Angewandte Chemie International Edition

Cover image for Vol. 56 Issue 6

Early View (Online Version of Record published before inclusion in an issue)

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemPhotoChem, ChemPlusChem, Zeitschrift für Chemie

  1. Communications

    1. Noble-Gas Compounds | Hot Paper

      Coordination of KrF2 to a Naked Metal Cation, Mg2+

      Dr. Matic Lozinšek, Dr. Hélène P. A. Mercier, Dr. David S. Brock, Prof. Boris Žemva and Prof. Gary J. Schrobilgen

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201611534

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      Krypton difluoride, a thermodynamically unstable and potent oxidative fluorinator, coordinates to Mg2+ to form the coordination complexes, [Mg(KrF2)4(AsF6)2] and [Mg(KrF2)4(AsF6)2]⋅2 BrF5. The complexes were characterized by low-temperature single-crystal X-ray diffraction and low-temperature Raman spectroscopy. Computational studies show that the Mg−F bonds are essentially non-covalent, weakly electrostatic interactions.

    2. Endohedral Fullerene SMM

      Mononuclear Clusterfullerene Single-Molecule Magnet Containing Strained Fused-Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster

      Dr. Fupin Liu, Dr. Song Wang, Dr. Cong-Li Gao, Dr. Qingming Deng, Xianjun Zhu, Aram Kostanyan, Dr. Rasmus Westerström, Fei Jin, Prof. Dr. Su-Yuan Xie, Dr. Alexey A. Popov, Prof. Dr. Thomas Greber and Prof. Dr. Shangfeng Yang

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201611345

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      Fused box: Mononuclear clusterfullerenes MNC@C76 (M=Tb, Y) which do not obey the isolated-pentagon rule (IPR) contain one pair of fused-pentagons stabilized by a nearly linear mononuclear cyanide cluster. This situation contrasts with the triangular MNC clusters within the analogous clusterfullerenes of IPR-obeying C82 cages. TbNC@C76 is identified to be a field-induced single-molecule magnet (SMM).

    3. Smart Materials

      Surface-Enhanced Raman Spectra Promoted by a Finger Press in an All-Solid-State Flexible Energy Conversion and Storage Film

      Haitao Li, Dr. Han Dai, Prof. Dr. Yihe Zhang, Dr. Wangshu Tong, Dr. Hua Gao and Dr. Qi An

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201610737

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      Use your fingers: A self-energizing SERS-active substrate was prepared by combining a piezoelectric high-permittivity composite film and Ag nanowire layers (SERS=surface-enhanced Raman scattering). The polymeric composite film converts film deformation from a finger press into in situ stored electrical energy and promotes the SERS intensity up to one order of magnitude.

    4. Foldamers

      Controlling the Helix Handedness of ααβ-Peptide Foldamers through Sequence Shifting

      Dr. Monika Szefczyk, Dr. Ewelina Węglarz-Tomczak, Paulina Fortuna, Agnieszka Krzysztoń, Dr. Ewa Rudzińska-Szostak and Dr. Łukasz Berlicki

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201610154

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      Rewinding peptides: Modification of the peptide termini through extension or sequence shifting enables control of the balance between right-handed and left-handed helices for ααβ-peptide foldamers containing cis-2-aminocyclopentanecarboxylic acid (red).

    5. DNA Hydrogels

      Clamped Hybridization Chain Reactions for the Self-Assembly of Patterned DNA Hydrogels

      Jianbang Wang, Prof. Dr. Jie Chao, Prof. Dr. Huajie Liu, Dr. Shao Su, Prof. Dr. Lianhui Wang, Prof. Dr. Wei Huang, Prof. Dr. Itamar Willner and Prof. Dr. Chunhai Fan

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201610125

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      A clamped hybridization chain reaction (C-HCR)-based strategy is developed to guide DNA self-assembly to form macroscopic hydrogels. H1, H2=DNA hairpin strands, I=initiator strand.

    6. Heterocycle Synthesis

      Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles

      Zhongyan Hu, Jinhuan Dong, Yang Men, Zhichen Lin, Jinxiong Cai and Prof. Xianxiu Xu

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201611024

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      The domino effect: An unprecedented [4+2] rather than [3+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the synthesis of aminoquinolones, naphthyridines, and phenanthrolines. The two isocyanides exhibit new reactivity profiles in this domino reaction, which proceeds by their heterodimerization followed by 1,3-amino migration and 6 π electrocyclization (see scheme).

    7. C−H Activation

      Ligand-Enabled Alkynylation of C(sp3)−H Bonds with Palladium(II) Catalysts

      Dr. Haiyan Fu, Peng-Xiang Shen, Jian He, Dr. Fanglin Zhang, Dr. Suhua Li, Dr. Peng Wang, Tao Liu and Prof. Dr. Jin-Quan Yu

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201610426

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      Pyridine-enabled: The palladium(II)-catalyzed β- and γ-alkynylation of amide C(sp3)−H bonds is enabled by pyridine-based ligands. This alkynylation reaction is compatible with substrates containing α-tertiary or α-quaternary carbon centers. The β-methylene C(sp3)−H bonds in various carbocyclic rings were also successfully alkynylated.

    8. Fuel Cells | Hot Paper

      Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells

      Solène Gentil, Dr. Noémie Lalaoui, Arnab Dutta, Yannig Nedellec, Dr. Serge Cosnier, Dr. Wendy J. Shaw, Dr. Vincent Artero and Alan Le Goff

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201611532

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      A dual-purpose catalyst: A carbon-nanotube-supported, biomimetic nickel catalyst was developed for efficient platinum-free H2 oxidation. The high activity of the complex over a wide pH range allows its integration in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell using Pt/C at the cathode.

    9. Molecular Switches

      Photoisomerization of a Chiral Imine Molecular Switch Followed by Matrix-Isolation VCD Spectroscopy

      Corina H. Pollok, Tim Riesebeck and Dr. Christian Merten

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201610918

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      Flip the switch! The chiroptical properties of the E- and Z-isomers of a camphorquinone imine derivative were studied by means of matrix-isolation vibrational circular dichroism spectroscopy. This technique can be used to characterize the switching states of chiral molecular motors.

    10. Bioconjugation

      Stable and Rapid Thiol Bioconjugation by Light-Triggered Thiomaleimide Ring Hydrolysis

      Dr. Dimpy Kalia, Sharad P. Pawar and Jyoti S. Thopate

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201609733

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      Light and water go together! A photoactivable reagent for stable thiol bioconjugation under ice-cold conditions has been rationally designed. The reagent first forms a covalent adduct with the biomolecule of interest, and then undergoes extremely rapid ring hydrolysis upon UV irradiation via intramolecular catalysis orchestrated by a protonated amino group to yield the stable bioconjugate.

    11. Transformation of CO2

      Low-Temperature Hydrogenation of Carbon Dioxide to Methanol with a Homogeneous Cobalt Catalyst

      Jacob Schneidewind, Dr. Rosa Adam, Dr. Wolfgang Baumann, Dr. Ralf Jackstell and Prof. Matthias Beller

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201609077

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      A humble catalyst with modest needs: A non-noble metal catalyst was developed for the efficient hydrogenation of CO2 to methanol. The catalyst formed in situ from [Co(acac)3], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos), and HNTf2 was able to produce methanol from CO2 at just 100 °C (see scheme).

    12. Homogeneous Catalysis

      Iron-Catalyzed Mild and Selective Hydrogenative Cross-Coupling of Nitriles and Amines to Form Secondary Aldimines

      Dr. Subrata Chakraborty, Dr. Gregory Leitus and Prof. David Milstein

      Version of Record online: 12 JAN 2017 | DOI: 10.1002/anie.201608537

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      Ace of base: A base-metal-catalyzed hydrogenative cross-coupling of nitriles and amines to form secondary aldimines is reported. The reaction is catalyzed under mild conditions by a well-defined (iPr-PNP)Fe(H)Br(CO) pincer pre-catalyst and catalytic tBuOK.

  2. Author Profiles

    1. Authors Profile

      Version of Record online: 11 JAN 2017 | DOI: 10.1002/anie.201611954

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  3. Communications

    1. Polyketide Biosynthesis | Hot Paper

      Characterization of Giant Modular PKSs Provides Insight into Genetic Mechanism for Structural Diversification of Aminopolyol Polyketides

      Lihan Zhang, Takuya Hashimoto, Bin Qin, Junko Hashimoto, Ikuko Kozone, Teppei Kawahara, Masahiro Okada, Takayoshi Awakawa, Takuya Ito, Prof. Yoshinori Asakawa, Masashi Ueki, Shunji Takahashi, Prof. Hiroyuki Osada, Toshiyuki Wakimoto, Prof. Haruo Ikeda, Prof. Kazuo Shin-ya and Prof. Ikuro Abe

      Version of Record online: 11 JAN 2017 | DOI: 10.1002/anie.201611371

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      Module swapping: Aminopolyols are a class of bioactive polyketides biosynthesized by giant modular polyketide synthases (PKSs). Heterologous expression of over 150 kbp PKS gene clusters afforded novel aminopolyols, and phylogenetic comparison of four aminopolyol PKS gene clusters illustrated the precise mechanism of PKS reprogramming in nature.

    2. Asymmetric Catalysis

      Regio- and Enantioselective Rhodium-Catalyzed Addition of 1,3-Diketones to Allenes: Construction of Asymmetric Tertiary and Quaternary All Carbon Centers

      Thorsten M. Beck and Prof. Dr. Bernhard Breit

      Version of Record online: 11 JAN 2017 | DOI: 10.1002/anie.201610577

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      Rh-Catalysis: A regio- and enantioselective atom-economic catalytic addition of 1,3-diketones to allenes is reported furnishing tertiary and quaternary all-carbon stereocenters under mild reaction conditions. The reaction shows a broad functional-group tolerance and numerous variations on both reaction partners highlight its synthetic utility.

    3. Diazo–Alkyne Coupling

      Rapid Asymmetric Synthesis of Disubstituted Allenes by Coupling of Flow-Generated Diazo Compounds and Propargylated Amines

      Jian-Siang Poh, Szabolcs Makai, Timo von Keutz, Dr. Duc N. Tran, Dr. Claudio Battilocchio, Dr. Patrick Pasau and Prof. Steven V. Ley

      Version of Record online: 11 JAN 2017 | DOI: 10.1002/anie.201611067

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      Flow-enabled coupling: An asymmetric copper-catalyzed coupling reaction between unstabilized flow-generated diazo compounds and terminal propargylamine derivatives is described. The process occurs rapidly with high enantioselectivities, wide functional group tolerance and is further applicable to late-stage functionalization.

    4. Phosphorus

      Assembly of Ring-Shaped Phosphorus within Carbon Nanotube Nanoreactors

      Dr. Jinying Zhang, Dan Zhao, Dingbin Xiao, Chuansheng Ma, Dr. Hongchu Du, Xin Li, Lihui Zhang, Jialiang Huang, Hongyang Huang, Prof. Chun-Lin Jia, Prof. David Tománek and Prof. Chunming Niu

      Version of Record online: 11 JAN 2017 | DOI: 10.1002/anie.201611740

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      Ring-shaped phosphorus: A new phosphorus allotrope, ring-shaped phosphorus, has been synthesized within nanoreactors of carbon nanotubes by a vapor-phase reaction. The self-assembled ring-shaped phosphorus nanostructures, consisting of sequential P8 and P2 structural units, within carbon nanotubes (inside diameter 5–8 nm) are stable under ambient conditions.

    5. Quantum Dots

      Colloidal Synthesis of CH3NH3PbBr3 Nanoplatelets with Polarized Emission through Self-Organization

      Lige Liu, Sheng Huang, Longfei Pan, Dr. Li-Jie Shi, Prof. Bingsuo Zou, Prof. Luogen Deng and Prof. Haizheng Zhong

      Version of Record online: 11 JAN 2017 | DOI: 10.1002/anie.201610619

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      The synthesis of CH3NH3PbBr3 nanoplatelets through a self-organization process from preformed spherical nanodots is reported. The shape transformation was supported by the material characterization and theoretical simulation, and the resulting nanoplatelets exhibited polarized photoluminescence properties.

  4. Book Reviews

    1. A World From Dust. How the Periodic Table Shaped Life By Ben McFarland.

      Uwe J. Meierhenrich

      Version of Record online: 11 JAN 2017 | DOI: 10.1002/anie.201612218

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      Oxford University Press 2016. 333 pp., hardcover, £ 22.99.—ISBN 978-0190275013

  5. Communications

    1. Sulfur–Nitrogen Compounds

      Heterocumulene Sulfinyl Radical OCNSO

      Zhuang Wu, Qifan Liu, Jian Xu, Hailong Sun, Dingqing Li, Chao Song, Dr. Diego M. Andrada, Prof. Dr. Gernot Frenking, Dr. Tarek Trabelsi, Prof. Dr. Joseph S. Francisco and Prof. Dr. Xiaoqing Zeng

      Version of Record online: 11 JAN 2017 | DOI: 10.1002/anie.201611576

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      Heterocumulene OCNSO an interpseudohalogen by sharing the central nitrogen atom, was generated in the gas phase through flash vacuum pyrolysis of CF3S(O)NCO at 1200 K. Two conformers of OCNSO and their reversible interconversion in cryogenic (2.8–15 K) matrices were observed.