Angewandte Chemie International Edition

Cover image for Vol. 54 Issue 21

May 18, 2015

Volume 54, Issue 21

Pages 6069–6369

  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. Minireview
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Stabilizing Two Classical Antiaromatic Frameworks: Demonstration of Photoacoustic Imaging and the Photothermal Effect in Metalla-aromatics (Angew. Chem. Int. Ed. 21/2015) (page 6069)

      Dr. Congqing Zhu, Yuhui Yang, Ming Luo, Caixia Yang, Jingjing Wu, Lina Chen, Prof. Dr. Gang Liu, Prof. Dr. Tingbin Wen, Dr. Jun Zhu and Prof. Dr. Haiping Xia

      Article first published online: 1 MAY 2015 | DOI: 10.1002/anie.201503578

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      Two classical antiaromatic molecules cyclobutadiene (CBD) and pentalene, were stabilized by introduction of one metal fragment through a [2+2] cycloaddition reaction of osmapentalyne with alkynes. As shown by J. Zhu, H. Xia et al. in their Communication on page 6181 ff., the metalla-aromatic molecules absorb broadly from the UV to the near-IR region and show photoacoustic and photothermal effects. Theoretical calculations reveal that the antiaromaticity of both CBD and pentalene is decreased.

    2. You have free access to this content
      Inside Cover: High-Pressure Synthesis of Cd(NH3)2[B3O5(NH3)]2: Pioneering the Way to the Substance Class of Ammine Borates (Angew. Chem. Int. Ed. 21/2015) (page 6070)

      M. Sc. Gerhard Sohr, Mag. Nina Ciaghi, M. Sc. Michael Schauperl, Dr. Klaus Wurst, Prof. Dr. Klaus R. Liedl and Prof. Dr. Hubert Huppertz

      Article first published online: 29 APR 2015 | DOI: 10.1002/anie.201503580

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      The first ammine borate Cd(NH3)2[B3O5(NH3)]2 is prepared by a formal amminization of an inorganic BO3 group at 4.7 GPa and 800 °C. In their Communication on page 6360 ff., H. Huppertz et al. report that the characteristic building block of ammine borates is the adduct of ammonia to an inorganic BO3 group which gives a BO3(NH3) tetrahedron. This tetrahedron is incorporated into a complex borate structure through shared oxygen atoms.

    3. You have free access to this content
      Inside Back Cover: Heterostructure of Si and CoSe2: A Promising Photocathode Based on a Non-noble Metal Catalyst for Photoelectrochemical Hydrogen Evolution (Angew. Chem. Int. Ed. 21/2015) (page 6371)

      Dr. Mrinmoyee Basu, Zhi-Wei Zhang, Chih-Jung Chen, Po-Tzu Chen, Kai-Chih Yang, Prof. Chong-Geng Ma, Dr. Chun Che Lin, Prof. Dr. Shu-Fen Hu and Prof. Dr. Ru-Shi Liu

      Article first published online: 29 APR 2015 | DOI: 10.1002/anie.201503452

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      Heterostructures of p-Si microwires and orthorhombic CoSe2 nanorods can function as an efficient photocathode for a solar-driven water-splitting system, as shown by S. F. Hu, R. S. Liu, and co-workers in their Communication on page 6211 ff. p-Si as a visible-light semiconductor absorbs sunlight and generates photoexcited carriers, which are immediately transferred to the electrolyte by the semimetallic CoSe2 co-catalyst.

    4. You have free access to this content
      Back Cover: Electrodeposited Cobalt-Phosphorous-Derived Films as Competent Bifunctional Catalysts for Overall Water Splitting (Angew. Chem. Int. Ed. 21/2015) (page 6372)

      Nan Jiang, Dr. Bo You, Meili Sheng and Dr. Yujie Sun

      Article first published online: 29 APR 2015 | DOI: 10.1002/anie.201503447

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      Catalysts for water splitting play a key role in the utilization of renewable energy. In their Communication on page 6251 ff., Y. Sun and co-workers report bifunctional catalysts derived from electrodeposited cobalt–phosphorous films, which exhibit remarkable electrocatalytic performance for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) under strongly basic conditions and can rival the performance of integrated Pt and IrO2 systems.

  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. Minireview
    10. Review
    11. Communications
    1. You have free access to this content
      Frontispiece: polyMOFs: A Class of Interconvertible Polymer-Metal-Organic-Framework Hybrid Materials

      Dr. Zhenjie Zhang, Ha Thi Hoang Nguyen, Prof. Dr. Stephen A. Miller and Prof. Dr. Seth M. Cohen

      Article first published online: 8 MAY 2015 | DOI: 10.1002/anie.201582161

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      Hybrid Materials In their Communication on page 6152 ff., S. M. Cohen et al. report the transformation of non-porous, one-dimensional, amorphous polymers into crystalline polymer-based metal–organic framework materials.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Minireview
    10. Review
    11. Communications
  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. Minireview
    10. Review
    11. 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. Minireview
    10. Review
    11. Communications
    1. Kamal Kumar (page 6092)

      Article first published online: 13 JAN 2015 | DOI: 10.1002/anie.201411798

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      “The secret of being a successful scientist is to pursue excellence and not success. The natural talent I would like to be gifted with is penning Urdu poetry …” This and more about Kamal Kumar can be found on page 6092.

  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. Minireview
    10. Review
    11. 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. Minireview
    10. Review
    11. Communications
    1. C-1 Building Blocks in Organic Synthesis. Science of Synthesis Workbench Edition. Edited by Piet W. N. M. van Leeuwen. (pages 6094–6095)

      Anders T. Lindhardt

      Article first published online: 29 APR 2015 | DOI: 10.1002/anie.201501947

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      Two-volume set. Georg Thieme Verlag, Stuttgart, 2014, 1168 pp., softcover, $ 549.00.—ISBN 978-3131765116

  8. Minireview

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

      Poly(phosphoester)s: A New Platform for Degradable Polymers (pages 6098–6108)

      Dr. Tobias Steinbach and Dr. Frederik R. Wurm

      Article first published online: 7 MAY 2015 | DOI: 10.1002/anie.201500147

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      Polymers with potential: Poly(phosphoester)s play an important role in nature (DNA, RNA, and pyrophosphates), but in contrast to classical polyesters they are rarely used for everyday applications. Recent developments are highlighted that may make phosphorus-based polymers attractive materials for future applications.

  9. Review

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

      Catenanes: Fifty Years of Molecular Links (pages 6110–6150)

      Dr. Guzmán Gil-Ramírez, Prof. David A. Leigh and Alexander J. Stephens

      Article first published online: 7 MAY 2015 | DOI: 10.1002/anie.201411619

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      Half a century after Schill and Lüttringhaus carried out the first directed synthesis of a [2]catenane, a plethora of strategies now exist for the construction of interlocked molecular rings. Effective template synthesis enables the synthesis of higher order interlocked systems. This Review outlines the diverse strategies that exist for forming catenanes, their applications, and the important challenges that remain in the field of chemical topology.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Minireview
    10. Review
    11. Communications
    1. Hybrid Materials | Hot Paper

      polyMOFs: A Class of Interconvertible Polymer-Metal-Organic-Framework Hybrid Materials (pages 6152–6157)

      Dr. Zhenjie Zhang, Ha Thi Hoang Nguyen, Prof. Dr. Stephen A. Miller and Prof. Dr. Seth M. Cohen

      Article first published online: 29 APR 2015 | DOI: 10.1002/anie.201502733

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      A bottom-up strategy is used to generate porosity from non-porous, one-dimensional, amorphous polymeric materials by their transformation into crystalline polyMOF materials. These materials harness the advantages of the porosity and crystallinity of MOFs along with certain attributes of the polymers, such as facile film formation and greater chemical stability.

    2. Amino Acid Labeling

      Metabolic Profiling of Bacteria by Unnatural C-terminated D-Amino Acids (pages 6158–6162)

      Sean E. Pidgeon, Jonathan M. Fura, William Leon, Morgan Birabaharan, Dr. Dmitri Vezenov and Dr. Marcos M. Pires

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201409927

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      Transpeptidase domains of penicillin binding proteins catalyze the incorporation of exogenous D-amino acids onto bacterial cell surfaces. The substrates can have diverse side chains (see picture, pink), and this promiscuous enzyme can also accommodate C-terminus variations (blue). Most importantly, fluorescence labeling differences within and between bacterial species could be profiled using a panel of compounds.

    3. Surface Architectures

      Orthogonal Insertion of Lanthanide and Transition-Metal Atoms in Metal–Organic Networks on Surfaces (pages 6163–6167)

      José I. Urgel, Dr. David Ecija, Dr. Willi Auwärter, Daphné Stassen, Prof. Dr. Davide Bonifazi and Prof. Dr. Johannes V. Barth

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201410802

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      Surface-confined d–f bimetallic 2D coordination nanosystems have been achieved by using a three-step procedure that exploits orthogonal coordination interactions of CN-functionalized free-base porphyrin linkers with rare-earth and transition-metal centers. By systematic STM investigations the assembly process was established and the resulting nanoarchitectures characterized at the molecular level.

    4. Mechanochemistry

      Mechanophores with a Reversible Radical System and Freezing-Induced Mechanochemistry in Polymer Solutions and Gels (pages 6168–6172)

      Dr. Keiichi Imato, Atsushi Irie, Takahiro Kosuge, Dr. Tomoyuki Ohishi, Dr. Masamichi Nishihara, Prof. Atsushi Takahara and Prof. Hideyuki Otsuka

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201412413

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      Freezing-induced mechanochemistry: A new diarylbibenzofuranone-based mechanophore showed reversible color change by external forces through radical mechanism. By incorporating the mechanophore into polymer chains, it was revealed that freezing gels induced mechanical force along the chains, but the force was not large enough to cleave common covalent bonds.

    5. Solid-Phase Labeling

      Highly Efficient Solid-Phase Labeling of Saccharides within Boronic Acid Functionalized Mesoporous Silica Nanoparticles (pages 6173–6176)

      Xianghua Pan, Yang Chen, Peixuan Zhao, Daojin Li and Dr. Zhen Liu

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201500331

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      A solid-phase approach is proposed for highly efficient labeling (see picture, orange) of saccharides (blue) by using boronic acid (green) functionalized mesoporous silica nanoparticles as a nanoreactor. Compared to conventional liquid-phase labeling, the solid-phase approach exhibited faster reaction speed (only 2 min), high product purity, and much lower applicable saccharide concentration (10−9M).

    6. Regioselective Catalysis

      Total Synthesis of Ellagitannins through Regioselective Sequential Functionalization of Unprotected Glucose (pages 6177–6180)

      Hironori Takeuchi, Dr. Kenji Mishiro, Dr. Yoshihiro Ueda, Yusuke Fujimori, Dr. Takumi Furuta and Prof. Dr. Takeo Kawabata

      Article first published online: 9 APR 2015 | DOI: 10.1002/anie.201500700

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      Short and sweet: Very short total syntheses of ellagitannins were achieved through sequential and regioselective functionalization of the hydroxy groups of unprotected glucose.

    7. Metallacycles

      Stabilizing Two Classical Antiaromatic Frameworks: Demonstration of Photoacoustic Imaging and the Photothermal Effect in Metalla-aromatics (pages 6181–6185)

      Dr. Congqing Zhu, Yuhui Yang, Ming Luo, Caixia Yang, Jingjing Wu, Lina Chen, Prof. Dr. Gang Liu, Prof. Dr. Tingbin Wen, Dr. Jun Zhu and Prof. Dr. Haiping Xia

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201501349

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      Two birds with one stone: Two classical antiaromatic molecules, cyclobutadiene and pentalene, were stabilized by introducing one metal fragment by a [2+2] cycloaddition reaction of osmapentalyne with alkynes. These metalla-aromatic molecules absorb broadly from the UV to the near-IR region and show significant photoacoustic and photothermal effects.

    8. Hydrogenation

      Highly Efficient Ruthenium-Catalyzed N-Formylation of Amines with H2 and CO2 (pages 6186–6189)

      Dr. Lei Zhang, Dr. Zhaobin Han, Xiaoyu Zhao, Dr. Zheng Wang and Prof. Dr. Kuiling Ding

      Article first published online: 7 APR 2015 | DOI: 10.1002/anie.201500939

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      Just a pinch: CO2 is efficiently hydrogenated for N-formylation of various amines using ruthenium-pincer catalysts, thus affording the corresponding formamides with extremely high turnover numbers (TONs). The catalyst was readily reused for 12 runs without significant loss of activity in N,N-dimethylformamide production, thus demonstrating potential for practical utilization of this cost-effective process.

    9. Self-Assembly

      Beyond Molecules: Mesoporous Supramolecular Frameworks Self-Assembled from Coordination Cages and Inorganic Anions (pages 6190–6195)

      Dong Luo, Prof. Dr. Xiao-Ping Zhou and Prof. Dr. Dan Li

      Article first published online: 7 APR 2015 | DOI: 10.1002/anie.201501081

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      Caught in the middle: A series of diamond-like supramolecular frameworks featuring mesoporous cavities have been assembled through multiple interactions (covalent bonds, dative bonds, and weak C[BOND]H⋅⋅⋅X (X=O, F, and π) hydrogen bonds) between metal-imidazolate coordination cages and various anions. The mesoporous cavities are large enough to trap organic dye molecules, coordination cages, and vitamin B12.

    10. EPR Spectroscopy

      Distance Measurement on an Endogenous Membrane Transporter in E. coli Cells and Native Membranes Using EPR Spectroscopy (pages 6196–6199)

      Dr. Benesh Joseph, Arthur Sikora, Prof. Dr. Enrica Bordignon, Prof. Dr. Gunnar Jeschke, Prof. Dr. David S. Cafiso and Prof. Dr. Thomas F. Prisner

      Article first published online: 31 MAR 2015 | DOI: 10.1002/anie.201501086

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      A novel general strategy was used for precise distance measurements on an outer membrane protein in whole E. coli cells and isolated outer membranes. This approach provides an elegant way to study conformational changes or protein–protein/ligand interactions under native conditions and provides a method to validate high-resolution structures of membrane proteins in their native environment.

    11. Polymers

      Self-Immolative Poly(4,5-dichlorophthalaldehyde) and its Applications in Multi-Stimuli-Responsive Macroscopic Plastics (pages 6200–6205)

      Anthony M. DiLauro, Gregory G. Lewis and Prof. Scott T. Phillips

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201501320

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      Selective laser sintering has been used to prepare synthetic materials from a new type of self-immolative polymer. These materials autonomously amplify macroscopic and nonlocalized changes in the material in response to specific molecular inputs, and alter the response of the material depending on the identity of an applied signal.

    12. Phase Transitions

      A Chemically Triggered and Thermally Switched Dielectric Constant Transition in a Metal Cyanide Based Crystal (pages 6206–6210)

      Chao Shi, Xi Zhang, Ying Cai, Prof. Ye-Feng Yao and Prof. Wen Zhang

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201501344

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      A dielectric constant transition is observed in (HPy)2[Na(H2O)Co(CN)6] (HPy=pyridinium cation). This transition is chemically triggered by water in a single-crystal-to-single-crystal transformation (see picture; right) and thermally switched (left) in a structural phase transition.

    13. Water Splitting | Hot Paper

      Heterostructure of Si and CoSe2: A Promising Photocathode Based on a Non-noble Metal Catalyst for Photoelectrochemical Hydrogen Evolution (pages 6211–6216)

      Dr. Mrinmoyee Basu, Zhi-Wei Zhang, Chih-Jung Chen, Po-Tzu Chen, Kai-Chih Yang, Prof. Chong-Geng Ma, Dr. Chun Che Lin, Prof. Dr. Shu-Fen Hu and Prof. Dr. Ru-Shi Liu

      Article first published online: 29 APR 2015 | DOI: 10.1002/anie.201502573

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      Heterostructures of semi-metallic CoSe2 nanorods and p-Si microwires behave as an efficient photocathode for the solar-driven hydrogen evolution reaction. Photocurrents as high as 9 mA cm−2 have been achieved at 0 V vs. reversible hydrogen electrode. The high photocurrents can be attributed to low charge transfer resistance between the Si and CoSe2 interfaces and between the CoSe2 and electrolyte interfaces.

    14. Bromodomain Inhibitors | Hot Paper

      You have full text access to this OnlineOpen article
      LP99: Discovery and Synthesis of the First Selective BRD7/9 Bromodomain Inhibitor (pages 6217–6221)

      Peter G. K. Clark, Dr. Lucas C. C. Vieira, Dr. Cynthia Tallant, Dr. Oleg Fedorov, Dr. Dean C. Singleton, Dr. Catherine M. Rogers, Octovia P. Monteiro, James M. Bennett, Dr. Roberta Baronio, Dr. Susanne Müller, Dr. Danette L. Daniels, Jacqui Méndez, Prof. Dr. Stefan Knapp, Dr. Paul E. Brennan and Prof. Dr. Darren J. Dixon

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201501394

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      BRD7 and BRD9 are bromodomain proteins and part of some chromatin-remodeling complexes. A fragment lead was rapidly optimized through structure-based design and exploitation of a stereoselective nitro-Mannich/lactamization cascade process to give the first potent and selective BRD7/9 inhibitor, LP99. Treatment with LP99 led to displacement of BRD7 and BRD9 from chromatin and down-regulation of the pro-inflammatory cytokine IL-6.

    15. Nonlinear Optics

      Large Optical Nonlinearity Induced by Singlet Fission in Pentacene Films (pages 6222–6226)

      Yunlong Liu, Prof. Chunfeng Zhang, Rui Wang, Bo Zhang, Prof. Zhanao Tan, Prof. Xiaoyong Wang and Prof. Min Xiao

      Article first published online: 2 APR 2015 | DOI: 10.1002/anie.201501396

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      In pentacene films singlet-fission-induced nonlinear optical response with a magnitude of nonlinear susceptibility up to 10−9 esu is observed. Such efficient nonlinear optical response has been successfully applied to demonstrate ultrafast optical switching.

    16. Porphycenes

      meso-Dibenzoporphycene has a Large Bathochromic Shift and a Porphycene Framework with an Unusual cis Tautomeric Form (pages 6227–6230)

      Dr. Koji Oohora, Ayumu Ogawa, Tamaki Fukuda, Dr. Akira Onoda, Prof. Dr. Jun-ya Hasegawa and Prof. Dr. Takashi Hayashi

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201501496

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      Put a ring on it: The insertion of two benzene moieties at the meso positions of a porphycene framework yields meso-dibenzoporphycene (mDBPc). The compound has a small electrochemical HOMO–LUMO gap (0.81 eV) and an NIR absorption band at 1047 nm. X-ray photoelectron spectroscopy and a theoretical study indicate that, unusually for a porphycene derivative, the cis tautomeric form of the porphycene framework is more stable than the trans form.

    17. Supramolecular Chemistry

      Facile Self-Assembly of Metallo-Supramolecular Ring-in-Ring and Spiderweb Structures Using Multivalent Terpyridine Ligands (pages 6231–6235)

      Jun-Hao Fu, Yin-Hsuan Lee, Yun-Jui He and Prof. Dr. Yi-Tsu Chan

      Article first published online: 7 APR 2015 | DOI: 10.1002/anie.201501507

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      A nano-spiderweb: The complexation of multivalent terpyridine ligands with CdII ions afforded various linker-dependent ring-in-ring structures. The two-step self-assembly process through a tetratopic intermediate was deciphered by a mechanistic study. This ligand design strategy was successfully utilized in the construction of a trilayered metallo-supramolecular spiderweb.

    18. Asymmetric Catalysis

      Direct Catalytic Asymmetric Aldol Reaction of an α-Azido Amide (pages 6236–6240)

      Dr. Karin Weidner, Zhongdong Sun, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201501607

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      The direct aldol reaction of an α-azido 7-azaindolinylamide is promoted by a Cu-based catalyst. Aromatic aldehydes bearing an ortho substituent exhibited diastereodivergency depending on the nature of the chiral ligands used. A vicinal azido alcohol unit led to the corresponding aziridine, and facile hydrolysis of the 7-azaindolinylamide moiety furnished enantioenriched β-hydroxy-α-azido carboxylic acid derivatives.

    19. Alkyne Metathesis

      Selective Formation of a Trisubstituted Alkene Motif by trans-Hydrostannation/Stille Coupling: Application to the Total Synthesis and Late-Stage Modification of 5,6-Dihydrocineromycin B (pages 6241–6245)

      M. Sc. Stephan M. Rummelt, M. Sc. Johannes Preindl, M. Sc. Heiko Sommer and Prof. Alois Fürstner

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201501608

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      Directed although indirect: The antibiotic dihydrocineromyin B is one of countless natural products featuring an E-configured 2-methylbut-2-en-1-ol substructure (see picture, RCAM=ring-closing alkyne metathesis). The key step in the synthesis was a ruthenium-catalyzed hydroxy-directed trans-hydrostannation of an alkyne. The method is efficient, broadly applicable, and suited to late-stage diversification.

    20. H2 Activation by Hydrogenases

      Multiscale Modeling of the Active Site of [Fe] Hydrogenase: The H2 Binding Site in Open and Closed Protein Conformations (pages 6246–6250)

      Dr. Erik Donovan Hedegård, Prof. Jacob Kongsted and Prof. Ulf Ryde

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201501737

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      Hydrogenases mediate the conversion of H2 into hydride and protons. Intermediates and transition structures for H2 activation and hydride transfer in [Fe] hydrogenase were investigated (see picture, with a side-on bound dihydrogen and a hydride intermediate). Inclusion of the full protein with QM/MM is mandatory because of large electrostatic effects that cannot be described properly by vacuum calculations or continuum models.

    21. Water Splitting

      Electrodeposited Cobalt-Phosphorous-Derived Films as Competent Bifunctional Catalysts for Overall Water Splitting (pages 6251–6254)

      Nan Jiang, Dr. Bo You, Meili Sheng and Dr. Yujie Sun

      Article first published online: 20 APR 2015 | DOI: 10.1002/anie.201501616

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      Split and polished: Electrodeposited cobalt-phosphorous-derived films (Co-P) can act as superior bifunctional catalysts for overall water splitting. When employed as catalysts on both the anode and cathode for water electrolysis, the Co-P/Co-P catalyst couple can rival the integrated performance of IrO2 and Pt in alkaline media. Such a bifunctional Co-P film is a promising catalyst candidate for overall water-splitting electrolysis.

    22. Alkaloids

      Catalytic Asymmetric Total Synthesis of (−)-Galanthamine and (−)-Lycoramine (pages 6255–6259)

      Lei Li, Qiao Yang, Dr. Yuan Wang and Prof. Yanxing Jia

      Article first published online: 2 APR 2015 | DOI: 10.1002/anie.201411338

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      How gallant: The catalytic asymmetric total synthesis of both (−)-galanthamine and (−)-lycoramine were achieved by using a conceptually new strategy. Two metal-catalyzed reactions were used as the key steps, and include a palladium-catalyzed intramolecular Larock annulation reaction and enantioselective conjugate addition reaction catalyzed by a ScIII/N,N′-dioxide complex. Boc=tert-butoxycarbonyl, TES=triethylsilyl.

    23. High-Energy-Density Materials

      Energetic Materials with Promising Properties: Synthesis and Characterization of 4,4′-Bis(5-nitro-1,2,3-2H-triazole) Derivatives (pages 6260–6264)

      Dr. Chunlin He and Prof. Jean'ne M. Shreeve

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201412303

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      The hunt for high energy: Derivatives of 4,4′-bis(5-nitro-1,2,3-2H-triazole) were synthesized by different functionalization strategies. Competitive detonation properties were achieved and compared to reported analogues of fully carbon-nitrated bis(azole) compounds.

    24. C[BOND]H Activation

      Palladium-Catalyzed Enantioselective C[BOND]H Arylation for the Synthesis of P-Stereogenic Compounds (pages 6265–6269)

      Zi-Qi Lin, Wei-Zhen Wang, Shao-Bai Yan and Prof. Dr. Wei-Liang Duan

      Article first published online: 2 APR 2015 | DOI: 10.1002/anie.201500201

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      Dressing up phosphorus: The title reaction of N-(o-bromoaryl)-diarylphosphinic amides is described for the synthesis of phosphorus compounds bearing a P-stereogenic center. The method provides good enantioselectivities and high yields. The products were readily transformed into P-chiral biphenyl monophosphine ligands.

    25. Mechanochromic Materials

      Linearly Tunable Emission Colors Obtained from a Fluorescent–Phosphorescent Dual-Emission Compound by Mechanical Stimuli (pages 6270–6273)

      Dr. Zhu Mao, Dr. Zhiyong Yang, Dr. Yingxiao Mu, Prof. Yi Zhang, Dr. Yi-Fan Wang, Prof. Zhenguo Chi, Dr. Chang-Cheng Lo, Prof. Siwei Liu, Dr. Alan Lien and Prof. Jiarui Xu

      Article first published online: 7 APR 2015 | DOI: 10.1002/anie.201500426

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      Grinding a rainbow: A purely organic compound with excellent room-temperature fluorescent–phosphorescent dual-emission (rFPDE) properties brought about by mechanical grinding has been demonstrated. It shows linearly tunable emission colors with a straight line across the white zone in the chromaticity diagram, following the principle of color mixing.

    26. Ammonia Activation

      Ammonia Activation by a Nickel NCN-Pincer Complex featuring a Non-Innocent N-Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium (pages 6274–6277)

      Rudy M. Brown, Dr. Javier Borau Garcia, Juuso Valjus, Christopher J. Roberts, Dr. Heikki M. Tuononen, Dr. Masood Parvez and Prof. Roland Roesler

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201500453

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      Fast and reversible ligand-assisted ammonia activation on a nickel-NCN pincer complex featuring a non-innocent N-heterocyclic carbene produced a solvent-dependent equilibrium mixture of ammine and amide complexes (see scheme, Dipp=2,6-diisopropylphenyl). These species were present in solution in comparable proportions, and EXSY NMR experiments as well as exchange with ND3 further supported the equilibrium.

    27. Anti-infective Agents

      Amphiphilic Tobramycins with Immunomodulatory Properties (pages 6278–6282)

      Dr. Goutam Guchhait, Anthony Altieri, Dr. Balakishan Gorityala, Xuan Yang, Dr. Brandon Findlay, Prof. George G. Zhanel, Prof. Neeloffer Mookherjee and Prof. Frank Schweizer

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201500598

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      Double duty: Amphiphilic antibacterial aminoglycosides with additional immunomodulatory properties similar to those of host-defense peptides can be generated by appending a lipophilic R group (blue oval) to tobramycin. These amphiphilic tobramycin analogues can boost innate immune responses and control inflammatory responses related to septic shock.

    28. Synthetic Methods

      Methylene Blue as a Photosensitizer and Redox Agent: Synthesis of 5-Hydroxy-1H-pyrrol-2(5H)-ones from Furans (pages 6283–6287)

      Dr. Dimitris Kalaitzakis, Antonia Kouridaki, Dimitris Noutsias, Dr. Tamsyn Montagnon and Prof. Georgios Vassilikogiannakis

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201500744

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      A reagent with two hats: A highly efficient and general singlet-oxygen-initiated one-pot transformation of readily accessible furans into 5-hydroxy-1H-pyrrol-2(5H)-ones was developed (see scheme, right) and extended to the synthesis of other high-value α,β-unsaturated γ-lactams. This useful set of transformations relies on both the photosensitizing ability and the redox properties of methylene blue (MB), the reactivity of which differs from that of Rose Bengal (RB).

    29. Asymmetric Synthesis

      Enantioselective Palladium(0)-Catalyzed Nazarov-Type Cyclization (pages 6288–6291)

      Dr. Kei Kitamura, Dr. Naoyuki Shimada, Dr. Craig Stewart, Dr. Abdurrahman C. Atesin, Prof. Tülay A. Ateşin and Prof. Dr. Marcus A. Tius

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201500881

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      Stereoselective cycles: A Nazarov-type Pd0-catalyzed asymmetric cyclization is reported. The reaction forms cyclopentenones as single diastereoisomers that incorporate two contiguous asymmetric centers in high yield and optical purity. The optimized ligand L incorporates a weakly coordinating pyridine ring into a TADDOL-derived phosphoramidite. dba=dibenzylideneacetone. MS=molecular sieves.

    30. Electron Transport

      Synthesis, Structure, and Air-stable N-type Field-Effect Transistor Behaviors of Functionalized Octaazanonacene-8,19-dione (pages 6292–6296)

      Chengyuan Wang, Dr. Jing Zhang, Dr. Guankui Long, Prof. Dr. Naoki Aratani, Prof. Dr. Hiroko Yamada, Prof. Dr. Yang Zhao and Prof. Dr. Qichun Zhang

      Article first published online: 31 MAR 2015 | DOI: 10.1002/anie.201500972

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      A field day: The large π-conjugated N-heteroquinone 6,10,17,21-tetra[(triisopropylsilyl)ethynyl]-5,7,9,11,16,18,20,22-octaazanonacene-8,19-dione (OANQ; see figure) has been successfully synthesized and characterized. A field-effect transistor device based on OANQ single crystals displays an electron mobility of up to 0.2 cm2 V−1 s−1 under ambient conditions.

    31. Sol–Gel Processes

      Sol Processing of Conjugated Carbon Nitride Powders for Thin-Film Fabrication (pages 6297–6301)

      Dr. Jinshui Zhang, Mingwen Zhang, Lihua Lin and Prof. Xinchen Wang

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201501001

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      Going strong: Sol engineering of graphitic carbon nitride solids with strong oxidizing acids (e.g. HNO3) generates a stable colloidal suspension, which can be translated into thin films by dip/disperse-coating techniques. The polymeric matrix and the reversible hydrogen bonding result in the thin-film electrodes derived from the sol solution having high mechanical stability with improved conductivity for charge transport.

    32. Synthetic Methods

      Palladium-Catalyzed Hydrocarboxylation of Alkynes with Formic Acid (pages 6302–6305)

      Jing Hou, Prof. Jian-Hua Xie and Prof. Qi-Lin Zhou

      Article first published online: 2 APR 2015 | DOI: 10.1002/anie.201501054

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      Nontoxic: Acrylic acids are an important chemical feedstock. The title reaction provides acrylic acid and derivatives in good yields with high regioselectivities without the need to handle toxic CO gas.

    33. Heterocycle Synthesis

      The Cyano Group as a Traceless Activation Group for the Intermolecular [3+2] Cycloaddition of Azomethine Ylides: A Five-Step Synthesis of (±)-Isoretronecanol (pages 6306–6310)

      Jundong Li, Huaibo Zhao, Xunjin Jiang, Xiance Wang, Haiming Hu, Lei Yu and Prof. Dr. Yandong Zhang

      Article first published online: 27 MAR 2015 | DOI: 10.1002/anie.201500961

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      Without a trace… A highly stereoselective cycloaddition strategy provided efficient access to a diverse array of 5-unsubstituted pyrrolidines and enabled a five-step total synthesis of isoretronecanol (see scheme). A novel role of sodium borohydride in reductive decyanation was observed.

    34. Porphyrinoids

      meso,β-Oligohaloporphyrins as Useful Synthetic Intermediates of Diphenylamine-Fused Porphyrin and meso-to-meso β-to-β Doubly Butadiyne-Bridged Diporphyrin (pages 6311–6314)

      Norihito Fukui, Prof. Dr. Hideki Yorimitsu and Prof. Dr. Atsuhiro Osuka

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201501149

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      Doubled over: Chlorination of β-haloporphyrins with 2-chloro-1,3-bis(methoxycarbonyl)guanidine (Palau'Chlor) proceeded selectively at the neighboring unsubstituted meso position to afford meso,β-oligohaloporphyrins, which are useful intermediates of porphyrin-based extended π systems. For example, meso-chloro-β-iodoporphyrin was transformed stepwise into an efficiently conjugated meso-to-meso,β-to-β doubly butadiyne-linked porphyrin dimer.

    35. Manganese Complexes

      Umpolung of Methylenephosphonium Ions in Their Manganese Half-Sandwich Complexes and Application to the Synthesis of Chiral Phosphorus-Containing Ligand Scaffolds (pages 6315–6319)

      Dr. Dmitry A. Valyaev, Dr. Oleg A. Filippov, Dr. Noël Lugan, Dr. Guy Lavigne and Prof. Dr. Nikolai A. Ustynyuk

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201501256

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      Reactivity trend reversal: Methylenephosphonium salts coordinated to a manganese center were found to exhibit “iminium-like” reactivity towards nucleophiles (see scheme). This unprecedented umpolung enables the instant formation of carbon–heteroatom bonds, highlighted by the synthesis of novel chiral pincer-type phosphine–NHC–phosphine ligands.

    36. Asymmetric Catalysis

      Organocatalytic Asymmetric Addition of Naphthols and Electron-Rich Phenols to Isatin-Derived Ketimines: Highly Enantioselective Construction of Tetrasubstituted Stereocenters (pages 6320–6324)

      Marc Montesinos-Magraner, Dr. Carlos Vila, Rubén Cantón, Prof. Dr. Gonzalo Blay, Dr. Isabel Fernández, Prof. Dr. M. Carmen Muñoz and Prof. Dr. José R. Pedro

      Article first published online: 2 APR 2015 | DOI: 10.1002/anie.201501273

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      Gentle persuasion: A quinine-derived thiourea organocatalyst was found to promote the asymmetric addition of naphthols and activated phenols to ketimines derived from isatins (see scheme; Boc=tert-butoxycarbonyl). The reaction under mild conditions afforded chiral 3-amino-2-oxindoles containing a quaternary stereocenter in high yields (up to 99 %) with excellent enantioselectivity (up to 99 % ee).

    37. Electrocatalysis

      Phosphorus-Modified Tungsten Nitride/Reduced Graphene Oxide as a High-Performance, Non-Noble-Metal Electrocatalyst for the Hydrogen Evolution Reaction (pages 6325–6329)

      Dr. Haijing Yan, Prof. Chungui Tian, Dr. Lei Wang, Dr. Aiping Wu, Meichen Meng, Lu Zhao and Prof. Honggang Fu

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201501419

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      Boosting HER activity by phosphorus modification of tungsten nitride/reduced graphene oxide leads to a low-cost, high-performance, non-noble metal electrocatalyst for the hydrogen evolution reaction. The catalyst has a very small onset overpotential, a low Tafel slope, a large exchange current density in acid, and was stable in accelerated durability testing.

    38. Protein Structure Determination

      The Double-Histidine Cu2+-Binding Motif: A Highly Rigid, Site-Specific Spin Probe for Electron Spin Resonance Distance Measurements (pages 6330–6334)

      Timothy F. Cunningham, Miriam R. Putterman, Astha Desai, Prof.  W. Seth Horne and Prof. Sunil Saxena

      Article first published online: 27 MAR 2015 | DOI: 10.1002/anie.201501968

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      That's great, DEER! When a double-histidine Cu2+-binding motif (shown in blue) assembled in situ from natural amino acid residues and a metal salt was used as a rigid spin probe for double electron–electron resonance (DEER) distance measurements, dramatically narrower and readily interpretable distance distributions were observed than with a commonly used flexible spin label (red). Molecular modeling of an unlabeled protein gave a distance within 0.5 Å of the experimental value.

    39. Energetic Materials

      The Many Faces of FOX-7: A Precursor to High-Performance Energetic Materials (pages 6335–6338)

      Prof. Dr. Haixiang Gao and Prof. Dr. Jean'ne M. Shreeve

      Article first published online: 30 MAR 2015 | DOI: 10.1002/anie.201501973

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      Fox in a box: New derivatives created from 1,1-diamino-2, 2-dinitroethene (FOX-7) often have properties superior to those of RDX. The compounds exhibit good thermal stability, high density, positive heats of formation, an acceptable oxygen balance, and excellent detonation properties. These findings contribute to the value of FOX-7 as an energetic precursor.

    40. Sensors | Hot Paper

      Next-Generation Sequencing as Input for Chemometrics in Differential Sensing Routines (pages 6339–6342)

      Sara Goodwin, Alexandra M. Gade, Michelle Byrom, Baine Herrera, Camille Spears, Dr. Eric V. Anslyn and Dr. Andrew D. Ellington

      Article first published online: 31 MAR 2015 | DOI: 10.1002/anie.201501822

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      Keeping score: Nucleic acid sequences and sequence counts were used as multivariate data without the necessity of a spatial array. Aptamers were used as semi-specific receptors for cell line differentiation, and cross-reactivity between the aptamers was observed. The principal component analysis (PCA) generates high-dimensionality score plots, thus differentiating a mixture of complex and subtly different analytes.

    41. Polymerization Catalysts

      Heterobi- and -trimetallic Ion Pairs of Zirconocene-Based Isoselective Olefin Polymerization Catalysts with AlMe3 (pages 6343–6346)

      Dr. Gabriel Theurkauff, Dr. Arnaud Bondon, Dr. Vincent Dorcet, Prof. Dr. Jean-François Carpentier and Dr. Evgueni Kirillov

      Article first published online: 7 APR 2015 | DOI: 10.1002/anie.201501967

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      Zirconocene-based AlMe3 adducts bind an additional AlMe3 molecule reversibly, affording heterotrimetallic intermediates. One of the AlMe3 adducts undergoes slow decomposition via C[BOND]H activation in a bridging methyl unit to yield a new species with a trimetallic {Zr(μ-CH2)(μ-Me)AlMe(μ-Me)AlMe2} core.

    42. B,N Azo Dyes | Hot Paper

      Formation of BN Isosteres of Azo Dyes by Ring Expansion of Boroles with Azides (pages 6347–6351)

      Prof. Dr. Holger Braunschweig, Dr. Mehmet Ali Celik, Florian Hupp, Dr. Ivo Krummenacher and Lisa Mailänder

      Article first published online: 25 MAR 2015 | DOI: 10.1002/anie.201500970

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      Azo borealis: The first 1,2-azaborinine-substituted azo dyes have been synthesized using sterically demanding boroles and organic azides. The ring-expansion mechanism of the unexpected formation of the bright yellow chromophores was investigated by DFT calculations.

    43. C[BOND]H Activation | Hot Paper

      C[BOND]H Alkenylations with Alkenyl Acetates, Phosphates, Carbonates, and Carbamates by Cobalt Catalysis at 23 °C (pages 6352–6355)

      M. Sc. Marc Moselage, M. Sc. Nicolas Sauermann, B. Sc. Sven C. Richter and Prof. Dr. Lutz Ackermann

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201412319

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      Inexpensive cobalt catalysis enabled the C[BOND]H alkenylation of unactivated (hetero)arenes with enol derivatives at ambient temperature. The versatile cobalt catalyst was employed for challenging C[BOND]H/C[BOND]O cleavage reactions with alkenyl acetates, carbamates, carbonates, and phosphates in a stereoconvergent fashion.

    44. Protein Electrochemistry

      Microscale Crystals of Cytochrome c and Calixarene on Electrodes: Interprotein Electron Transfer between Defined Sites (pages 6356–6359)

      Dr. Róise E. McGovern, Dr. Sven C. Feifel, Prof. Dr. Fred Lisdat and Dr. Peter B. Crowley

      Article first published online: 1 APR 2015 | DOI: 10.1002/anie.201500191

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      Crystal contact. A calixarene “molecular glue” (blue) can be used to grow crystals of cytochrome c (gray; heme red) directly on Au–SAM electrodes. Characterization by cyclic voltammetry revealed remarkable electroactivity in the crystals. The amount of electrode-addressable protein is several orders of magnitude larger than in standard multilayer systems.

    45. Ammine Borates

      High-Pressure Synthesis of Cd(NH3)2[B3O5(NH3)]2: Pioneering the Way to the Substance Class of Ammine Borates (pages 6360–6363)

      M. Sc. Gerhard Sohr, Mag. Nina Ciaghi, M. Sc. Michael Schauperl, Dr. Klaus Wurst, Prof. Dr. Klaus R. Liedl and Prof. Dr. Hubert Huppertz

      Article first published online: 27 APR 2015 | DOI: 10.1002/anie.201500706

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      Ammonize me! The first compound in the class of ammine borates has been synthesized by a multi-anvil high-pressure/high-temperature experiment. The previously unknown adduct of ammonia to an inorganic BO3 group of a borate can be stabilized with this method, resulting in a BO3(NH3) tetrahedron as a new structural element.

    46. Drug Carriers

      Regioselective Ring-Opening Polymerization of a Polyhydroxycarboxylic Acid for the Synthesis of a Nanoscale Carrier Material with pH-Dependent Stability and Sustained Drug Release (pages 6364–6369)

      Dipl.-Chem. Alexander Ewe, Dr. Anita Jansen de Salazar, Dipl.-Phys. Katharina Lemmnitzer, Michael Marsch, Prof. Dr. Achim Aigner and Prof. Dr. Armin Geyer

      Article first published online: 13 APR 2015 | DOI: 10.1002/anie.201412055

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      Polyhydroxycarboxylic acid for nanoscale carrier formation: By ring-opening polymerization with high regioselectivity, a polyester (BICpoly) is obtained which can be precipitated in water as nanoparticles or as a thin film. Its complete stability at low pH values, its residue-free hydrolysis to biocompatible monomers at higher pH values, and its capability for drug loading and sustained drug release, make BICpoly an attractive carrier material for medical applications.

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