branson, Dr. Tom E. McAllister, Jaime Garcia-Hartjes, Dr. Martin A. Fascione, Dr. James F. Ross, Dr. Stuart L. Warriner, Dr. Tom Wennekes, Prof. Han Zuilhof and Dr. W. Bruce Turnbull

      Article first published online: 2 JUL 2014 | DOI: 10.1002/anie.201405672

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      The cholera toxin B-subunit has been re-engineered to create a potent inhibitor of the parent toxin. Toxin adhesion can be blocked by a nonbinding mutant of the B subunit, which was modified with five copies of the carbohydrate ligand, as shown by W. B Turnbull and co-workers in their Communication on page 8323 ff. Site-specific modification of a protein scaffold that is matched in both size and valency to the target toxin may become a general strategy for inhibitor design.

    3. You have free access to this content
      Inside Back Cover: Concurrent Stabilization of π-Donor and π-Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)2] Complexes (Angew. Chem. Int. Ed. 32/2014) (page 8523)

      Michael G. Mazzotta, Dr. Kothanda Rama Pichaandi, Dr. Phillip E. Fanwick and Prof. Dr. Mahdi M. Abu-Omar

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201405439

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      A dioxocarbonyl organometallic complex has been isolated and characterized by Abu-Omar and co-workers, as described in their Communication on page 8320 ff. π-donor oxo (orange) and π-acceptor carbonyl (blue) ligands are typically in conflict with one another, rarely coexisting in metal complexes. However, in this case, the synergistic interaction between ligands stabilizes the high-valent rhenium(V) pincer complex and may have important implications in catalysis.

    4. You have free access to this content
      Back Cover: MnxOy/NC and CoxOy/NC Nanoparticles Embedded in a Nitrogen-Doped Carbon Matrix for High-Performance Bifunctional Oxygen Electrodes (Angew. Chem. Int. Ed. 32/2014) (page 8524)

      Dr. Justus Masa, Dr. Wei Xia, Dr. Ilya Sinev, Anqi Zhao, Dr. Zhenyu Sun, Stefanie Grützke, Philipp Weide, Prof. Dr. Martin Muhler and Prof. Dr. Wolfgang Schuhmann

      Article first published online: 1 JUL 2014 | DOI: 10.1002/anie.201405941

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      Dual function oxygen-reduction and oxygen-evolution catalysts are vital for the realization of rechargeable metal–air batteries and unitized regenerative fuel-cell systems. In their Communication on page 8508 ff., W. Schuhmann, M. Muhler et al. report exceptionally active bifunctional catalysts for oxygen-reduction and -evolution based on Co, Mn, and Ni oxides embedded in nitrogen-doped carbon, which outperform archetypical Pt, Ir, and Ru-based catalysts.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Frontispiece: Simultaneous Arrangement of up to Three Different Molecules on the Pore Surface of a Metal–Macrocycle Framework: Cooperation and Competition (page 8254)

      Dr. Shohei Tashiro, Tsutomu Umeki, Dr. Ryou Kubota and Prof. Dr. Mitsuhiko Shionoya

      Article first published online: 1 AUG 2014 | DOI: 10.1002/anie.201483271

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      Molecular Arrangement

  3. Graphical Abstract

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 32/2014 (pages 8257–8270)

      Article first published online: 1 AUG 2014 | DOI: 10.1002/anie.201490030

  4. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Yingfu Li (page 8276)

      Article first published online: 9 APR 2014 | DOI: 10.1002/anie.201403018

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      “My favorite molecule is DNA, because it is simple yet mysterious. When I was eighteen I wanted to be a novelist …” This and more about Yingfu Li can be found on page 8276.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. The Antidote. Inside the World of New Pharma. By Barry Werth. (pages 8278–8279)

      Herbert Waldmann

      Article first published online: 1 AUG 2014 | DOI: 10.1002/anie.201405216

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      Simon & Schuster, New York, 2014. 448 pp., hardcover, $ 30.00.—ISBN 978-1451655667

  8. Highlight

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. CO2 Fixation

      The Elusive Cyanoformate: An Unusual Cyanide Shuttle (pages 8282–8284)

      Christian Hering, Dr. Jan von Langermann and Prof. Dr. Axel Schulz

      Article first published online: 2 JUL 2014 | DOI: 10.1002/anie.201405339

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      Catch me if you can: CO2 is shown to reversibly bind to CN, forming the elusive cyanoformate anion, which is on the verge of breakdown. This is a significant finding with respect to the understanding of biological processes in enzymes and for molecular CO2-based shuttle systems.

  9. Minireview

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

      The Biocatalytic Repertoire of Natural Biaryl Formation (pages 8286–8293)

      Dipl.-Chem. Hülya Aldemir, Dipl.-Biol. René Richarz and Prof. Dr. Tobias A. M. Gulder

      Article first published online: 9 JUL 2014 | DOI: 10.1002/anie.201401075

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      Enzymes crossing: The structural diversity and biomedical potential of biaryl natural products is tremendous. Equally intriguing are the biosynthetic tools nature has evolved to construct this privileged structural feature. This Minireview discusses selected examples of biocatalytic oxidative cross-coupling strategies in the biosynthesis of natural products.

  10. Review

    1. Top of page
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    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Trifluoromethylation

      Trifluoromethylation of Alkenes with Concomitant Introduction of Additional Functional Groups (pages 8294–8308)

      Dr. Hiromichi Egami and Prof. Dr. Mikiko Sodeoka

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201309260

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      CF3 and more: The trifluoromethyl group is the most widely studied fluorine-containing functional group. Many methods are available for the introduction of a trifluoromethyl group into organic molecules. This Review summarizes recent advances in the trifluoromethylation of alkenes with concomitant introduction of additional functional groups.

  11. Communications

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

      Simultaneous Arrangement of up to Three Different Molecules on the Pore Surface of a Metal–Macrocycle Framework: Cooperation and Competition (pages 8310–8315)

      Dr. Shohei Tashiro, Tsutomu Umeki, Dr. Ryou Kubota and Prof. Dr. Mitsuhiko Shionoya

      Article first published online: 30 MAY 2014 | DOI: 10.1002/anie.201404179

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      Three different molecules in a single pore: TTF (tetrathiafulvalene), ferrocene, and fluorene are incorporated simultaneously on the pore surface of a porous crystalline metal–macrocycle framework (MMF), as revealed by single-crystal XRD analysis. The anchoring effects of hydrogen bonding with the hydroxy groups of the guest molecules and inter-guest cooperation and competition are critical control factors in the adsorption behavior of the guest molecules.

    2. Nanotechnology

      Fast Prediction of Adsorption Properties for Platinum Nanocatalysts with Generalized Coordination Numbers (pages 8316–8319)

      Dr. Federico Calle-Vallejo, Dr. José I. Martínez, Prof. Juan M. García-Lastra, Dr. Philippe Sautet and Dr. David Loffreda

      Article first published online: 11 JUN 2014 | DOI: 10.1002/anie.201402958

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      The trends in the adsorption energies of oxygen- and hydrogen-containing adsorbates on various platinum nanoparticles and extended surfaces are analyzed. By means of generalized coordination numbers, it is possible to unify the trends among dissimilar structures and sizes. Adsorption energies for terraces, edges, corners, and adatoms and finite-size effects could be accurately described.

    3. Organometallics

      Concurrent Stabilization of π-Donor and π-Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)2] Complexes (pages 8320–8322)

      Michael G. Mazzotta, Dr. Kothanda Rama Pichaandi, Dr. Phillip E. Fanwick and Prof. Dr. Mahdi M. Abu-Omar

      Article first published online: 28 MAY 2014 | DOI: 10.1002/anie.201403788

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      The best of both worlds! The synthesis of [(PNN)Re(CO)(O)2] marks the first isolable dioxo carbonyl organometallic complex. These species have previously only been identified in transient states, as they feature electronically conflicting ligands. DFT calculations indicate a synergistic relationship between these ligands and the metal center in this novel rhenium pincer complex.

    4. Multivalent Inhibitors | Very Important Paper

      You have full text access to this OnlineOpen article
      A Protein-Based Pentavalent Inhibitor of the Cholera Toxin B-Subunit (pages 8323–8327)

      Dr. Thomas R. Branson, Dr. Tom E. McAllister, Jaime Garcia-Hartjes, Dr. Martin A. Fascione, Dr. James F. Ross, Dr. Stuart L. Warriner, Dr. Tom Wennekes, Prof. Han Zuilhof and Dr. W. Bruce Turnbull

      Article first published online: 2 JUL 2014 | DOI: 10.1002/anie.201404397

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      Cholera versus cholera: The inhibition of multivalent protein/carbohydrate interactions between toxins and glycolipids in cell membranes can prevent the toxins from entering cells. The site-specific modification of a protein scaffold, matched in both size and valency to the target toxin, led to a multivalent inhibitor with an IC50 value of 104 pM for the cholera toxin B-subunit.

    5. DNA Hydrogels

      Construction of Three-Dimensional DNA Hydrogels from Linear Building Blocks (pages 8328–8332)

      Dr. Tanja Nöll, Prof. Dr. Holger Schönherr, Dr. Daniel Wesner, Dr. Michael Schopferer, Dr. Thomas Paululat and Dr. Gilbert Nöll

      Article first published online: 25 JUN 2014 | DOI: 10.1002/anie.201402497

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      Genetic jelly: A 3D DNA hydrogel was generated by self-assembly of short linear double-stranded DNA (dsDNA) building blocks equipped with sticky ends. The supramolecular structures comprising the highly thermoresponsive hydrogel were studied with diffusion-ordered NMR spectroscopy (DOSY NMR), rheology, and atomic force microscopy (AFM). At room temperature, densely packed structures of entangled chains, which are also expected to contain multiple interlocked rings, were observed.

    6. Synthetic Methods

      Transition-Metal-Free Tunable Chemoselective N Functionalization of Indoles with Ynamides (pages 8333–8337)

      Alexandre Hentz, Dr. Pascal Retailleau, Prof. Dr. Vincent Gandon, Dr. Kevin Cariou and Dr. Robert H. Dodd

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201402767

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      Two birds with one stone: Under basic reaction conditions, two distinct manners of functionalizing the nitrogen atom of indoles with ynamides are reported. Unsubstituted N-tosyl-N-alkyl ynamides undergo addition at the β-position to yield (Z)-2-indolo-etheneamide with complete regioselectivity, whereas N-phenyl and/or N-carboxyl ynamides undergo addition at the α-position, albeit with the concomitant loss of the electron-withdrawing group.

    7. Gold Nanoparticles

      Dynamic and Quantitative Control of the DNA-Mediated Growth of Gold Plasmonic Nanostructures (pages 8338–8342)

      Dr. Jianlei Shen, Lifeng Xu, Dr. Chunpeng Wang, Dr. Hao Pei, Prof.Dr. Renzhong Tai, Prof.Dr. Shiping Song, Prof.Dr. Qing Huang, Prof.Dr. Chunhai Fan and Prof.Dr. Gang Chen

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201402937

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      A heart of gold: A quantitative approach to intercept the evolution of size, surface morphology, and the optical properties of Au plasmonic nanostructures is demonstrated by dynamic control of the DNA-mediated growth. The structural parameters of these nanostructures correlate well with their optical properties, obtained from small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM).

    8. Materials Synthesis

      Synthesis and Properties of Lanthanide Ruthenium(III) Oxide Perovskites (pages 8343–8347)

      Dr. Alexandra Sinclair, Dr. Jennifer A. Rodgers, Craig V. Topping, Dr. Martin Míšek, Ross D. Stewart, Dr. Winfried Kockelmann, Dr. Jan-Willem G. Bos and Prof. J. Paul Attfield

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201403223

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      Putting the squeeze on Ru: An extensive series of new LnRuO3 perovskites has been synthesized at high pressure. They are ruthenium deficient, with compositions close to LnRu0.9O3, and stabilize ruthenium(III), which has not been previously well characterized in oxides. They adopt orthorhombic perovskite superstructures in which strong spin-orbit coupling leads to tetragonal compression of the RuO6 octahedra and Mott insulator behavior.

    9. Heterogeneous Catalysis

      Hydrogenation of Sulfoxides to Sulfides under Mild Conditions Using Ruthenium Nanoparticle Catalysts (pages 8348–8351)

      Dr. Takato Mitsudome, Yusuke Takahashi, Dr. Tomoo Mizugaki, Prof. Dr. Koichiro Jitsukawa and Prof. Dr. Kiyotomi Kaneda

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201403425

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      Ru nanoparticles supported on TiO2 promote the selective hydrogenation of various functionalized sulfoxides at atmospheric H2 pressure. The corresponding sulfides are obtained in excellent yields. The redox ability of Ru nanoparticles plays a crucial role in this hydrogenation reaction.

    10. DNA Nanostructures

      Self-Assembly of DNA–Oligo(p-phenylene-ethynylene) Hybrid Amphiphiles into Surface-Engineered Vesicles with Enhanced Emission (pages 8352–8357)

      Shine K. Albert, Hari Veera Prasad Thelu, Murali Golla, Nithiyanandan Krishnan, Soma Chaudhary and Dr. Reji Varghese

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201403455

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      Surface engineering: DNA–oligomer hybrid amphiphiles self-assemble into surface-functionalized vesicles with enhanced emission. Sequence-specific DNA hybridization allows the assembly of functional molecules onto the surface of the vesicle, providing a unique opportunitie to study the distance-dependent electronic interaction of chromophore stacks with other molecules.

    11. Bioanalysis | Hot Paper

      A Supercharged Fluorescent Protein as a Versatile Probe for Homogeneous DNA Detection and Methylation Analysis (pages 8358–8362)

      Chunyang Lei, Dr. Yan Huang, Prof. Dr. Zhou Nie, Jun Hu, Lijun Li, Guoyan Lu, Yitao Han and Prof. Dr. Shouzhuo Yao

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201403615

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      Supercharged protein sensor: Taking supercharged green fluorescent protein (ScGFP) as the signal reporter, a simple turn-on homogeneous method for DNA detection and methylation analysis of cancer tissue samples has been developed based on the polyionic nanoscale complex of ScGFP/DNA and toehold-mediated strand displacement.

    12. Hybrid Nanoparticles

      One-Step Synthesis of Collagen Hybrid Gold Nanoparticles and Formation on Egyptian-like Gold-Plated Archaeological Ivory (pages 8363–8366)

      Dr. Jolanda Spadavecchia, Emilande Apchain, Marie Albéric, Elisabeth Fontan and Dr. Ina Reiche

      Article first published online: 25 JUN 2014 | DOI: 10.1002/anie.201403567

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      Time matters: From purple to gold: Collagen hybrid AuNPs have been synthesized by a simple one-step method. The determined mechanism explains the formation of AuNPs found in purple stains on formerly gilded archaeological ivories. This finding can serve as a new criterion for authenticating ancient gold-plated ivories that cannot be identified in a non-invasive way.

    13. Structurally Uniform Nanosheets | Hot Paper

      Structurally Homogeneous Nanosheets from Self-Assembly of a Collagen-Mimetic Peptide (pages 8367–8371)

      Tao Jiang, Dr. Chunfu Xu, Dr. Xiaobing Zuo and Prof. Vincent P. Conticello

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201403780

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      Amp-ed up self-assembly: A triblock collagen-mimetic peptide, NSIII, self-assembles into a monodisperse population of nanosheets of defined size and shape. The experimental evidence suggests that the presence of 4S-aminoproline (amp) in the peptide sequence imposes stereoelectronic constraints on the conformation of the triple helix that restricts the size distribution of the resultant nanosheets.

    14. Zeolite Synthesis | Hot Paper

      Synthesis of a Specified, Silica Molecular Sieve by Using Computationally Predicted Organic Structure-Directing Agents (pages 8372–8374)

      Joel E. Schmidt, Dr. Michael W. Deem and Dr. Mark E. Davis

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404076

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      Experimental validation has been realized of a computational method that is able to screen a large number of organic structure-directing agents (OSDAs). The study shows that the method is able to successfully predict OSDAs for a specified framework by using known chemical reactions, and yield predicted occupancies that are measured in the products (see the calculated structure of STW with occluded pentamethylimidazolium).

    15. Phase-Transfer Catalysis

      Discovery and Application of Doubly Quaternized Cinchona-Alkaloid-Based Phase-Transfer Catalysts (pages 8375–8378)

      Bangping Xiang, Kevin M. Belyk, Robert A. Reamer and Nobuyoshi Yasuda

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404084

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      A doubly positive development: N,N′-Disubstituted cinchona alkaloids were found to be highly efficient phase-transfer catalysts for the assembly of stereogenic quaternary centers. In comparison to traditional cinchona-alkaloid phase-transfer catalysts they afforded substantial improvements in enantioselectivity and reactivity in intramolecular spirocyclization reactions at catalyst loadings as low as 0.3 mol % under mild conditions (see example).

    16. NMR Spectroscopy

      Pure In-Phase Heteronuclear Correlation NMR Experiments (pages 8379–8382)

      Laura Castañar, Josep Saurí, Dr. Robert Thomas Williamson, Prof. Albert Virgili and Dr. Teodor Parella

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404136

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      Clean spectra: A general NMR approach to provide pure in-phase (PIP) multiplets in heteronuclear correlation experiments is described. The implementation of a z-filter suppresses unwanted anti-phase contributions that usually distort the multiplet pattern of cross-peaks. The clean pattern obtained is suitable for a direct extraction of coupling constants and for a peak-fitting process from a reference signal.

    17. Proton Conducting Materials

      pH-Dependent Proton Conducting Behavior in a Metal–Organic Framework Material (pages 8383–8387)

      Won Ju Phang, Woo Ram Lee, Kicheon Yoo, Dae Won Ryu, Dr. BongSoo Kim and Prof. Chang Seop Hong

      Article first published online: 1 JUL 2014 | DOI: 10.1002/anie.201404164

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      A fuel cell candidate: Treatment of the metal–organic framework [Ni2(dobdc)] with sulfuric acid afforded a new proton conducting framework, H+@Ni2(dobdc). This acidified MOF displays one of the highest proton conductivities reported for MOFs and is characterized by a exceptionally low activation energy of proton transfer.

    18. Metallopolymers

      Temperature- and Voltage-Induced Ligand Rearrangement of a Dynamic Electroluminescent Metallopolymer (pages 8388–8391)

      Demet Asil, Dr. Jonathan A. Foster, Dr. Asit Patra, Dr. Xavier de Hatten, Dr. Jesús del Barrio, Dr. Oren A. Scherman, Prof. Jonathan R. Nitschke and Prof. Richard H. Friend

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404186

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      Tunable LECs: A dynamic-covalent metal-containing polymer which can reversibly rearrange its structure in response to high temperature or electric field is reported. In solution, the polymers form heat-set gels at high temperatures. When incorporated into light-emitting electrochemical cells (LECs), the wavelength of emission depends on the applied voltage.

    19. Bio-reduction | Hot Paper

      Bio-reduction of Redox-Sensitive Albumin Conjugates in FcRn-Expressing Cells (pages 8392–8396)

      Lorine Brülisauer, Gina Valentino, Sakura Morinaga, Kübra Cam, Dr. Jens Thostrup Bukrinski, Prof. Dr. Marc A. Gauthier and Prof. Dr. Jean-Christophe Leroux

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404238

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      Disulfide-containing IgG-, Fc-, or albumin-based prodrugs that rely on FcRn-trafficking by endothelial cells for prolonged circulation in the body might be hampered by premature bio-reduction processes during FcRn-recycling events. A detailed bio-reduction analysis of redox-sensitive albumin conjugates in two FcRn-expressing cell lines has been performed. New insights are provided to improve the performance of these classes of therapeutics.

    20. Prebiotic Cell Membranes

      Prebiotic Cell Membranes that Survive Extreme Environmental Pressure Conditions (pages 8397–8401)

      Dr. Shobhna Kapoor, Melanie Berghaus, Saba Suladze, Daniel Prumbaum, Sebastian Grobelny, Dr. Patrick Degen, Prof. Dr. Stefan Raunser and Prof. Dr. Roland Winter

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201404254

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      Prebiotic membranes under high pressure: Prebiotic membranes not only withstand extreme temperatures, but also serve as robust models of protocells operating in extreme pressure environments. Pressure not only increases the stability of vesicular systems but also limits their flexibility and permeability to solutes, while keeping the membrane in an overall fluid-like and thus functional state under deep-sea-like conditions.

    21. DNA Nanotechnology

      Synchronization of Two Assembly Processes To Build Responsive DNA Nanostructures (pages 8402–8405)

      Prof. Dr. Zhou Nie, Pengfei Wang, Cheng Tian and Prof. Dr. Chengde Mao

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404307

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      A ladder to higher places: A strategy to synchronize otherwise independent self-assembly processes (represented schematically in green and orange) enabled the assembly of complex DNA nanostructures. As a proof-of-concept, ladderlike and ringlike DNA nanostructures were assembled.

    22. Nanoparticles for Imaging Cartilage

      Tantalum Oxide Nanoparticles for the Imaging of Articular Cartilage Using X-Ray Computed Tomography: Visualization of Ex Vivo/In Vivo Murine Tibia and Ex Vivo Human Index Finger Cartilage (pages 8406–8410)

      Jonathan D. Freedman, Dr. Hrvoje Lusic, Prof. Brian D. Snyder and Prof. Mark W. Grinstaff

      Article first published online: 30 JUN 2014 | DOI: 10.1002/anie.201404519

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      Cartilage imaging: Tantalum oxide (Ta2O5) nanoparticles serve as X-ray contrast media for imaging articular cartilage by microcomputed tomography. The cationic nanoparticles are attracted to the anionic glycosaminoglycans in the cartilage tissue.

    23. Asymmetric Synthesis

      Direct Asymmetric Mannich-Type Reaction of α-Isocyanoacetates with Ketimines using Cinchona Alkaloid/Copper(II) Catalysts (pages 8411–8415)

      Masashi Hayashi, Masaru Iwanaga, Noriyuki Shiomi, Dr. Daisuke Nakane, Prof. Dr. Hideki Masuda and Prof. Dr. Shuichi Nakamura

      Article first published online: 1 JUL 2014 | DOI: 10.1002/anie.201404629

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      The enantioselective direct Mannich-type reaction of ketimines with α-isocyanoacetates has been developed. Excellent yields and enantioselectivities were observed for the reaction of various ketimines and α-isocyanoacetates using cinchona alkaloid/Cu(OTf)2 and a base. Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. This process offers an efficient route for the synthesis of α,β-diamino acids.

    24. Synthetic Methodology

      Continuous Flow Synthesis of Ketones from Carbon Dioxide and Organolithium or Grignard Reagents (pages 8416–8420)

      Dr. Jie Wu, Dr. Xiaoqing Yang, Dr. Zhi He, Dr. Xianwen Mao, Prof. Dr. T. Alan Hatton and Prof. Dr. Timothy F. Jamison

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201405014

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      Known chemistry in flow: The continuous flow synthesis of ketones using CO2 and organolithium or Grignard reagents exhibits significant advantages over conventional batch conditions. Undesired symmetric ketone and alcohol by-products are suppressed and an unprecedented solvent-dependence of the organolithium reactivity was used to achieve the desired selectivity.

    25. Protein–Protein Interaction

      Discovery of Cell-Permeable Inhibitors That Target the BRCT Domain of BRCA1 Protein by Using a Small-Molecule Microarray (pages 8421–8426)

      Zhenkun Na, Sijun Pan, Dr. Mahesh Uttamchandani and Prof. Dr. Shao Q. Yao

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201405169

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      Array and break: By using microarray-based screening platforms the first cell-permeable small-molecule-like protein–protein interaction inhibitors against BRCA1 were identified (see picture). These compounds possess potent in vitro inhibitory activity against BRCA1 (BRCT)2. In cancer cells they disrupt BRCA1 (BRCT)2–protein interactions, and in combination with Olaparib, cause cell death synergistically by activation of the apoptosis pathway.

    26. Low-Coordinate Complexes

      Two-Coordinate Fe0 and Co0 Complexes Supported by Cyclic (alkyl)(amino)carbenes (pages 8427–8431)

      Dr. Gaël Ung, Jonathan Rittle, Dr. Michele Soleilhavoup, Prof. Guy Bertrand and Prof. Jonas C. Peters

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201404078

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      A delightfully lack of coordination: The CAAC [CAAC=cyclic (alkyl)(amino)carbene] family of carbene ligands allow access to the first examples of two-coordinate formal Fe0 and Co0 [M(CAAC)2] complexes. These compounds are prepared by reduction of their corresponding two-coordinate cationic FeI and CoI precursors. Their stability arises from the strong σ-donating and π-accepting properties of the supporting CAAC ligands, as well as steric protection.

    27. Iron(0) Reagents

      (Aminocarbene)(Divinyltetramethyldisiloxane)Iron(0) Compounds: A Class of Low-Coordinate Iron(0) Reagents (pages 8432–8436)

      Hezhong Zhang, Zhenwu Ouyang, Yuesheng Liu, Qiang Zhang, Lei Wang and Prof. Dr. Liang Deng

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404677

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      The low-down on iron: The use of carbene ligands, both NHC and CAAC, enables the access of low-coordinate iron(0) alkene compounds 13 that can effectively deliver their low-coordinate iron(0) fragments to perform redox reactions with hydrosilanes, chalcogen elements, and organic azides.

    28. Homogeneous Catalyst

      Exploring Bis(cyclometalated) Ruthenium(II) Complexes as Active Catalyst Precursors: Room-Temperature Alkene–Alkyne Coupling for 1,3-Diene Synthesis (pages 8437–8440)

      Jing Zhang, Dr. Angel Ugrinov, Prof. Dr. Yong Zhang and Prof. Dr. Pinjing Zhao

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201402098

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      C[BOND]H activation: The ruthenium catalyst 1 promoted coupling between acrylic esters and amides with internal alkynes to form 1,3-diene products at room temperature. A proposed catalytic cycle involves C[BOND]C bond formation by oxidative cyclization, β-hydride elimination, and C[BOND]H bond reductive elimination.

    29. 19F NMR Spectroscopy

      Chemical-Shift-Resolved 19F NMR Spectroscopy between 13.5 and 135 MHz: Overhauser–DNP-Enhanced Diagonal Suppressed Correlation Spectroscopy (pages 8441–8444)

      Dr. Christy George and Prof. Narayanan Chandrakumar

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201402320

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      Overhauser–DNP-enhanced homonuclear 2D 19F correlation spectroscopy with diagonal suppression is presented for small molecules in solution at moderate fields (13.5–135 MHz; DNP=dynamic nuclear polarization). At these relatively low fields, structural information is nevertheless accessible without a sensitivity penalty. This powerful general approach avoids the special requirements of high-field 19F NMR spectroscopy.

    30. Biferrocene Polymers

      Multifunctional Redox Polymers: Electrochrome, Polyelectrolyte, Sensor, Electrode Modifier, Nanoparticle Stabilizer, and Catalyst Template (pages 8445–8449)

      Christophe Deraedt, Amalia Rapakousiou, Yanlan Wang, Dr. Lionel Salmon, Melanie Bousquet and Prof. Didier Astruc

      Article first published online: 28 MAY 2014 | DOI: 10.1002/anie.201403062

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      Very versatile: New metallopolymers were designed and prepared by “click” polycondensation between bis(ethynyl)biferrocene and poly(ethylene glycol) (PEG400 and PEG1000) fragments. These can be used for multiple functions and uses including the improvement of water solubility and biocompatibility, the stabilization of Pd and Au nanoparticles, in catalysis, electrode derivatization, and sensing, and as a polyelectrochrome and polyelectrolyte.

    31. Natural Products

      Enantioselective Organocatalytic Michael/Aldol Sequence: Anticancer Natural Product (+)-trans-Dihydrolycoricidine (pages 8450–8454)

      Dr. James McNulty and Carlos Zepeda-Velázquez

      Article first published online: 20 JUN 2014 | DOI: 10.1002/anie.201403065

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      Taking steps: A stepwise organocatalytic Michael addition/aldol sequence is described involving secondary-amine-catalyzed regioselective addition of azidoacetone to cinnamaldehyde derivatives followed by intramolecular aldolization. Application of this route to aminocyclitols is demonstrated by a short, asymmetric synthesis of the anticancer natural product (+)-trans-dihydrolycoricidine.

    32. Group 14 Chemistry

      Group II Metal Complexes of the Germylidendiide Dianion Radical and Germylidenide Anion (pages 8455–8458)

      Dr. Siew-Peng Chia, Dr. Emma Carter, Dr. Hong-Wei Xi, Dr. Yongxin Li and Dr. Cheuk-Wai So

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201404357

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      Germanium heterocycle: The reaction of 1 with excess calcium in THF at room temperature afforded 2 (see picture). X-ray crystallography and theoretical studies show that the germanium center in 2 has two lone pairs of electrons and that the radical is delocalized over the germanium-containing heterocycle.

    33. Natural Product Synthesis

      Total Synthesis of Marinomycin A Based on a Direct Dimerization Strategy (pages 8459–8462)

      Tatsuya Nishimaru, Masashi Kondo, Kimito Takeshita, Dr. Keisuke Takahashi, Dr. Jun Ishihara and Prof. Dr. Susumi Hatakeyama

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404408

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      Seeing double: The asymmetric total synthesis of (+)-marinomycin A, a 44-membered macrodiolide antitumor agent and antibiotic, is reported. The key features of the synthesis include the highly convergent stereocontrolled construction of the monomeric hydroxy salicylate starting from asymmetric epoxidation of the σ-symmetrical dialkenyl carbinol, and an unprecedented direct dimerization through NaHMDS-promoted double transesterification.

    34. Reaction Mechanisms

      Functionalization of Alkynes by a (Salen)ruthenium(VI) Nitrido Complex (pages 8463–8466)

      Dr. Wai-Lun Man, Jianhui Xie, Po-Kam Lo, Dr. William W. Y. Lam, Dr. Shek-Man Yiu, Dr. Kai-Chung Lau and Prof. Tai-Chu Lau

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404421

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      Alkyne nitrogenation: Reaction of a (salen)ruthenium(VI) nitrido complex with various alkynes in different solvents affords novel (salen)ruthenium(III) imine complexes, which have been evidenced by their X-ray structures. This reaction opens a new nitrogenation pathway for preparing N-containing materials.

    35. Asymmetric Catalysis

      Rhodium-Catalyzed Asymmetric Hydrogenation of Unprotected NH Imines Assisted by a Thiourea (pages 8467–8470)

      Qingyang Zhao, Jialin Wen, Renchang Tan, Kexuan Huang, Pedro Metola, Prof. Rui Wang, Prof. Eric V. Anslyn and Prof. Xumu Zhang

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201404570

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      In a bind: A bis(phosphine)-thiourea ligand was successfully used in the rhodium-catalyzed asymmetric hydrogenation of unprotected iminium salts. Control experiments and 1H NMR studies implied that the anion binding between the thiourea and chloride ions was involved in the mechanism. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine.

    36. C[BOND]H Activation

      Iridium-Catalyzed Regioselective Silylation of Aromatic and Benzylic C[BOND]H Bonds Directed by a Secondary Amine (pages 8471–8474)

      Dr. Qian Li, Prof. Dr. Matthias Driess and Prof. Dr. John F. Hartwig

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404620

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      A 'SiN'ch: In the title reaction of benzylamines or anilines, (hydrido)silyl amines are generated in situ which undergo selective silylation at the C[BOND]H bond γ to the amino group. The silylation products can be further functionalized through oxidation, halogenation, and cross-coupling reactions. cod=1,5-cyclooctadiene, nbe=norbornene.

    37. Enzyme Catalysis

      Elucidation of Pseurotin Biosynthetic Pathway Points to Trans-Acting C-Methyltransferase: Generation of Chemical Diversity (pages 8475–8479)

      Dr. Yuta Tsunematsu, Manami Fukutomi, Dr. Takayoshi Saruwatari, Prof. Dr. Hiroshi Noguchi, Prof. Dr. Kinya Hotta, Prof. Dr. Yi Tang and Prof. Dr. Kenji Watanabe

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201404804

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      A maze: Pseurotins are a family of structurally related bioactive natural products from Aspergilli. Through genetic and biochemical studies, the biosynthetic pathway for the formation of azaspirene, synerazol, and pseurotin A/D have been elucidated, and reveal the combinatorial nature of their biosyntheses. PsoF was identified as bifunctional epoxidase methyltransferase enzyme, thus providing the first example of a trans-acting polyketide C-methyltransferase.

    38. Helical Structures

      Enantioselective Synthesis of [9]- and [11]Helicene-like Molecules: Double Intramolecular [2+2+2] Cycloaddition (pages 8480–8483)

      Yuki Kimura, Naohiro Fukawa, Yuta Miyauchi, Prof. Dr. Keiichi Noguchi and Prof. Dr. Ken Tanaka

      Article first published online: 25 JUN 2014 | DOI: 10.1002/anie.201404810

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      Link up: The enantioselective synthesis of completely ortho-fused [9]- and [11]helicene-like molecules has been achieved through a rhodium-mediated, intramolecular, double [2+2+2] cycloaddition of phenol- or 2-naphthol-linked hexaynes. The crystal structures and photophysical properties of these molecules have also been disclosed.

    39. Synthetic Methods | Hot Paper

      Synthesis of (Carbo)nucleoside Analogues by [3+2] Annulation of Aminocyclopropanes (pages 8484–8487)

      Sophie Racine, Florian de Nanteuil, Eloisa Serrano and Prof. Dr. Jérôme Waser

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201404832

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      (Carbo)nucleoside derivatives constitute an important class of pharmaceuticals. The first synthesis of thymine-, uracil-, and 5-fluorouracil-substituted diester donor–acceptor cyclopropanes and their use in indium- and tin-catalyzed [3+2] annulations with aldehydes, ketones, and enol ethers is described. The method gave access to (carbo)nucleoside analogues in only a few steps and will be highly useful for the synthesis of libraries of bioactive compounds.

    40. Cage Compounds

      1,3-Dehydro-o-Carborane: Generation and Reaction with Arenes (pages 8488–8491)

      Da Zhao, Jiji Zhang and Prof. Dr. Zuowei Xie

      Article first published online: 1 JUL 2014 | DOI: 10.1002/anie.201405023

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      Rattle the cage: 1,3-Dehydro-o-carborane featuring a cage, with C[BOND]B bonds having multiple bonding characters, has been efficiently generated by reaction of 3-diazonium-o-carborane tetrafluoroborate with non-nucleophilic bases. The resulting reactive intermediate can undergo Diels–Alder and aromatic ene reactions with a series of arenes (see scheme).

    41. Pyrrole Synthesis | Hot Paper

      Catalyst-Dependent Divergent Synthesis of Pyrroles from 3-Alkynyl Imine Derivatives: A Noncarbonylative and Carbonylative Approach (pages 8492–8497)

      Gen-Qiang Chen, Xiao-Nan Zhang, Yin Wei, Dr. Xiang-Ying Tang and Dr. Min Shi

      Article first published online: 25 JUN 2014 | DOI: 10.1002/anie.201405215

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      Carbonylation or not: A novel Ru0- and RhI-catalyzed noncarbonylative and carbonylative synthesis of multisubstituted pyrroles from readily available 3-alkynyl imine derivatives has been developed. The key steps involve an oxidative addition and a 1,2-alkyl shift, respectively.

    42. Mesoporous Polymeric Catalyst

      A Nanospherical Ordered Mesoporous Lewis Acid Polymer for the Direct Glycosylation of Unprotected and Unactivated Sugars in Water (pages 8498–8502)

      Dr. Fang Zhang, Chao Liang, Xiaotao Wu and Prof. Dr. Hexing Li

      Article first published online: 23 JUL 2014 | DOI: 10.1002/anie.201404353

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      Xanthone glycosides from sugars: A novel nanospherical ordered mesoporous Lewis acid polymer was synthesized by functionalizing the mesoporous phenol-formaldehyde polymer with scandium triflate groups. The functionalized polymer showed good catalytic activity, selectivity, and recyclability in the C-glycosylation reaction between simple sugars and cyclohexane-1,3-dimedone in water.

    43. Peptide Biosynthesis

      Radical S-Adenosyl Methionine Epimerases: Regioselective Introduction of Diverse D-Amino Acid Patterns into Peptide Natural Products (pages 8503–8507)

      Dr. Brandon I. Morinaka, Dr. Anna L. Vagstad, Maximilian J. Helf, Dr. Muriel Gugger, Dr. Carsten Kegler, Dr. Michael F. Freeman, Prof. Dr. Helge B. Bode and Prof. Dr. Jörn Piel

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201400478

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      A radical change: Radical S-adenosyl methionine (SAM) epimerases is a new family of architecturally and functionally distinct bacterial enzymes. Three members from cyanobacteria were shown to introduce diverse D-amino acid patterns into all-L peptides. Their high regioselectivity, substrate promiscuity, and irreversible action provide interesting opportunities for peptide engineering.

    44. Bifunctional Catalysts

      MnxOy/NC and CoxOy/NC Nanoparticles Embedded in a Nitrogen-Doped Carbon Matrix for High-Performance Bifunctional Oxygen Electrodes (pages 8508–8512)

      Dr. Justus Masa, Dr. Wei Xia, Dr. Ilya Sinev, Anqi Zhao, Dr. Zhenyu Sun, Stefanie Grützke, Philipp Weide, Prof. Dr. Martin Muhler and Prof. Dr. Wolfgang Schuhmann

      Article first published online: 27 JUN 2014 | DOI: 10.1002/anie.201402710

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      A dual finds its right setting: To improve the efficiency of metal–air batteries and unitized regenerative fuel-cell systems dual-function catalysts that can accomplish both water oxidation and oxygen reduction are required. Low-cost bifunctional catalysts based on Co, Mn, and Ni oxides embedded in N-doped carbon (NC) are synthesized and outperform Pt-, Ir- and, Ru-based catalysts.

    45. Natural Product Synthesis

      The Total Synthesis of (−)-Nitidasin (pages 8513–8517)

      Dr. Daniel T. Hog, Dipl.-Chem. Florian M. E. Huber, Dr. Peter Mayer and Prof. Dr. Dirk Trauner

      Article first published online: 24 JUN 2014 | DOI: 10.1002/anie.201403605

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      Put a ring on it: The first total synthesis of nitidasin, a complex sesterterpenoid with a 5-8-6-5 skeleton, is reported. It involves the addition of a tetrasubstituted alkenyl lithium compound to a trans-hydrindanone and an olefin metathesis to form a highly substituted eight-membered ring at an unexpected site. The absolute configuration of nitidasin was established with our highly stereoselective and convergent synthesis.

    46. Protein–Protein Interactions | Hot Paper

      The Structure of a Transient Complex of a Nonribosomal Peptide Synthetase and a Cytochrome P450 Monooxygenase (pages 8518–8522)

      Kristina Haslinger, Dr. Clara Brieke, Dr. Stefanie Uhlmann, Lina Sieverling, Prof. Dr. Roderich D. Süssmuth and Dr. Max J. Cryle

      Article first published online: 9 JUL 2014 | DOI: 10.1002/anie.201404977

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      Caught in the act: The structural characterization of a transient complex between the carrier protein (CP) domain of a nonribosomal peptide synthetase (NRPS) and a cytochrome P450 oxidase was made possible through the use of covalent inhibitor-type compounds. The structure reveals a novel binding site on the CP for such tailoring enzymes and suggests that the selectivity involves manipulation of the CP tertiary structure.

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