Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 9

February 24, 2014

Volume 53, Issue 9

Pages 2253–2507

  1. Cover Pictures

    1. Top of page
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    3. Graphical Abstract
    4. Flashback
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Total Synthesis of Resveratrol-Based Natural Products Using a Palladium-Catalyzed Decarboxylative Arylation and an Oxidative Heck Reaction (Angew. Chem. Int. Ed. 9/2014) (page 2253)

      Felix Klotter and Prof. Dr. Armido Studer

      Version of Record online: 6 FEB 2014 | DOI: 10.1002/anie.201400659

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      Resveratrol-based natural products can be selectively synthesized by a novel highly modular approach. In their Communication on page 2473 ff., A. Studer and F. Klotter report the use of Pd-catalyzed decarboxylative arylation and an oxidative Heck reaction to introduce structurally important aryl groups to a common building block, which is readily available on a large scale. The modular approach is convincingly documented by the syntheses of quadrangularin A, ampelopsin D, and pallidol.

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      Inside Cover: Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants (Angew. Chem. Int. Ed. 9/2014) (page 2254)

      Kasper S. Pedersen, Dr. Giulia Lorusso, Juan José Morales, Dr. Thomas Weyhermüller, Dr. Stergios Piligkos, Saurabh Kumar Singh, Dennis Larsen, Magnus Schau-Magnussen, Dr. Gopalan Rajaraman, Dr. Marco Evangelisti and Prof. Dr. Jesper Bendix

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201400663

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      Molecular refrigerators consisting of unusual fourth-row metal-ion–lanthanide complexes with bridging fluoride ions are presented by M. Evangelisti and J. Bendix in their Communication on page 2394 ff. The combination of lightweight auxiliary ligands and tunable interactions by choice of metal ion makes these systems interesting modules for low-temperature cooling applications.

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      Inside Back Cover: Transcription of Click-Linked DNA in Human Cells (Angew. Chem. Int. Ed. 9/2014) (page 2509)

      Dr. Charles N. Birts, Dr. A. Pia Sanzone, Dr. Afaf H. El-Sagheer, Dr. Jeremy P. Blaydes, Prof. Tom Brown and Dr. Ali Tavassoli

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201400939

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      Click-linked DNA encoding the fluorescent protein mCherry is shown to be functional in human cells by A. Tavassoli and co-workers in their Communication on page 2362 ff. Shown are human MCF-7 cells microinjected with the click-linked mCherry gene. They display the red fluorescence associated with mCherry expression, thus indicating correct transcription through the click-linked DNA.

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      Back Cover: Constrained Peptides with Target-Adapted Cross-Links as Inhibitors of a Pathogenic Protein–Protein Interaction (Angew. Chem. Int. Ed. 9/2014) (page 2510)

      Adrian Glas, David Bier, Dr. Gernot Hahne, Dr. Christoph Rademacher, Dr. Christian Ottmann and Dr. Tom N. Grossmann

      Version of Record online: 7 FEB 2014 | DOI: 10.1002/anie.201400778

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      Target-adapted hydrophobic cross-links were used to conformationally constrain a peptide (see picture, pink). In their Communication on page 2489 ff., T. N. Grossmann et al. present the iterative and rational evolution of these cross-links (yellow) based on X-ray crystal structures. The resulting macrocyclic peptides inhibit the protein–protein interaction between bacterial virulence factor ExoS and human protein 14-3-3.

  2. Graphical Abstract

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    3. Graphical Abstract
    4. Flashback
    5. Corrigendum
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    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
  3. Flashback

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    13. Communications
    1. 50 Years Ago ... (page 2266)

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/anie.201400409

  4. Corrigendum

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      Corrigendum: Metal/N-Heterocyclic Carbene Complexes: Opportunities for the Development of Anticancer Metallodrugs (page 2269)

      Dr. Federico Cisnetti and Dr. Arnaud Gautier

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/anie.201400280

      This article corrects:

      Metal/N-Heterocyclic Carbene Complexes: Opportunities for the Development of Anticancer Metallodrugs

      Vol. 52, Issue 46, 11976–11978, Version of Record online: 2 OCT 2013

  5. News

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    13. Communications
  6. Author Profile

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    13. Communications
    1. Koji Hirano (page 2276)

      Version of Record online: 7 NOV 2013 | DOI: 10.1002/anie.201309185

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      “My worst nightmare is getting a terrible stomach ache from eating uncooked chicken. My biggest motivation is to share the joy, success, and sometimes failure of research with my students …” This and more about Koji Hirano can be found on page 2276.

  7. News

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  8. Book Review

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    13. Communications
    1. Nitrenes and Nitrenium Ions. Wiley Series on Reactive Intermediates in Chemistry and Biochemistry, Volume 6. Edited by Daniel E. Falvey and Anna D. Gudmundsdottir. (page 2279)

      Paul Wenthold

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/anie.201309993

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      John Wiley & Sons, Hoboken, 2013. 606 pp., hardcover, € 135.00.—ISBN 978-0470390597

  9. Highlights

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    1. Asymmetric Heck Reaction

      Breaking News on the Enantioselective Intermolecular Heck Reaction (pages 2282–2285)

      Prof. Dr. Martin Oestreich

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201310585

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      Glowing results with less phosphorus: Tremendous progress has been made recently in asymmetric intermolecular Heck chemistry. Previously unprecedented enantioselective Heck–Matsuda reactions have been accomplished, and mixed phosphine/phosphine oxides have been shown to be superior ligands in enantioselective Mizoroki–Heck reactions. All of this was achieved with chiral ligands containing few or even no phosphorus donors (see scheme).

    2. Cancer Immunotherapy

      Programmed Death-1: Therapeutic Success after More than 100 Years of Cancer Immunotherapy (pages 2286–2288)

      Prof. Alexander Dömling and Prof. Tad A. Holak

      Version of Record online: 28 JAN 2014 | DOI: 10.1002/anie.201307906

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      No other cancer therapy target class caused more excitement than the programmed death-1 (PD-1) pathway related. Antibodies against PD-1 and PD-1 ligands represent a therapeutic breakthrough and are the first examples of broadly efficacious and durable cancer immunotherapies. Cancer for the first time seems to have transformed from an often incurable to a “clinically manageable” disease.

  10. Minireview

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    13. Communications
    1. Dyes/Pigments

      Luminescent Materials: Locking π-Conjugated and Heterocyclic Ligands with Boron(III) (pages 2290–2310)

      Dr. Denis Frath, Dr. Julien Massue, Dr. Gilles Ulrich and Dr. Raymond Ziessel

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201305554

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      Dye by boron: N,N or N,O complexes of boron(III) are easy to prepare and handle, and they display outstanding fluorescence properties in both solution and the solid state. These novel dyes were classified by the number of atoms in the ring systems and by the number of aromatic rings participating in the π conjugation. The optical properties are discussed, and various applications in light-emitting devices as well as probes are anticipated.

  11. Review

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    1. Drug Design

      Small-Molecule Control of Intracellular Protein Levels through Modulation of the Ubiquitin Proteasome System (pages 2312–2330)

      Dr. Dennis L. Buckley and Prof. Craig M. Crews

      Version of Record online: 23 JAN 2014 | DOI: 10.1002/anie.201307761

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      Targeted assault: With two FDA-approved proteasome inhibitors, the ubiquitin proteasome system (UPS) has established itself as a validated metabolic pathway for drug development. Recent advances include the development of inhibitors of alternative targets within the UPS that promise increased specificity, as well as the design of chemical inducers of targeted degradation by the UPS.

  12. Communications

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    1. Bioactive Surfaces

      Chemically Orthogonal Three-Patch Microparticles (pages 2332–2338)

      Sahar Rahmani, Dr. Sampa Saha, Dr. Hakan Durmaz, Alessandro Donini, Asish C Misra, Dr. Jaewon Yoon and Prof. Dr. Joerg Lahann

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201310727

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      Patchwork family: Three-patch microparticles (see scheme) containing functionalized poly(lactide) derivatives in select compartments were fabricated through the electrohydrodynamic (EHD) co-jetting process. The microparticles were characterized by Raman confocal microspectroscopy and the bio-orthogonal surface modification of each patch was demonstrated.

    2. Nano-Heterostructures

      A 1D/2D Helical CdS/ZnIn2S4 Nano-Heterostructure (pages 2339–2343)

      Biao Xu, Peilei He, Huiling Liu, Pengpeng Wang, Prof. Dr. Gang Zhou and Prof. Dr. Xun Wang

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201310513

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      Rotate and connect! The shape evolution of a helical 1D/2D semiconductor nano-heterostructure (NHS) consisting of CdS and ZnIn2S4 is demonstrated. This NHS exhibits enhanced performance in photoelectrochemical cells, which is explained by the interface electronic states and the tailored band alignment.

    3. Microfluidic Systems

      Mesenchymal-Mode Migration Assay and Antimetastatic Drug Screening with High-Throughput Microfluidic Channel Networks (pages 2344–2348)

      Dr. Yuanqing Zhang, Dr. Weijia Zhang and Prof. Lidong Qin

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309885

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      A high-throughput microfluidic chip with 3120 microchambers was used to monitor mesenchymal migration. Through imaging of the whole chip and statistical analysis (see picture), the percentage of migrating cells and the migration velocity were evaluated at different cell densities. The device was also used to screen drugs for their ability to inhibit mesenchymal migration and thus prevent metastatic malignancy.

    4. Real-Time NMR Spectroscopy

      Quantitative Analysis of Location- and Sequence-Dependent Deamination by APOBEC3G Using Real-Time NMR Spectroscopy (pages 2349–2352)

      Dr. Ayako Furukawa, Dr. Kenji Sugase, Dr. Ryo Morishita, Prof. Takashi Nagata, Prof. Tsutomu Kodaki, Prof. Akifumi Takaori-Kondo, Prof. Akihide Ryo and Prof. Masato Katahira

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309940

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      APOBEC3G (A3G) efficiently deaminates cytidines that are located close to the 5′ end of the single-stranded minus DNA of the HIV-1 genome. This process could be quantitatively analyzed using a newly developed real-time NMR spectroscopy method. As a result, the location-dependent deamination can be explained by two catalytic rate constants that depend on the direction of the approach to the target cytidine.

    5. Catalysis

      Activation of Oxygen on Gold and Silver Nanoparticles Assisted by Surface Plasmon Resonances (pages 2353–2357)

      Dr. Yi-Fan Huang, Meng Zhang, Liu-Bin Zhao, Dr. Jia-Min Feng, Prof. Dr. De-Yin Wu, Prof. Dr. Bin Ren and Prof. Dr. Zhong-Qun Tian

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201310097

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      Plasmon-assisted reactions: Surface plasmon resonances (SPRs) support the activation of oxygen to yield metallic oxides and hydroxides on surfaces of Au and Ag nanoparticles, which selectively oxidize molecular species on the surface by laser light illumination. The electron donation to oxygen as well as a local heating effect in the presence of SPRs account for the activation of oxygen.

    6. Protein Folding

      An Off-Pathway Folding Intermediate of an Acyl Carrier Protein Domain Coexists with the Folded and Unfolded States under Native Conditions (pages 2358–2361)

      Dr. Jackwee Lim, Tianshu Xiao, Dr. Jingsong Fan and Prof. Daiwen Yang

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/anie.201308512

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      Neither U(p) nor (dow)N: Acyl carrier protein from Micromonospora echinospora adopts three conformations; one folded (N), one unfolded (U), and one intermediate (I). These undergo slow conformational exchange under native conditions. The intermediate state, which is an off-pathway rather than on-pathway product, may mediate the formation of oligomers in vitro and play an important role in the recognition of partner enzymes in vivo.

    7. Synthetic Biology

      You have full text access to this OnlineOpen article
      Transcription of Click-Linked DNA in Human Cells (pages 2362–2365)

      Dr. Charles N. Birts, Dr. A. Pia Sanzone, Dr. Afaf H. El-Sagheer, Dr. Jeremy P. Blaydes, Prof. Tom Brown and Dr. Ali Tavassoli

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/anie.201308691

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      Just a click away: Human cells are shown to correctly transcribe through a non-natural DNA-backbone linker. Triazole-linked DNA encoding the red fluorescent protein mCherry is shown to be functional in human cells without the need for nucleotide excision repair. These results challenge the idea that a phosphodiester backbone is essential for the biological function of DNA and open up the possibility of total chemical synthesis of genes by click DNA ligation.

    8. Self-Assembly

      Multifunctional Porous Microspheres Based on Peptide–Porphyrin Hierarchical Co-Assembly (pages 2366–2370)

      Dr. Qianli Zou, Dr. Lu Zhang, Prof. Dr. Xuehai Yan, Dr. Anhe Wang, Prof. Dr. Guanghui Ma, Prof. Dr. Junbai Li, Prof. Dr. Helmuth Möhwald and Prof. Dr. Stephen Mann

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201308792

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      Simple but multifunctional: Photocatalytically active microspheres with highly hydrated, accessible multi-chambered interiors have been prepared by cooperative self-assembly of simple dipeptides and porphyrins (see picture). They serve as a plausible photosynthetic model that could be potentially developed towards studying aspects of primitive abiotic cellularity.

    9. Drug Delivery

      DNA-Hybrid-Gated Multifunctional Mesoporous Silica Nanocarriers for Dual-Targeted and MicroRNA-Responsive Controlled Drug Delivery (pages 2371–2375)

      Penghui Zhang, Fangfang Cheng, Ri Zhou, Dr. Juntao Cao, Dr. Jingjing Li, Prof. Dr. Clemens Burda, Dr. Qianhao Min and Prof. Dr. Jun-Jie Zhu

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/anie.201308920

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      Endogenous uncapping key: A traceable, dual-targeted, and microRNA-controlled drug delivery system was constructed by capping a programmable DNA hybrid onto mesoporous silica-coated quantum dots. Once the nanocarriers had been delivered into the targeted HeLa cells by aptamer-mediated recognition and endocytosis, the overexpressed endogenous miR-21 served as an exclusive key to unlock the gate by competitive hybridization with DNA hybrids.

    10. Fluorescent Nanoclusters

      A 200-fold Quantum Yield Boost in the Photoluminescence of Silver-Doped AgxAu25−x Nanoclusters: The 13 th Silver Atom Matters (pages 2376–2380)

      Shuxin Wang, Xiangming Meng, Anindita Das, Tao Li, Yongbo Song, Tiantian Cao, Xiuyi Zhu, Prof. Manzhou Zhu and Prof. Rongchao Jin

      Version of Record online: 28 JAN 2014 | DOI: 10.1002/anie.201307480

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      Shine on, you crazy cluster: Highly fluorescent, silver-doped AgxAu25−x nanoclusters (II; x=1–13; QY=40.1 %) have been successfully synthesized through the reaction of a silver thiolate complex with Au11 clusters. In contrast, species with x=1–12 (I) and undoped Au25 nanoclusters are only weakly fluorescent (QY=0.21 % and 0.1 %, respectively).

    11. Supported Catalysts

      The Direct Synthesis of Hydrogen Peroxide Using Platinum-Promoted Gold–Palladium Catalysts (pages 2381–2384)

      Dr. Jennifer K. Edwards, James Pritchard, Li Lu, Marco Piccinini, Greg Shaw, Dr. Albert F. Carley, David J. Morgan, Prof. Christopher J. Kiely and Prof. Graham J. Hutchings

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201308067

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      Small change with great effect: The addition of a small amount of Pt to a AuPd/CeO2 catalyst can significantly enhance its performance in the direct synthesis of H2O2. The contour diagram shows the productivity of catalysts with different metal ratios (blue/yellow: low/high productivity).

    12. Structure Elucidation

      Crystal Structure of Metallo DNA Duplex Containing Consecutive Watson–Crick-like T–HgII–T Base Pairs (pages 2385–2388)

      Dr. Jiro Kondo, Tom Yamada, Chika Hirose, Dr. Itaru Okamoto, Dr. Yoshiyuki Tanaka and Prof. Akira Ono

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309066

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      Paired up: The first crystal structure of a metallo DNA duplex containing consecutive Watson–Crick-like T–HgII–T base pairs has been solved. The structure itself and the HgII-induced structural switching from a nonhelical form to the B-form provide the basis for structure-based design of metal-conjugated nucleic acid nanomaterials.

    13. MicroRNA Imaging

      Toehold-initiated Rolling Circle Amplification for Visualizing Individual MicroRNAs In Situ in Single Cells (pages 2389–2393)

      Ruijie Deng, Dr. Longhua Tang, Qianqian Tian, Dr. Ying Wang, Lei Lin and Prof. Dr. Jinghong Li

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/anie.201309388

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      Ready to roll: A toehold-initiated strand-displacement (TMSD) process was used to initiate the rolling circle amplification (RCA) of individual miRNAs through the use of a structure-switchable dumbbell-shaped probe. High specificity was achieved through the fine sequence discrimination of TMSD. The amplification produces an extremely long chain containing hundreds of tandem repeats, which allows the visualization of individual microRNAs in situ in single cells.

    14. Molecular Refrigeration

      Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants (pages 2394–2397)

      Kasper S. Pedersen, Dr. Giulia Lorusso, Juan José Morales, Dr. Thomas Weyhermüller, Dr. Stergios Piligkos, Saurabh Kumar Singh, Dennis Larsen, Magnus Schau-Magnussen, Dr. Gopalan Rajaraman, Dr. Marco Evangelisti and Prof. Dr. Jesper Bendix

      Version of Record online: 6 FEB 2014 | DOI: 10.1002/anie.201308240

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      Molecular coolers: Even labile fluoride complexes (see picture; Gd purple, Cr/Fe/Ga orange, F green, O red) are useful precursors for polynuclear, fluoride-bridged 3d–4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight auxiliary ligand sphere, gives rise to extremely large magnetic entropy changes.

    15. Modified Graphitic Networks

      Direct Solvothermal Synthesis of B/N-Doped Graphene (pages 2398–2401)

      Sun-Min Jung, Eun Kwang Lee, Min Choi, Dongbin Shin, In-Yup Jeon, Jeong-Min Seo, Prof. Hu Young Jeong, Prof. Noejung Park, Prof. Joon Hak Oh and Prof. Jong-Beom Baek

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/anie.201310260

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      Mixing it up a bit: B/N-doped graphene was directly synthesized from the reaction of CCl4, BBr3, and N2 in the presence of potassium. It has good dispersibility in N-methyl-2-pyrrolidone, allowing solution casting for the fabrication of field-effect transistors with an on/off ratio of 10.7 and an optical band gap of 3.3 eV. The method is scalable and solution processable, making it suitable for many applications.

    16. Catalyst-Transfer Polycondensation

      Palladium-Catalyzed Chain-Growth Polycondensation of AB-type Monomers: High Catalyst Turnover and Polymerization Rates (pages 2402–2407)

      Dr. Roman Tkachov, Dr. Volodymyr Senkovskyy, Dr. Tetyana Beryozkina, Dr. Kseniya Boyko, Prof. Dr. Vasiliy Bakulev, Dr. Albena Lederer, Dr. Karin Sahre, Prof. Dr. Brigitte Voit and Dr. Anton Kiriy

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310045

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      Kicking it into high gear: Pd/PtBu3-catalyzed Negishi chain-growth polycondensation of AB-type monomers into semiconducting polymers proceeds with unprecedented TONs as high as 100 000 and turnover frequencies of up to 280 s−1. In contrast, related AA/BB-type step-growth polycondensation proceeds with two orders of magnitude lower TONs and TOFs. Similar trends were observed in Suzuki polycondensation.

    17. Conjugated Molecules

      A Core-Expanded Subphthalocyanine Analogue with a Significantly Distorted Conjugated Surface and Unprecedented Properties (pages 2408–2412)

      Dr. Soji Shimizu, Shota Nakano, Ayaka Kojima and Prof. Nagao Kobayashi

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201310028

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      All in a flutter: Significant distortion of the bowl-shaped structure of subphthalocyanine upon the introduction of a seven-membered ring in place of two five-membered rings (see scheme) led to unusual properties and reactivity. Fluttering-dynamic-motion-induced rapid exchange of the P and M enantiomers as well as markedly split Q-band absorption and distinct ring-current effects arising from the convex and concave surfaces were observed.

    18. Carbohydrates

      One-Pot Synthesis of N-Acetyl- and N-Glycolylneuraminic Acid Capped Trisaccharides and Evaluation of Their Influenza A(H1 N1) Inhibition (pages 2413–2416)

      Dr. Yun Hsu, Hsiu-Hwa Ma, Larry S. Lico, Dr. Jia-Tsrong Jan, Prof. Dr. Koichi Fukase, Dr. Yosuke Uchinashi, Dr. Medel Manuel L. Zulueta and Prof. Dr. Shang-Cheng Hung

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201309646

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      Flu the coop: A stereoselective one-pot assembly and divergent transformation enabled the synthesis of six N-acetyl- and N-glycolylneuraminic-acid-capped trisaccharides. Two of the N-glycolylneuraminic-acid-capped trisaccharides showed inhibitory activities against a common human influenza virus. Bz=benzoyl, NIS=N-iodosuccinimide, Tf=trifluoromethanesulfonyl, TMS=trimethylsilyl.

    19. Reaction Mechanisms

      Spectroscopic and Computational Study of a Nonheme Iron Nitrosyl Center in a Biosynthetic Model of Nitric Oxide Reductase (pages 2417–2421)

      Dr. Saumen Chakraborty, Julian Reed, Matthew Ross, Dr. Mark J. Nilges, Igor D. Petrik, Dr. Soumya Ghosh, Prof. Dr. Sharon Hammes-Schiffer, Prof. Dr. J. Timothy Sage, Prof. Dr. Yong Zhang, Prof. Dr. Charles E. Schulz and Prof. Dr. Yi Lu

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201308431

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      Ironed out: A nonheme iron nitrosyl complex has been prepared at a rationally designed FeB site within a myoglobin-based biosynthetic model of nitric oxide reductases (NORs) that contains a zinc protoporphyrin IX. The designed FeII-ZnPPFeBMb1 forms a nitrosyl complex [FeB2+-NO.] at the nonheme site. The radical nature of NO is implied to promote N[BOND]N bond formation by radical coupling, thus supporting the trans mechanism of NORs.

    20. Cross-Couplings

      Stereospecific Nickel-Catalyzed Cross-Coupling Reactions of Alkyl Grignard Reagents and Identification of Selective Anti-Breast-Cancer Agents (pages 2422–2427)

      Ivelina M. Yonova, A. George Johnson, Charlotte A. Osborne, Dr. Curtis E. Moore, Prof. Naomi S. Morrissette and Prof. Elizabeth R. Jarvo

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201308666

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      β-Hydrogen atoms welcome! Alkyl Grignard reagents that contain β-hydrogen atoms were used in a stereospecific nickel-catalyzed cross-coupling reaction to form C(sp3)[BOND]C(sp3) bonds (es=enantiospecificity). Aryl Grignard reagents were also utilized to synthesize 1,1-diarylalkanes. Several compounds that were synthesized by this method exhibited selective inhibition of proliferation of MCF-7 breast cancer cells.

    21. Heterocycles

      Synthesis of Bis(heteroaryl) Ketones by Removal of Benzylic CHR and CO Groups (pages 2428–2432)

      Arun Maji, Sujoy Rana, Akanksha and Prof. Debabrata Maiti

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201308785

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      Snip snip: A copper-catalyzed method for synthesis of diaryl ketones by removal of benzylic CH2, CO, and CHR groups has been discovered. A number of symmetrical and unsymmetrical heterocyclic ketones, which are usually difficult to synthesize, can be prepared in good to excellent yields. Preliminary mechanistic studies indicate that an active Cu/O2 species mediates the rearrangement.

    22. Oxygen Reduction Reaction

      Highly Efficient Electrocatalysts for Oxygen Reduction Based on 2D Covalent Organic Polymers Complexed with Non-precious Metals (pages 2433–2437)

      Dr. Zhonghua Xiang, Dr. Yuhua Xue, Prof. Dapeng Cao, Ling Huang, Prof. Jian-Feng Chen and Prof. Liming Dai

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201308896

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      Metal-containing (M=Fe, Co, Mn) 2D covalent organic polymers with precisely controlled locations of N heteroatoms and holes were synthesized from metal–porphyrin complexes by a nickel-catalyzed Yamamoto reaction. Subsequent carbonization led to graphene analogues, which are efficient electrocatalysts for oxygen reduction in both alkaline and acid media and are free from methanol-crossover/CO poisoning.

    23. NMR Spectroscopy

      Quadruple-Resonance Magic-Angle Spinning NMR Spectroscopy of Deuterated Solid Proteins (pages 2438–2442)

      Dr. Ümit Akbey, Dr. Andrew J. Nieuwkoop, Dr. Sebastian Wegner, Anja Voreck, Dr. Britta Kunert, Dr. Priyanga Bandara, Dr. Frank Engelke, Prof. Dr. Niels Chr. Nielsen and Prof. Dr. Hartmut Oschkinat

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201308927

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      Proton-detected magic-angle spinning solid-state NMR spectroscopy using deuterated proteins facilitates structural biology. Solid deuterated proteins that cannot be unfolded/refolded to exchange the deuterons back with protons and proteins that can only be studied in their native environments show a low intrinsic sensitivity in NMR experiments. For such systems, initial excitation of the deuterons can be very useful.

    24. Heterocycles

      Palladium-Catalyzed Oxidative Carbonylation of N-Allylamines for the Synthesis of β-Lactams (pages 2443–2446)

      Wu Li, Dr. Chao Liu, Prof. Heng Zhang, Keyin Ye, Guanghui Zhang, Wangzheng Zhang, Zhengli Duan, Prof. Shuli You and Prof. Aiwen Lei

      Version of Record online: 28 JAN 2014 | DOI: 10.1002/anie.201309081

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      Four corners: The β-lactam scaffold is considered to be an ideal building block for the synthesis of nitrogen-containing compounds. A new, simple, and convenient palladium-catalyzed oxidative carbonylation of N-allylamines for the synthesis of α-methylene-β-lactams is reported. DFT calculations suggest that the formation of the β-lactam via a four-membered-ring transition state is favorable.

    25. Biocatalysis

      You have full text access to this OnlineOpen article
      A Regio- and Stereoselective ω-Transaminase/Monoamine Oxidase Cascade for the Synthesis of Chiral 2,5-Disubstituted Pyrrolidines (pages 2447–2450)

      Dr. Elaine O'Reilly, Cesar Iglesias, Dr. Diego Ghislieri, Dr. Jennifer Hopwood, Dr. James L. Galman, Dr. Richard C. Lloyd and Prof. Nicholas J. Turner

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309208

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      Mirror mirror on the wall: A ω-transaminase (ω-TA)/monoamine oxidase (MAO-N) cascade process for the asymmetric synthesis of chiral 2,5-disubstituted pyrrolidines is reported. The methodology exploits the complementary regio- and stereoselectivity displayed by both enzymes, which ensures that the stereogenic center established by the TA reaction is not affected by the MAO-N catalyzed step.

    26. Aminosulfonylation

      Metal-Free Aminosulfonylation of Aryldiazonium Tetrafluoroborates with DABCO⋅(SO2)2 and Hydrazines (pages 2451–2454)

      Danqing Zheng, Yuanyuan An, Dr. Zhenhua Li and Prof. Dr. Jie Wu

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309851

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      The coupling of aryldiazonium tetrafluoroborates, DABCO⋅(SO2)2, and hydrazines under metal-free conditions leads to the formation of aryl N-aminosulfonamides. The reaction proceeds under mild reaction conditions, is fast, has a broad substrate scope, and gives the products in high yiels (21 examples). A plausible mechanism that involves a radical process is also proposed.

    27. C[BOND]H Activation

      Substrate-Directed Hydroacylation: Rhodium-Catalyzed Coupling of Vinylphenols and Nonchelating Aldehydes (pages 2455–2459)

      Stephen K. Murphy, Dr. Achim Bruch and Dr. Vy M. Dong

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309987

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      COs with a local branch: A hydroacylation of vinylphenols with aryl, alkenyl, and alkyl aldehydes gave the branched products: α-aryl ketone precursors to benzofurans. This cross-coupling enabled access to eupomatenoid natural products in four steps or less from eugenol (see scheme; cod=1,5-cyclooctadiene). Aldehyde decarbonylation was avoided by use of an anionic directing group on the alkene and a small-bite-angle diphosphine ligand.

    28. Giant Fullerenes

      Chlorination of IPR C100 Fullerene Affords Unconventional C96Cl20 with a Nonclassical Cage Containing Three Heptagons (pages 2460–2463)

      Prof. Dr. Shangfeng Yang, Song Wang, Prof. Dr. Erhard Kemnitz and Prof. Dr. Sergey I. Troyanov

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201310099

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      Three heptagons in the fullerene cage were found for the first time in C96Cl20 with a nonclassical cage, which was obtained by chlorination of isolated-pentagon-rule C100 fullerene. Most of 15 cage pentagons are fused resulting fused pentagon pairs and triples (see structure: gray C, green Cl; pentagons red, heptagons blue).

    29. Vibrational Spectroscopy

      Vibrational Spectroscopy of the Dehydrogenated Uracil Radical by Autodetachment of Dipole-Bound Excited States of Cold Anions (pages 2464–2468)

      Dr. Hong-Tao Liu, Prof. Dr. Chuan-Gang Ning, Dao-Ling Huang and Prof. Dr. Lai-Sheng Wang

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201310323

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      The vibrational spectrum of the dehydrogenated uracil radical has been measured by autodetachment from dipole-bound states of cold deprotonated uracil anions. The spectrum shows observed rotational profiles (blue circles) for mode ν16 at 577 cm−1 (c-type) and mode ν24 at 615 cm−1 (b-type), in comparison with the simulated rotational profiles (red line).

    30. Silica Analogues

      A High-Pressure Polymorph of Phosphorus Nitride Imide (pages 2469–2472)

      Alexey Marchuk, Florian J. Pucher, Friedrich W. Karau and Prof. Dr. Wolfgang Schnick

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/anie.201309020

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      A new form is born: The first high-pressure polymorph of phosphorus nitride imide, β-PN(NH), has been synthesized by treating a single-source precursor at 6 GPa and 1000 °C using the multianvil technique. By adding catalytic amounts of NH4Cl as a mineralizer single crystals of the product could be obtained and isolated.

    31. Natural Product Synthesis

      Total Synthesis of Resveratrol-Based Natural Products Using a Palladium-Catalyzed Decarboxylative Arylation and an Oxidative Heck Reaction (pages 2473–2476)

      Felix Klotter and Prof. Dr. Armido Studer

      Version of Record online: 5 FEB 2014 | DOI: 10.1002/anie.201310676

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      Palladium mediates! A common building block readily available on a large scale serves as the starting material in the title reactions for the introduction of structurally important aryl groups in resveratrol-based natural products. The modular concept is convincingly documented by the synthesis of three racemic resveratrol-based natural products (including pallidol).

    32. C[BOND]H Activation

      Nickel-Catalyzed C[BOND]H Alkylations: Direct Secondary Alkylations and Trifluoroethylations of Arenes (pages 2477–2480)

      M. Sc. Weifeng Song, M. Sc. Sebastian Lackner and Prof. Dr. Lutz Ackermann

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201309584

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      In an absence of activation: A robust nickel(II) catalyst enabled secondary alkylations of unactivated aryl C[BOND]H bonds with secondary alkyl bromides and chlorides with ample substrate scope. Based on this system the first C[BOND]H trifluoroethylations of arenes with unactivated C[BOND]H bonds could be carried out (see scheme; Q=8-quinolinyl).

    33. Detoxification

      Magnetic Titanium Dioxide Nanocomposites for Surface-Enhanced Resonance Raman Spectroscopic Determination and Degradation of Toxic Anilines and Phenols (pages 2481–2484)

      Dr. Xiao Xia Han, Dr. Lei Chen, Dr. Uwe Kuhlmann, Claudia Schulz, Prof. Inez M. Weidinger and Prof. Peter Hildebrandt

      Version of Record online: 28 JAN 2014 | DOI: 10.1002/anie.201310123

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      Magnetic TiO2 nanocomposites (M-TiO2 NCs) are fabricated and functionalized for determination and elimination of toxic anilines and phenols. The compounds, bound to M-TiO2 NCs by azo coupling, may be degraded by TiO2-assisted photocatalysis, making the NCs recyclable. Addition of Ag nanoparticles allows the detection and identification of the azo products by surface-enhanced resonance Raman spectroscopy and accelerates photocatalytic detoxification.

    34. C[BOND]H Activation

      Propane Activation by Palladium Complexes with Chelating Bis(NHC) Ligands and Aerobic Cooxidation (pages 2485–2488)

      Dr. Dominik Munz and Prof. Thomas Strassner

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201309568

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      Reoxidation by dioxygen: The combination of C[BOND]H activation by a homogeneous catalytic palladium complex with a vanadiumoxo co-catalyst allows the selective aerobic oxidation of propane with dioxygen (see scheme).

    35. PPI Inhibitors

      Constrained Peptides with Target-Adapted Cross-Links as Inhibitors of a Pathogenic Protein–Protein Interaction (pages 2489–2493)

      Adrian Glas, David Bier, Dr. Gernot Hahne, Dr. Christoph Rademacher, Dr. Christian Ottmann and Dr. Tom N. Grossmann

      Version of Record online: 6 FEB 2014 | DOI: 10.1002/anie.201310082

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      Irregular peptide structures were stabilized using hydrophobic cross-links that replace residues crucially involved in target binding. The cross-links were designed in a rational and iterative process that involved X-ray crystallography. The resulting peptides inhibit the protein–protein interaction between virulence factor ExoS and human protein 14-3-3.

    36. Oxidative Coupling

      Powerful Fluoroalkoxy Molybdenum(V) Reagent for Selective Oxidative Arene Coupling Reaction (pages 2494–2497)

      Moritz Schubert, Jana Leppin, Dr. Kathrin Wehming, Dr. Dieter Schollmeyer, Prof. Dr. Katja Heinze and Prof. Dr. Siegfried R. Waldvogel

      Version of Record online: 29 JAN 2014 | DOI: 10.1002/anie.201309287

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      Wait a Mo: A novel molybdenum(V) reagent (see scheme) is superior to the performance of MoCl5 in the oxidative coupling reaction of aryls leading to less by-products and significantly increased yields.

    37. Stapled Peptides

      Direct Targeting of Rab-GTPase–Effector Interactions (pages 2498–2503)

      Jochen Spiegel, Philipp M. Cromm, Prof. Dr. Aymelt Itzen, Prof. Dr. Roger S. Goody, Dr. Tom N. Grossmann and Prof. Dr. Herbert Waldmann

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201308568

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      Targeting small GTPases: A library of hydrocarbon-stapled peptides was designed to target Rab GTPases and yielded peptides with significantly increased target affinity. One peptide demonstrates selective binding of activated Rab8a and inhibition of a Rab8a–effector interaction. This work suggests that peptide stapling may enable the development of inhibitors for other small GTPases.

    38. Competitive Deactivation Pathways

      Wavepacket Splitting and Two-Pathway Deactivation in the Photoexcited Visual Pigment Isorhodopsin (pages 2504–2507)

      Dr. Dario Polli, Dr. Oliver Weingart, Dr. Daniele Brida, Emiliano Poli, Margherita Maiuri, Dr. Katelyn M. Spillane, Prof. Andrea Bottoni, Dr. Philipp Kukura, Prof. Richard A. Mathies, Prof. Giulio Cerullo and Dr. Marco Garavelli

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201309867

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      Follow the right path! In the visual pigment analogue isorhodopsin, the photo-excited wavepacket branches in two competitive deactivation pathways involving two distinct conical intersections. This scenario is deduced from high-level QM/MM simulations of the photoinduced dynamics and is responsible both for the recorded non-exponential two-component decay and for the reduced isomerization quantum yield with respect to rhodopsin.

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