Angewandte Chemie International Edition

Cover image for Vol. 55 Issue 7

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

Chefredakteur: Peter Gölitz, Stellvertreter: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

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

  1. Communications

    1. Melanoma Diagnosis

      Monitoring Tyrosinase Expression in Non-metastatic and Metastatic Melanoma Tissues by Scanning Electrochemical Microscopy

      Tzu-En Lin, Alexandra Bondarenko, Andreas Lesch, Horst Pick, Fernando Cortés-Salazar and Prof. Hubert H. Girault

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201509397

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      Black mark: Tyrosinase levels in melanoma skin biopsies of various patients were monitored by using scanning electrochemical microscopy. The employed probe, made from soft and flexible polymeric materials, scans the tissue sections in a gentle contact mode without inducing damage. The different expression levels and distributions of tyrosinase in metastatic and non-metastatic melanomas were mapped.

    2. Quantum Dots

      Halide–Amine Co-Passivated Indium Phosphide Colloidal Quantum Dots in Tetrahedral Shape

      Kyungnam Kim, Dongsuk Yoo, Hyekyoung Choi, Dr. Sudarsan Tamang, Jae-Hyeon Ko, Sungwoo Kim, Prof. Yong-Hyun Kim and Prof. Sohee Jeong

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201600289

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      InP colloidal tetrahedral nanocrystals were synthesized through a simple acid-free approach using tris(dimethylamino) phosphine and indium trichloride dissolved in oleylamine. Their formation was attributed to the unique stabilization of the In-rich (111) facets by co-passivation with halide and primary amine.

    3. Drug Delivery

      A Telomerase-specific Doxorubicin-releasing Molecular Beacon for Cancer Theranostics

      Yi Ma, Zhaohui Wang, Min Zhang, Zhihao Han, Dan Chen, Qiuyun Zhu, Weidong Gao, Prof. Dr. Zhiyu Qian and Prof. Dr. Yueqing Gu

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201509182

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      Telomerase beacons: A molecular-beacon-based drug delivery system was designed for both detection of telomerase activity in living cells and telomerase-triggered drug release. This molecular beacon could specifically distinguish tumor cells and normal cells on the basis of telomerase activity, release doxorubicin, and avoid toxicity in healthy organs.

    4. Nanomedicine | Hot Paper

      Polymeric Nanoparticles Amenable to Simultaneous Installation of Exterior Targeting and Interior Therapeutic Proteins

      Dr. Xi Zhu, Dr. Jun Wu, Wei Shan, Dr. Wei Tao, Dr. Lili Zhao, Dr. Jong-Min Lim, Mathew D'Ortenzio, Prof. Rohit Karnik, Prof. Yuan Huang, Prof. Jinjun Shi and Prof. Omid C. Farokhzad

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201509183

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      Drug delivery: A novel polymeric nanoparticle platform that is capable of installing protein ligands on the particle surface and simultaneously carrying therapeutic proteins inside was developed by self-assembly. The surface coating with transferrin drastically changed the cellular behavior of the nanoparticles and enhanced the transepithelial transport by transcytosis.

    5. Synthetic Methods

      Palladium-Catalyzed C−H Arylation of α,β-Unsaturated Imines: Catalyst-Controlled Synthesis of Enamine and Allylic Amine Derivatives

      Minyan Li, Dr. María González-Esguevillas, Dr. Simon Berritt, Prof. Xiaodong Yang, Dr. Ana Bellomo and Prof. Dr. Patrick J. Walsh

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201509757

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      A tale of two catalysts: One was the best α-arylation catalyst, one was the worst (it gave only γ-arylation). Their opposite regioselectivity in a unique umpolung C−H arylation of palladium azapentadienyl intermediates enabled the selective synthesis of allylic amine and enamine derivatives (see scheme). A cation–π interaction with the heterobimetallic Pd/Na NiXantphos catalyst is proposed to be responsible for the unusual γ-regioselectivity.

    6. Biosynthesis

      A Unique Tryptophan C-Prenyltransferase from the Kawaguchipeptin Biosynthetic Pathway

      Anirudra Parajuli, Daniel H. Kwak, Luca Dalponte, Dr. Niina Leikoski, Tomas Galica, Ugochukwu Umeobika, Dr. Laurent Trembleau, Andrew Bent, Prof. Kaarina Sivonen, Matti Wahlsten, Dr. Hao Wang, Dr. Ermanno Rizzi, Prof. Gianluca De Bellis, Prof. James Naismith, Prof. Marcel Jaspars, Prof. Xinyu Liu, Dr. Wael Houssen and Dr. David Peter Fewer

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201509920

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      The macrocyclic undecapeptides Kawaguchipeptin A and B from Microcystis aeruginosa NIES-88 were shown to be products of the cyanobactin biosynthetic pathway. The 9 kb kawaguchipeptin (kgp) gene cluster was identified as being responsible for their production through heterologous expression in Escherichia coli, and the KgpF prenyltransferase was shown to prenylate C-3 of Trp residues in both linear and cyclic peptides in vitro.

    7. Dioxygen Activation

      Quercetin 2,4-Dioxygenase Activates Dioxygen in a Side-On O2–Ni Complex

      Dr. Jae-Hun Jeoung, Dr. Dimitrios Nianios, Prof. Dr. Susanne Fetzner and Prof. Dr. Holger Dobbek

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201510741

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      On side: Crystal structures of Ni-quercetinase in three different states (free E, ES-complex, and ES:O2 complex) provide direct insight how quercetin and O2 are activated at the Ni2+ ion. Conformational change of a glutamate residue upon quercetin binding weakens the interaction between Ni and a water ligand (W), thereby priming Ni2+ to bind O2 side-on and attack quercetin.

    8. Bioisosteres

      Validating Eaton's Hypothesis: Cubane as a Benzene Bioisostere

      Dr. Benjamin A. Chalmers, Hui Xing, Sevan Houston, Dr. Charlotte Clark, Dr. Sussan Ghassabian, Dr. Andy Kuo, Benjamin Cao, Andrea Reitsma, Cody-Ellen P. Murray, Dr. Jeanette E. Stok, Dr. Glen M. Boyle, Carly J. Pierce, Stuart W. Littler, Prof. David A. Winkler, Prof. Paul V. Bernhardt, Dr. Cielo Pasay, Prof. James J. De Voss, Prof. James McCarthy, Prof. Peter G. Parsons, Prof. Gimme H. Walter, Prof. Maree T. Smith, Prof. Helen M. Cooper, Prof. Susan K. Nilsson, Dr. John Tsanaktsidis, Dr. G. Paul Savage and Prof. Craig M. Williams

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201510675

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      Over 25 years ago, Eaton proposed that cubane could act as a benzene bioisostere. This hypothesis has now been confirmed with the synthesis and evaluation of cubane derivatives of five biologically important molecules: Two cubane analogues showed increased bioactivity compared to their benzene counterparts whereas two further analogues were of equal bioactivity.

    9. Zinc Clusters

      Atom-Precise Organometallic Zinc Clusters

      Hung Banh, Katharina Dilchert, Christine Schulz, Dr. Christian Gemel, Dr. Rüdiger W. Seidel, Dr. Régis Gautier, Dr. Samia Kahlal, Prof. Dr. Jean-Yves Saillard and Prof. Dr. Roland A. Fischer

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201510762

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      The bottom-up wet chemical synthesis of the ligand-protected oligonuclear clusters {[Zn10](Cp*)6Me}+, {[Zn9](Cp*)6}, and {[Zn8](Cp*)5(tBuNC)3)}+ is described. According to the Wade–Mingos rules, these zinc clusters are electron-deficient; quantum-chemical calculations reveal this to be due to the lack of π-type frontier orbitals on the apical ZnCp* units for cluster bonding.

    10. Metal–Organic Frameworks

      Framework Cationization by Preemptive Coordination of Open Metal Sites for Anion-Exchange Encapsulation of Nucleotides and Coenzymes

      Dr. Xiang Zhao, Chengyu Mao, Karen Tu Luong, Dr. Qipu Lin, Dr. Quan-Guo Zhai, Prof. Dr. Pingyun Feng and Prof. Dr. Xianhui Bu

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201510812

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      New traps for bio-anions. Using a preemptive coordination approach, highly porous cationic frameworks were made that allow immobilization of anionic nucleotides and coenzymes, in addition to charge- and size-selective capture and separation of organic dyes.

    11. Photoelectrochemistry

      Acid Treatment Enables Suppression of Electron–Hole Recombination in Hematite for Photoelectrochemical Water Splitting

      Yi Yang, Mark Forster, Dr. Yichuan Ling, Dr. Gongming Wang, Dr. Teng Zhai, Prof. Yexiang Tong, Prof. Alexander J. Cowan and Prof. Yat Li

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201510869

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      A simple acid treatment method is reported to increase the photoelectrochemical activity of hematite photoanodes. The enhanced photocurrent was due to the combination of improved efficiency of charge separation and suppressed electron–hole recombination, resulting in a greater yield of trapped photoelectrons being extracted to the external circuit.

    12. Metal–Organic Frameworks

      A Solvent-Free Hot-Pressing Method for Preparing Metal–Organic-Framework Coatings

      Yifa Chen, Siqing Li, Xiaokun Pei, Dr. Junwen Zhou, Prof. Dr. Xiao Feng, Shenghan Zhang, Yuanyuan Cheng, Haiwei Li, Ruodan Han and Prof. Dr. Bo Wang

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201511063

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      Hot off the press: A solvent-free approach for producing stable MOF coatings through a hot-pressing (HoP) method is presented. In the HoP method, temperature and pressure are applied simultaneously to facilitate the rapid growth of MOF nanocrystals onto desired substrates. This strategy was proven to be applicable to various MOFs and substrates.

    13. B−H Activation

      Capturing HBCy2: Using N,O-Chelated Complexes of Rhodium(I) and Iridium(I) for Chemoselective Hydroboration

      Marcus W. Drover, Prof. Dr. Laurel L. Schafer and Prof. Dr. Jennifer A. Love

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201511448

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      Cooperative activation of HBCy2 provided six-membered genuine rhoda- and iridacycles containing a δ-[M]⋅⋅⋅H−B agostic interaction. The treatment of these Shimoi-type borane adducts with an aldehyde and an alkene resulted in chemoselective aldehyde hydroboration and reformation of the 1,3-N,O-chelated starting material (see scheme). In contrast, free HBCy2 is selective for alkene hydroboration.

    14. Protein Structure | Very Important Paper

      You have full text access to this OnlineOpen article
      Charge-Induced Unzipping of Isolated Proteins to a Defined Secondary Structure

      Ana Isabel González Flórez, Eike Mucha, Dr. Doo-Sik Ahn, Sandy Gewinner, Dr. Wieland Schöllkopf, Prof. Dr. Kevin Pagel and Dr. Gert von Helden

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201510983

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      Ultracold gas-phase IR spectroscopy reveals that highly charged protein ions adopt highly ordered, regular secondary structures that are characterized by intramolecular C5 hydrogen bonds. This transition in secondary structure is supported by a simple electrostatic model and is most likely universal for isolated proteins.

    15. Nitrogen Heterocycles | Hot Paper

      Stereoselective Synthesis of Functionalized Pyrrolidines by the Diverted N−H Insertion Reaction of Metallocarbenes with β-Aminoketone Derivatives

      Simon M. Nicolle, Dr. William Lewis, Prof. Dr. Christopher J. Hayes and Prof. Dr. Christopher J. Moody

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201511433

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      The metal-catalyzed reaction of diazocarbonyl compounds with β-aminoketone derivatives leads to highly substituted pyrrolidines with excellent diastereoselectivity under mild reaction conditions. The reaction starts as a metallocarbene N−H insertion but is diverted by an intermolecular aldol reaction.

    16. Mass Spectrometry

      The Role of the Interface in Thin Film and Droplet Accelerated Reactions Studied by Competitive Substituent Effects

      Yafeng Li, Xin Yan and Prof. R. Graham Cooks

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201511352

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      On the face of it: A series of competitive substituent effect studies on a Claisen–Schmidt reaction reveal that interfacial processes play an important role in accelerating reaction rates in thin films and droplets. The additional acceleration of the methyl-substituted reagent and the changes of the Hammett ρ values for bulk and droplet-based reactions suggest that transport to the interface controls reaction rates.

  2. Highlights

    1. Solar Cells

      Molecular Engineering Combined with Cosensitization Leads to Record Photovoltaic Efficiency for Non-ruthenium Solar Cells

      Jonathan P. Hill

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201511506

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      Here comes the sun: By using a combined strategy of molecular engineering and cosensitization, impressively high Jsc and Voc values were achieved for porphyrin dyes, resulting in high photovoltaic efficiencies up to 11.5 %, a record for non-ruthenium dye-sensitized solar cells (DSSCs) with the I/I3 electrolyte. The results provide insight into furthering the development of efficient DSSCs through synergistically enhanced photovoltage and photocurrent.

  3. Communications

    1. Asymmetric Catalysis

      Chemo-, Diastereo-, and Enantioselective Iridium-Catalyzed Allylic Intramolecular Dearomatization Reaction of Naphthol Derivatives

      Qiang Cheng, Ye Wang and Prof. Dr. Shu-Li You

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201511519

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      Triple challenge: The challenges addressed in the title reaction include chemoselectivity between C and O as nucleophiles, diastereoselectivity when contiguous chiral centers are generated, and enantioselective control for constructing an all-carbon quaternary stereocenter. The [{Ir(dbcot)Cl}2]/(S,Sa)-L system leads to a general method for the dearomatization of naphthols. dbcot=dibenzocyclooctatetraene.

    2. Fullerenes

      New Isolated-Pentagon-Rule and Skeletally Transformed Isomers of C100 Fullerene Identified by Structure Elucidation of their Chloro Derivatives

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

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201511928

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      Chloride is key: Three isomers of C100 fullerene which obey the isolated pentagon rule (IPR) have been isolated and characterized by X-ray structure determination of their chloro derivatives. Although the IPR cages in C1-C100(425)Cl22 and C2-C100(18)Cl28/30 retain cage connectivities, Cs-C100(417)Cl28 transforms into the nonclassical (NC) isomer C1-C98(NC)Cl26 by loss of a C2 fragment (see picture; C=gray; Cl=green).

    3. Asymmetric Hydrogenation

      Asymmetric Hydrogenation of Vinylthioethers: Access to Optically Active 1,5-Benzothiazepine Derivatives

      Dr. Wei Li, Christoph Schlepphorst, Constantin Daniliuc and Prof. Dr. Frank Glorius

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201512032

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      Popular heterocycles: A method for the asymmetric hydrogenation of vinylthioethers provides optically active 2,3-dihydro-1,5-benzothiazepinones. Excellent enantioselectivities (up to 95 % ee) and high yields (up to 99 %) were obtained for a variety of substrates using a ruthenium(II) NHC complex (NHC=N-heterocyclic carbene). This methodology was directly applied to the synthesis of the antidepressant drug R-(−)-thiazesim.

    4. Alkaloids

      Enantioselective Formal Syntheses of 11 Nuphar Alkaloids and Discovery of Potent Apoptotic Monomeric Analogues

      Hui Li, Dr. Alexander Korotkov, Charles W. Chapman, Prof. Alan Eastman and Prof. Jimmy Wu

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201600106

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      From Supersilyl to Super Killers: Enantiopure monomeric nuphar alkaloids having apoptotic activity were discovered (see example), and concise enantioselective formal syntheses of 11 nuphar alkaloids were achieved. The syntheses featured the unprecedented use of supersilyl groups to control the regio-, diastereo-, and enantioselectivity of vinylogous Mukaiyama–Mannich reactions.

  4. News

  5. Cover Pictures

    1. Breakable Hybrid Organosilica Nanocapsules for Protein Delivery

      Dr. Eko Adi Prasetyanto, Dr. Alessandro Bertucci, Dr. Dedy Septiadi, Prof. Roberto Corradini, Dr. Pablo Castro-Hartmann and Prof. Luisa De Cola

      Article first published online: 5 FEB 2016 | DOI: 10.1002/anie.201600937

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      A breakable shell for the encapsulation of proteins allows their delivery into cells and subsequent release. In their Communication (DOI: 10.1002/anie.201508288), L. de Cola et al. describe the construction of a breakable shell comprising silica units that are held together by disulfide bridges. Once the encapsulated proteins are internalized in cells, the reduction of the disulfide groups results in disintegration of the shells and release of the proteins, which retain their activity throughout the process.

  6. Communications

    1. Sodium-Ion Batteries

      Boosted Charge Transfer in SnS/SnO2 Heterostructures: Toward High Rate Capability for Sodium-Ion Batteries

      Yang Zheng, Tengfei Zhou, Chaofeng Zhang, Jianfeng Mao, Prof. Huakun Liu and Prof. Zaiping Guo

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201510978

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      Tin anodes: Ultrafine SnS/SnO2 heterostructures were fabricated and applied as anodes for sodium-ion batteries. The as-prepared material shows excellent performance and outstanding cycling stability at high rates, which can be ascribed to the charge-transfer driving force, good structural stability, and excellent electrical conductivity.

    2. STED Microscopy

      Fluorescent Rhodamines and Fluorogenic Carbopyronines for Super-Resolution STED Microscopy in Living Cells

      Dr. Alexey N. Butkevich, Dr. Gyuzel Yu. Mitronova, M. Sc. Sven C. Sidenstein, B. Sc. Jessica L. Klocke, Dr. Dirk Kamin, M. Sc. Dirk N. H. Meineke, Dr. Elisa D'Este, Dr. Philip-Tobias Kraemer, Dr. Johann G. Danzl, Dr. Vladimir N. Belov and Prof. Dr. Stefan W. Hell

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201511018

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      Bright, photostable, and cell-permeant rhodamines, carbopyronines, and Si-rhodamines were designed as specific fluorescent markers for living cells. Cytoskeletal filaments, labeled by HaloTag fusion technology, were stained with 1 μm dye conjugates emitting green or red light. Light microscopy with stimulated emission depletion (STED) provided one- and two-color images with an optical resolution of 40–60 nm.

    3. Heterocycle Synthesis

      Synthesis of Enantioenriched Indolines by a Conjugate Addition/Asymmetric Protonation/Aza-Prins Cascade Reaction

      Blake E. Daniels, Jane Ni and Prof. Sarah E. Reisman

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201510972

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      The artist formerly known as Prins: The title cyclization reaction has been developed and is catalyzed by a zirconium-derived Lewis-acid-assisted Brønsted acid. The protocol enables the synthesis of a range of polycyclic indolines in good yields and with high enantioselectivity.

    4. Enantioselective Catalysis | Hot Paper

      Catalytic SN2′- and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis

      Ying Shi and Prof. Amir H. Hoveyda

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201600309

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      Combination catalysis: The first examples of catalytic enantioselective allylic substitution reactions that introduce a CH2−B(pin) unit are described (pin=pinacolato). In combination with various catalytic cross-coupling processes, a range of important organic molecules are now readily accessible.

    5. Natural Product Synthesis

      Total Synthesis of (±)-Strictamine

      Dr. Weiwu Ren, Dr. Qian Wang and Prof. Dr. Jieping Zhu

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201511638

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      Strictly business: Strictamine, containing an unusual methanoquinolizidine core, was synthesized in nine steps from cyclohexenone 1. The method involved: a) build-up of the functionalized 2-azabicyclo[3.3.1]nonan-9-one skeleton 2 from 1, b) late-stage construction of the indolenine unit, and c) a Ni-promoted cyclization.

    6. Electronic Spectroscopy

      Electronic Characterization of Reaction Intermediates: The Fluorenylium, Phenalenylium, and Benz[f]indenylium Cations and Their Radicals

      Dr. Jan Fulara, Arghya Chakraborty and Prof. Dr. John P. Maier

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201511230

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      The fluorenylium, phenalenylium, and benz[f]indenylium cations and their radicals, which are key intermediates in organic reactions, were electronically characterized in 6 K neon matrices after mass-selected deposition of C13H9+ ions. The structural assignments were based on calculated excitation energies.

    7. Diamagnetic Raman Optical Activity

      Diamagnetic Raman Optical Activity of Chlorine, Bromine, and Iodine Gases

      Dr. Jaroslav Šebestík, Dr. Josef Kapitán, Ondřej Pačes and Prof. Petr Bouř

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201600058

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      Rotating diamagnetic molecules are supposed not to interact much with external magnetic field because their magnetic dipole moment is small. However, a strong magnetic Raman optical activity of Cl2, Br2 and I2 gases was measured. This activity was rationalized by paramagnetic excited electronic states participating in the Raman scattering.

  7. Author Profiles

    1. Oliver Trapp

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201600299

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      My not-so-secret passion is stereochemistry. If I were not a scientist, I would be an astronaut.

  8. Cover Pictures

    1. You have free access to this content
      The Largest Metalloid Group 14 Cluster, Ge18[Si(SiMe3)3]6: An Intermediate on the Way to Elemental Germanium

      Dr. Oleksandr Kysliak, Dr. Claudio Schrenk and Prof. Dr. Andreas Schnepf

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201600531

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      The seemingly simple process of the formation or dissolution of a metal is highly dynamic and mostly unknown on the atomic scale. In their Communication (DOI: 10.1002/anie.201510831), A. Schnepf et al. show that the oxidation of [Ge9(Hyp)3] (Hyp=Si(SiMe3)3) with an iron(II) salt leads to Ge18(Hyp)6, the largest metalloid Group 14 cluster that has been structurally characterized to date. This cluster can be regarded as a first trapped intermediate of the formation of Ge(cF136) from Ge9 units.

    2. You have free access to this content
      Mechanochromism and Mechanical Force-Triggered Cross-Linking from a Single Reactive Moiety Incorporated into Polymer Chains

      Dr. Huan Zhang, Fei Gao, Xiaodong Cao, Yanqun Li, Prof. Yuanze Xu, Prof. Wengui Weng and Prof. Roman Boulatov

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201600533

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      Just as mechanical force applied to the strings of a violin produces beautiful sounds, mechanical stress acting on polymers leads to interesting chemical reactions. In their Communication (DOI: 10.1002/anie.201510171), W. Weng et al. show that when mechanically loaded a spirothiopyran-containing polymer turns bright green and undergoes cross-linking. Two distinct chemical responses to a mechanical load are combined in a single reactive site.

  9. Communications

    1. Photodynamic Therapy

      Remote-Controlled Release of Singlet Oxygen by the Plasmonic Heating of Endoperoxide-Modified Gold Nanorods: Towards a Paradigm Change in Photodynamic Therapy

      Dr. Safacan Kolemen, Dr. Tugba Ozdemir, Dayoung Lee, Gyoung Mi Kim, Tugce Karatas, Prof. Juyoung Yoon and Prof. Engin U. Akkaya

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201510064

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      EPT sees the light: When gold nanorods with tethered endoperoxides are irradiated with near-infrared light, the endoperoxides undergo thermal cycloreversion, resulting in the generation of singlet oxygen. The amount of singlet oxygen generated by these nanocomposites is sufficient for triggering apoptosis in cell cultures.

  10. Cover Pictures

    1. You have free access to this content
      Charge-Induced Unzipping of Isolated Proteins to a Defined Secondary Structure

      Ana Isabel González Flórez, Eike Mucha, Dr. Doo-Sik Ahn, Sandy Gewinner, Dr. Wieland Schöllkopf, Prof. Dr. Kevin Pagel and Priv.-Doz. Dr. Gert von Helden

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201600680

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      Charge-induced unzipping of isolated proteins leads to a defined secondary structure characterized by intramolecular C5 hydrogen bonds. The cover picture illustrates how Coulomb repulsion can pull apart helical elements to form an extended linear conformation similar to a single-strand β sheet. As G. von Gelden and co-workers report in their Communication (DOI: 10.1002/anie.201510983), this conformation is likely a universal form of secondary structure in highly charged protein ions.

    2. You have free access to this content
      A Multi-RNAi Microsponge Platform for Simultaneous Controlled Delivery of Multiple Small Interfering RNAs

      Prof. Young Hoon Roh, Dr. Jason Z. Deng, Dr. Erik C. Dreaden, Jae Hyon Park, Dr. Dong Soo Yun, Dr. Kevin E. Shopsowitz and Prof. Paula T. Hammond

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201600877

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      RNA interference (RNAi) has been intensively investigated as a powerful approach for therapeutic applications. In their Communication (DOI: 10.1002/anie.201508978), P. T. Hammond et al. describe a modular platform for generating multiple polymeric RNAi molecules that self-assemble into composite sponge-like porous microstructures. The cover illustrates the precise ratiometric formation of microstructures from two polymeric RNAi molecules.

  11. Communications

    1. Fluorescent Probes

      Development of a Two-Photon Fluorescent Probe for Imaging of Endogenous Formaldehyde in Living Tissues

      Yonghe Tang, Dr. Xiuqi Kong, An Xu, Dr. Baoli Dong and Prof. Weiying Lin

      Article first published online: 4 FEB 2016 | DOI: 10.1002/anie.201510373

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      Shine a little light: The first two-photon fluorescent formaldehyde probe, Na-FA, was engineered by condensation of a hydrazine moiety with FA. This unique strategy grants the probe highly favorable properties: a very large turn-on signal, a low detection limit, and a very fast onset, which collectively enable tracking of endogenous FA in living tissues for the first time.

  12. Reviews

    1. Contiguous Quaternary C Atoms

      Synthetic Strategies toward Natural Products Containing Contiguous Stereogenic Quaternary Carbon Atoms

      Dr. Martin Büschleb, Dr. Stéphane Dorich, Prof. Dr. Stephen Hanessian, Daniel Tao, Kyle B. Schenthal and Prof. Dr. Larry E. Overman

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201507549

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      Raising the bar: The impressive achievements in the total synthesis of complex natural products containing two or three stereogenic contiguous quaternary carbon centers since 1953 are showcased through the many creative strategies. The height of the “synthesis bar” can now be raised to consider hitherto unconquered molecules with multiple contiguous quaternary carbon atoms, each residing on a stereogenic carbon atom.

  13. Communications

    1. High Dipole Moments

      Hexasubstituted Benzenes with Ultrastrong Dipole Moments

      Jakob Wudarczyk, Dr. George Papamokos, Vasilis Margaritis, Dr. Dieter Schollmeyer, Dr. Felix Hinkel, Prof. Dr. Martin Baumgarten, Prof. Dr. George Floudas and Prof. Dr. Klaus Müllen

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201508249

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      Just a moment: Molecules with high dipole moments are desirable materials for organic electronic applications such as nonlinear optics and ferroelectrics. Hexasubstitution of benzene and a novel method to synthesize dihydrobenzimidazoles has allowed charge-free compounds to be generated with dipole moments above 10 debye.

    2. Polymers

      Thiophene-S,S-dioxidized Indophenine: A Quinoid-type Building Block with High Electron Affinity for Constructing n-Type Polymer Semiconductors with Narrow Band Gaps

      Dr. Yunfeng Deng, Bin Sun, Yinghui He, Jesse Quinn, Dr. Chang Guo and Prof. Dr. Yuning Li

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201508781

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      Three isomers of thiophene-S,S-dioxidized indophenine (IDTO) were conveniently synthesized through oxidation of an indophenine compound. Two of the three isomers could be converted into the most stable isomer, (E,E,E)-IDTO, by heating at 110 °C. The conjugated polymer PIDTOTT based on (E,E,E)-IDTO displayed unipolar n-type semiconductor characteristics with surprisingly high electron mobility (up to 0.14 cm2 V−1 s−1).

    3. Interlocked Systems

      You have full text access to this OnlineOpen article
      Synthesis and Dynamics of Nanosized Phenylene–Ethynylene–Butadiynylene Rotaxanes and the Role of Shape Persistence

      Christopher Schweez, Dr. Philip Shushkov, Prof. Dr. Stefan Grimme and Prof. Dr. Sigurd Höger

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201509702

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      Escape artist extraordinaire: How shape-persistent is “shape-persistent”? Novel phenylene–ethynylene–butadiynylene rotaxanes synthesized by a covalent-template approach were found to undergo unthreading of the wheel from the axis (see picture). The detailed unthreading mechanism was investigated theoretically by state-of-the-art DFT-based molecular mechanics and a string method for the simulation of rare events.

    4. Biosynthesis

      Mechanistic Insights into the Radical S-adenosyl-l-methionine Enzyme NosL From a Substrate Analogue and the Shunt Products

      Xinjian Ji, Dr. Yongzhen Li, Youli Jia, Prof. Dr. Wei Ding and Prof. Dr. Qi Zhang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201509900

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      Two roads diverged: The radical S-adenosyl-L-methionine enzyme NosL, which catalyzes the transformation of L-tryptophan into 3-methyl-2-indolic acid (MIA), was investigated with the substrate analogue 2-methyl-3-(indol-3-yl)propanoic acid (MIPA). Radical-mediated hydrogen abstraction was found to be from the amino group of L-tryptophan and occurs at two different sites of MIPA, thus partitioning the substrate into different reaction pathways.

    5. Cell-Penetrating Peptides

      An Intrinsically Disordered Peptide Facilitates Non-Endosomal Cell Entry

      Dr. Scott H. Medina, Dr. Stephen E. Miller, Allison I. Keim, Dr. Alexander P. Gorka, Dr. Martin J. Schnermann and Dr. Joel P. Schneider

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510518

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      Disorder imparts order: CLIP6, an intrinsically disordered peptide, mediates cellular entry through non-endosomal physical translocation across the membrane. This activity, defined by its unstructured state, facilitates the delivery of membrane-impermeable cargo to the interior of cells.

    6. Asymmetric Catalysis

      Bifunctional Brønsted Base Catalyzes Direct Asymmetric Aldol Reaction of α-Keto Amides

      Haizea Echave, Dr. Rosa López and Prof. Dr. Claudio Palomo

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510482

      Thumbnail image of graphical abstract

      New players in town: The enantioselective direct cross-aldol reaction of α-keto amides with aldehydes was accomplished using ureidopeptide-based Brønsted base catalysts. The reaction provides stereodefined syn-aldol adducts without self-condensation, competitive aldehyde enolization, aldol dehydration, and lactonization products, which are usually observed when using α-keto esters as donor partners. Cbz=benzyloxycarbonyl.

    7. Biocatalysis

      Catalytic Promiscuity of Transaminases: Preparation of Enantioenriched β-Fluoroamines by Formal Tandem Hydrodefluorination/Deamination

      Dr. Aníbal Cuetos, Marina García-Ramos, Eva-Maria Fischereder, Dr. Alba Díaz-Rodríguez, Prof. Gideon Grogan, Prof. Vicente Gotor, Prof. Wolfgang Kroutil and Dr. Iván Lavandera

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510554

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      A night out for TAs: Transaminases (TAs) are shown to react with aromatic β-fluoroamines, thus leading to enantioselective dehalogenation and deamination to form the corresponding acetophenone derivatives. Racemic β-fluoroamines are resolved in a kinetic resolution by tandem hydrodefluorination/deamination, thus giving the corresponding amines with up to greater than 99 % ee. This method exploits the catalytic promiscuity of TAs as a tool for novel transformations.

    8. Singlet Fission in Oligoacenes

      Intramolecular Singlet Fission in Oligoacene Heterodimers

      Samuel N. Sanders, Dr. Elango Kumarasamy, Andrew B. Pun, Dr. Michael L. Steigerwald, Dr. Matthew Y. Sfeir and Prof. Luis M. Campos

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510632

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      Organic electronics: A series of oligoacene heterodimers was synthesized to test the energetic requirements for singlet fission—a photophysical process that yields two triplet excitons from a single photon. Thus a possibility is offered to tune this process.

    9. C−H activation

      Cobalt(III)-Catalyzed Redox-Neutral Synthesis of Unprotected Indoles featuring an N−N Bond Cleavage

      Andreas Lerchen, Suhelen Vásquez-Céspedes and Prof. Dr. Frank Glorius

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510705

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      This is aN-Nulation! A redox-neutral cobalt(III)-catalyzed synthesis of free indoles featuring an N−N bond cleavage has been achieved. An increase of reactivity could be observed on tuning the directing group at the hydrazine-β-nitrogen atom, which turned out to be the crucial factor for the reaction.

    10. Host–Guest Systems

      Guest-Induced Breathing Effect in a Flexible Molecular Crystal

      Yujie Sheng, Prof. Qibin Chen, Junyao Yao, Dr. Yunxiang Lu, Prof. Honglai Liu and Prof. Sheng Dai

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510637

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      The Age of Gemini: A breathing effect is realized by cell expansion and alkyl transformation of a flexible molecular crystal containing Gemini units. This breath-like transition endows the crystal with preferential chloroform adsorption.

    11. Self-Assembly

      Halogen-Bond-Templated [2+2] Photodimerization in the Solid State: Directed Synthesis and Rare Self-Inclusion of a Halogenated Product

      Michael A. Sinnwell and Prof. Dr. Leonard R. MacGillivray

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510912

      Thumbnail image of graphical abstract

      This way, please: A ditopic halogen-bond acceptor organizes a halogenated stilbene for a stereoselective [2+2] photodimerization reaction to take place between two stilbenes in the solid state. The resultant halogen-functionalized cyclobutane product self-assembles to form a host–guest compound that exhibits a very rare form of self-inclusion. Atom colors: C=gray; I=purple; N=blue; F=green.

    12. Frustrated Lewis Pairs

      A P−H Functionalized Al/P Frustrated Lewis Pair: Substrate Activation and Selective Hydrogen Transfer

      M. Sc. Lukas Keweloh, M. Sc. Hans Klöcker, Prof. Dr. Ernst-Ulrich Würthwein and Prof. Dr. Werner Uhl

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511048

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      Cooperative activation and hydrogen shift is observed as a new reactivity pattern upon treatment of a P−H functionalized Al/P frustrated Lewis pair with various unsaturated substrates. Unusual highly functionalized phosphorus compounds were obtained, such as a phosphinyltriazene or phosphaurea. With benzonitrile, the sequence adduct formation, activation and H-shift gives an iminophosphine (see scheme).

    13. Natural Product Synthesis

      Epicochalasines A and B: Two Bioactive Merocytochalasans Bearing Caged Epicoccine Dimer Units from Aspergillus flavipes

      Hucheng Zhu, Chunmei Chen, Qingyi Tong, Xiao-Nian Li, Jing Yang, Yongbo Xue, Zengwei Luo, Jianping Wang, Guangmin Yao and Yonghui Zhang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511315

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      Adamantly original: Two bioactive merocytochalasans isolated from the liquid culture broth of Aspergillus flavipes represent a new class of cytochalasans with unexpected scaffolds consisting of fused aspochalasin and epicoccine dimer moieties. Epicochalasines A (1) and B both possess a hendecacyclic 5/6/11/5/6/5/6/5/6/6/5 ring system with an adamantyl cage but have different carbon skeletons.

    14. Synthetic Methods

      Nickel-Catalyzed Decarboxylative Difluoroalkylation of α,β-Unsaturated Carboxylic Acids

      Gang Li, Tao Wang, Fan Fei, Dr. Yi-Ming Su, Dr. Yan Li, Dr. Quan Lan and Prof. Dr. Xi-Sheng Wang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511321

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      Nickel and F: The title reaction has been developed using commonly available fluoroalkyl halides. This novel transformation demonstrates broad substrate scope, excellent functional-group tolerance, mild reaction conditions, and excellent stereoselectivity. Mechanistic investigations indicate that a fluoroalkyl radical is involved in the catalytic cycle. dppp=1,3-bis(diphenylphosphino)propane.

    15. Epigenetics

      Modified Nucleotides for Discrimination between Cytosine and the Epigenetic Marker 5-Methylcytosine

      Janina von Watzdorf, Kim Leitner and Prof. Dr. Andreas Marx

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511520

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      The most common epigenetic marker in eukaryotic cells—5-methyl-2′-deoxycytosine (5mC)—plays a key role in gene regulation. Therefore, the detection of 5mC can serve as an important biomarker for diagnostics. Direct detection of 5mC can be achieved by either incorporation of modified nucleotides or extension of 3′-modified primers by employing thermostable polymerases.

  14. Highlights

    1. Germanides

      [Ge=Ge]4− Dumbbells in the Zintl Phase Li3NaGe2

      Prof. Dr. Uwe Ruschewitz

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201600424

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      Ge−Ge double bonds: The reaction of elemental lithium, sodium, and germanium at 750 °C results in the Zintl phase Li3NaGe2, which, according to the Zintl–Klemm concept, contains [Ge=Ge]4− dumbbells with unprecedented short Ge−Ge distances. Based on structural, spectroscopic, and theoretical considerations, convincing evidence is given that Ge−Ge double bonds are in fact present.

  15. News

  16. Communications

    1. Chirality

      Monolayer Filaments versus Multilayer Stacking of Bent-Core Molecules

      Dr. Joanna Matraszek, Neha Topnani, Prof. Natasa Vaupotič, Prof. Hideo Takezoe, Prof. Jozef Mieczkowski, Dr. Damian Pociecha and Prof. Ewa Gorecka

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510123

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      Bent on being different: When lamellar crystals (B4 phase) of bent-core molecules were dissolved in organic solvents, gels composed of helical ribbons built up of molecular monolayers and bilayers were formed (see picture). Spontaneous chiral symmetry breaking occurred at the microscale in the B4 phase and the gels but only led to optical activity in the B4 phase. A dramatic increase in fluorescence was observed upon the transition to the gel state.

    2. Chemical Probes

      You have full text access to this OnlineOpen article
      Insights into 6-Methylsalicylic Acid Bio-assembly by Using Chemical Probes

      James S. Parascandolo, Dr. Judith Havemann, Helen K. Potter, Dr. Fanglu Huang, Dr. Elena Riva, Jack Connolly, Dr. Ina Wilkening, Dr. Lijiang Song, Prof. Peter F. Leadlay and Dr. Manuela Tosin

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201509038

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      Chemical probes capable of reacting with KS (ketosynthase)-bound biosynthetic intermediates were utilized for the investigation of the model type I iterative polyketide synthase 6-methylsalicylic acid synthase (6-MSAS) in vivo and in vitro. From the fermentation of fungal and bacterial 6-MSAS hosts in the presence of chain termination probes, a full range of biosynthetic intermediates was isolated (see examples) and characterized.

    3. Adhesive Coatings

      Nanomechanics of Poly(catecholamine) Coatings in Aqueous Solutions

      Chanoong Lim, Jun Huang, Sunjin Kim, Prof. Haeshin Lee, Prof. Hongbo Zeng and Prof. Dong Soo Hwang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510319

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      Give it some stick: The adhesive strength of self-polymerized catecholic coating layers was measured with a surface forces apparatus. The adhesive strength between poly(catecholamine) layers is 30-times higher than that between poly(catechol) layers. The origin of the strong attraction between poly(catecholamine) layers is possibly due to surface salt displacement, π–π stacking, and cation–π interactions involving the primary amine moiety.

    4. Protein Engineering

      A Rhizavidin Monomer with Nearly Multimeric Avidin-Like Binding Stability Against Biotin Conjugates

      Dr. Jeong Min Lee, Jung A. Kim, Tzu-Chi Yen, Dr. In Hwan Lee, Byungjun Ahn, Prof. Younghoon Lee, Dr. Chia-Lung Hsieh, Prof. Ho Min Kim and Prof. Yongwon Jung

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510885

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      Extremely high binding stability against various biotin conjugates has been observed in a monomeric avidin-like protein—enhanced monoavidin—that was developed from naturally dimeric rhizavidin by minimally disturbing the protein rigidity and additionally shielding the bound biotin. This stable monomeric biotin linker protein was further engineered to generate an unprecedented 24-meric avidin probe.

    5. Asymmetric Organocatalysis

      Exploiting the Multidentate Nature of Chiral Disulfonimides in a Multicomponent Reaction for the Asymmetric Synthesis of Pyrrolo[1,2-a]indoles: A Remarkable Case of Enantioinversion

      Dr. Alicia Galván, Dr. Adán B. González-Pérez, Prof. Dr. Rosana Álvarez, Prof. Dr. Angel R. de Lera, Prof. Dr. Francisco J. Fañanás and Prof. Félix Rodríguez

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511231

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      One way or the other: Some exceptional features of chiral disulfonimide organocatalysts are demonstrated in the context of a new highly selective synthesis of pyrrolo[1,2-a]indoles. A three-point coordination model explains the high enantioselectivity observed. An unusual switch of enantioselectivity was observed upon simple structural modification of the catalyst (see scheme).

    6. Agostic Interactions

      Experimental and Theoretical Evidence for an Agostic Interaction in a Gold(III) Complex

      Feriel Rekhroukh, Dr. Laura Estévez, Dr. Christian Bijani, Dr. Karinne Miqueu, Dr. Abderrahmane Amgoune and Dr. Didier Bourissou

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511111

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      Striking gold: The first direct evidence for an agostic interaction in a gold complex is reported. Low-temperature NMR spectroscopy is used to characterize a tricoordinate gold(III) alkyl complex featuring a C−H⋅⋅⋅Au agostic interaction. Theoretical analyses confirmed the presence of an attractive interaction between the C−H bond and the gold center.

    7. Drug Discovery

      Drug Repurposing Identifies Inhibitors of Oseltamivir-Resistant Influenza Viruses

      Dr. Ju Bao, Dr. Bindumadhav Marathe, Dr. Elena A. Govorkova and Prof. Jie J. Zheng

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511361

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      Finding a new purpose: A structure-based computational screen identified the FDA-approved drugs nalidixic acid and dorzolamide as potent inhibitors of the influenza H275Y neuraminidase mutant, but not the wild-type enzyme. H275Y is the most common drug-resistance mutation in neuraminidase, and this screening method enables rapid identification of inhibitors for newly emerging mutations.

  17. Cover Pictures

    1. Target-Induced and Equipment-Free DNA Amplification with a Simple Paper Device

      Dr. Meng Liu, Christy Y. Hui, Dr. Qiang Zhang, Jimmy Gu, Dr. Balamurali Kannan, Dr. Sana Jahanshahi-Anbuhi, Prof. Dr. Carlos D. M. Filipe, Prof. Dr. John D. Brennan and Prof. Dr. Yingfu Li

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201600678

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      A simple paper-based device for DNA amplification is described by J. D. Brennan, Y. Li, and co-workers in their Communication (DOI: 10.1002/anie.201509389). The paper device is printed with all enabling reagents, such as DNA polymerase, circular DNA template, and small building blocks, for building long-chain DNA molecules for visual detection. DNA amplification is automatically activated upon addition of a test sample that contains the DNA or RNA sequence of interest.

    2. Stretch-Induced Drug Delivery from Superhydrophobic Polymer Composites: Use of Crack Propagation Failure Modes for Controlling Release Rates

      Julia Wang, Dr. Jonah A. Kaplan, Dr. Yolonda L. Colson and Prof. Mark W. Grinstaff

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201600735

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      Strain-dependent release of agents can be realized by stretching of a multilayered polymer composite device. In their Communication (10.1002/anie.201511052), M. W. Grinstaff et al. demonstrate the use of crack propagation in electrosprayed superhydrophobic coatings to deliver anticancer agents (cisplatin, SN-38) in vitro to OE33 cells, and fluorescein diacetate to ex vivo bovine esophagus after integration of the device with an esophageal stent.

    3. Graphene Oxide Catalyzed C−H Bond Activation: The Importance of Oxygen Functional Groups for Biaryl Construction

      Dr. Yongjun Gao, Pei Tang, Hu Zhou, Dr. Wei Zhang, Hanjun Yang, Prof. Dr. Ning Yan, Dr. Gang Hu, Prof. Dr. Donghai Mei, Prof. Dr. Jianguo Wang and Prof. Dr. Ding Ma

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201600740

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      A heterogeneous, inexpensive, and environmentally friendly graphene oxide catalytic system can be used for the C−H bond arylation of benzene for the synthesis of biaryl compounds. In their Communication (DOI: 10.1002/anie.201510081), J. Wang, D. Ma, and co-workers show that added K+ ions are immobilized by oxygen-containing groups at the defect sites of the graphene oxide catalyst, which is essential for the catalytic activity.

  18. Reviews

    1. Synthetic Methods

      Stereoselective Halogenation in Natural Product Synthesis

      Prof. Won-jin Chung and Prof. Christopher D. Vanderwal

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201506388

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      With thousands of natural products containing halogen-bearing stereogenic centers, a wealth of methods have been developed for their stereocontrolled introduction in the context of total synthesis. This Review highlights the creative ways in which organic chemists have dealt with the challenges of stereochemically rich, halogenated natural products.

    2. Drug Discovery

      You have full text access to this OnlineOpen article
      Capturing Biological Activity in Natural Product Fragments by Chemical Synthesis

      Dr. Erika A. Crane and Prof. Dr. Karl Gademann

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201505863

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      Less is more: The desired biological activity of structurally complex natural products can be captured in small, truncated fragments. This process is enabled by chemical synthesis, which guides the discovery process and allows the secrets enshrined in natural products to be unlocked.

  19. Communications

    1. Organic Electronics | Hot Paper

      Synthesis of Nitrogen-Containing Rubicene and Tetrabenzopentacene Derivatives

      Dr. Young S. Park, Dr. David J. Dibble, Dr. Juhwan Kim, Robert C. Lopez, Eriberto Vargas and Prof. Alon A. Gorodetsky

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510320

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      Variants of classic polycyclic aromatic hydrocarbons: Nitrogen-containing rubicenes and tetrabenzopentacenes were prepared via a straightforward approach. The reported synthetic method may enable the development of electron transporting organic semiconductors and the eventual construction of larger carbonaceous systems.

    2. Homogeneous Catalysis

      Enantioselective Cyanosilylation of Ketones with Lithium(I) Dicyanotrimethylsilicate(IV) Catalyzed by a Chiral Lithium(I) Phosphoryl Phenoxide

      Dr. Manabu Hatano, Katsuya Yamakawa, Tomoaki Kawai, Dr. Takahiro Horibe and Prof. Dr. Kazuaki Ishihara

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510682

      Thumbnail image of graphical abstract

      Joint effort: A highly enantioselective cyanosilylation of ketones was developed by using a chiral lithium phosphoryl phenoxide aqua complex as an acid/base cooperative catalyst. The pentacoordinate silicate generated in situ from Me3SiCN/LiCN acts as a reactive cyano reagent. Moreover, a 30 gram scale reaction and the synthesis of the key precursor to (+)-13-hydroxyisocyclocelabenzine are described.

    3. Natural Product Synthesis

      Total Syntheses of (+)-Grandilodine C and (+)-Lapidilectine B and Determination of their Absolute Stereochemistry

      Masaya Nakajima, Prof. Dr. Shigeru Arai and Prof. Dr. Atsushi Nishida

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510561

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      Enantioselective total syntheses and determination of the absolute stereochemistry of the Kopsia alkaloids (+)-grandilodine C and (+)-lapidilectine B were accomplished. A key intermediate, spirodiketone, was synthesized in 3 steps and following enantioselective deprotonation, lactone formation, vinylation, allylic amination, and ring-closing metathesis, gave the above alkaloids in optically active form.

    4. Molecular Magnetism

      Rotating Magnetocaloric Effect in an Anisotropic Molecular Dimer

      Dr. Giulia Lorusso, Dr. Olivier Roubeau and Dr. Marco Evangelisti

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510468

      Thumbnail image of graphical abstract

      Molecular refrigerants: The magnetocaloric effect of anisotropic hydrated dysprosium acetate was studied. Possible applications as molecular refrigerant are discussed. Cooling is attained by rotating aligned single-crystal samples in a constant applied magnetic field (see picture).

    5. RNA Folding Stability

      You have full text access to this OnlineOpen article
      RNA Hairpin Folding in the Crowded Cell

      Mimi Gao, David Gnutt, Axel Orban, Dr. Bettina Appel, Francesco Righetti, Prof. Dr. Roland Winter, Prof. Dr. Franz Narberhaus, Prof. Dr. Sabine Müller and Prof. Dr. Simon Ebbinghaus

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201510847

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      From the test tube to the cell: In-cell folding experiments spatio-temporally resolve RNA hairpin stability in the living cell. The folding stability inside cells is found to be comparable to that in dilute physiological buffer.

    6. Hydrogen Bonding

      Dithienophosphole-Based Phosphinamides with Intriguing Self-Assembly Behavior

      Zisu Wang, Benjamin S. Gelfand and Prof. Dr. Thomas Baumgartner

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511171

      Thumbnail image of graphical abstract

      New HOPe: Dithienophosphole-based phosphinamides (see structure) display rotationally flexible hydrogen bonding that contrasts with that of their carboxamide cousins. Besides the novel hydrogen-bonding motif, these compounds also demonstrated unique photophysical and amphiphilic properties as a result of hydrogen-bond-directed self-assembly.

    7. Protein Catenanes

      Cellular Synthesis of Protein Catenanes

      Xiao-Wei Wang and Prof. Dr. Wen-Bin Zhang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201511640

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      Let's get together: The combination of a protein dimerization domain and genetically encoded SpyTag–SpyCatcher protein chemistry enables the cellular synthesis of topologically complex protein catenanes and mechanically interlocked protein “tadpoles” through programmed posttranslational modification.

  20. Cover Pictures

    1. Catalytically Active Rh Sub-Nanoclusters on TiO2 for CO Oxidation at Cryogenic Temperatures

      Hongling Guan, Dr. Jian Lin, Dr. Botao Qiao, Dr. Xiaofeng Yang, Dr. Lin Li, Dr. Shu Miao, Prof. Jingyue Liu, Prof. Aiqin Wang, Prof. Xiaodong Wang and Prof. Tao Zhang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/anie.201600636

      Thumbnail image of graphical abstract

      Three milestones in the history of CO oxidation are shown in this picture. One century ago Langmuir investigated CO oxidation using Pt group metals which work at temperatures higher than 373 K. In the 1980s Haruta et al. discovered that Au nanoparticles with sizes of 2 nm are active for oxidation of CO at 200 K. In their Communication (DOI: 10.1002/anie.201510643), X. Wang, T. Zhang et al. show that CO is oxidized at 173 K using Rh sub-nanoclusters supported on TiO2.

  21. Communications

    1. Reaction Mechanisms

      You have full text access to this OnlineOpen article
      19F NMR and DFT Analysis Reveal Structural and Electronic Transition State Features for RhoA-Catalyzed GTP Hydrolysis

      Dr. Yi Jin, Dr. Robert W. Molt Jr., Prof. Dr. Jonathan P. Waltho, Prof. Dr. Nigel G. J. Richards and Prof. Dr. G. Michael Blackburn

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201509477

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      Guanosine 5′-triphosphate hydrolysis by the small G protein, RhoA, was analyzed by combining X-ray, 19F NMR, and DFT calculations. A transition state model based on 19F NMR spectra is proposed for nucleophilic attack of water on GTP, founded on an extensive network of 20 hydrogen bonds. This network disrupts inhibitory hydrogen bonds that stabilize an unreactive ground state conformation.

    2. Oxygen Electrochemistry

      Experimental and Computational Analysis of the Solvent-Dependent O2/Li+-O2 Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

      David G. Kwabi, Dr. Vyacheslav S. Bryantsev, Thomas P. Batcho, Dr. Daniil M. Itkis, Prof. Carl V. Thompson and Prof. Yang Shao-Horn

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201509143

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      The free-energy landscape of reactions involved in the Li oxygen reduction reaction (ORR) were obtained by rotating ring disk (RRD) measurements and calculations. Differences in redox potentials of O2/O2 and O2/Li+-O2 couples vs. Li+/Li in dimethoxyethane (DME) and dimethylsulfoxide (DMSO) reflect the influence of increasing solvation on the free energy of O2 formation vs. Li+/Li and Li+−O2 coupling.

    3. Electrodeposition

      Dendrite-Free Nanocrystalline Zinc Electrodeposition from an Ionic Liquid Containing Nickel Triflate for Rechargeable Zn-Based Batteries

      Dr. Zhen Liu, Tong Cui, Dr. Giridhar Pulletikurthi, Dr. Abhishek Lahiri, Dr. Timo Carstens, Mark Olschewski and Prof. Dr. Frank Endres

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201509364

      Thumbnail image of graphical abstract

      Deposits and returns: A dendrite-free zinc deposit with a nanocrystalline structure is obtained when nickel triflate is used as an additive in a zinc triflate containing ionic liquid (IL). The formation of a thin layer of Zn–Ni alloy and a solid electrolyte interface (SEI) layer on the electrode affect the nucleation and growth of zinc.

    4. Disilane Chromophores

      Bright Solid-State Emission of Disilane-Bridged Donor–Acceptor–Donor and Acceptor–Donor–Acceptor Chromophores

      Masaki Shimada, Mizuho Tsuchiya, Dr. Ryota Sakamoto, Dr. Yoshinori Yamanoi, Prof. Eiji Nishibori, Dr. Kunihisa Sugimoto and Prof. Hiroshi Nishihara

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201509380

      Thumbnail image of graphical abstract

      Disilane-bridged donor–acceptor–donor (D-Si-Si-A-Si-Si-D) molecules and acceptor–donor–acceptor (A-Si-Si-D-Si-Si-A) compounds display strong solid-state emission (see picture) and aggregation-induced emission (AIE). X-ray diffraction reveals there is no π–π stacking in crystals to suppress intermolecular interaction.

    5. Boron OLEDs | Hot Paper

      Pyridyl Pyrrolide Boron Complexes: The Facile Generation of Thermally Activated Delayed Fluorescence and Preparation of Organic Light-Emitting Diodes

      Yi-Jiun Shiu, Yung-Chen Cheng, Wei-Lung Tsai, Prof. Chung-Chih Wu, Chun-Tien Chao, Dr. Chin-Wei Lu, Prof. Yun Chi, Yi-Ting Chen, Dr. Shih-Hung Liu and Prof. Pi-Tai Chou

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201509231

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      Reducing the gap: Using a boron atom as the spiro linker between an electron-deficient pyridyl pyrrolide and an electron-donating phenylcarbazolyl or triphenylamine fragment, boron complexes with a narrow HOMO–LUMO orbital overlap, small singlet–triplet energy gap (down to 38 meV), and strong thermally activated delayed fluorescence (TADF) were prepared. For the first time boron-complex-based OLEDs show a significant TADF contribution.

    6. Gelators

      A Sugar-Based Gelator for Marine Oil-Spill Recovery

      Amol M. Vibhute, Dr. Venkatanarayana Muvvala and Prof. Dr. Kana M. Sureshan

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510308

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      Solid solidifier: Simple, cheap, and easy-to-prepare sugar-based phase-selective gelators were prepared that can selectively congeal oil from a mixture of oil and water and can be spread in solid powder form. Efficient crude-oil recovery from a mixture of water and crude oil was demonstrated.

    7. Bioprocess-Inspired Synthesis

      Mussel-Directed Synthesis of Nitrogen-Doped Anatase TiO2

      Dr. Jingjing Xie, Prof. Hao Xie, Prof. Bao-Lian Su, Prof. Yi-bing Cheng, Prof. Xiaodong Du, Dr. Hui Zeng, Dr. Menghu Wang, Prof. Weimin Wang, Prof. Hao Wang and Prof. Zhengyi Fu

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201509906

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      The pearl is the oyster′s autobiography: Based on a natural pearl culture process, hierarchically meso/macroporous nitrogen-doped TiO2 is obtained directly in living Cristaria plicata at ambient temperature, demonstrating enhanced visible-light photocatalytic activity in both chemical waste remediation and hydrogen generation. Intracellular proteins are found to be involved in the formation of TiO2.

    8. Thin Films

      Solution Layer Deposition: A Technique for the Growth of Ultra-Pure Manganese Oxides on Silica at Room Temperature

      Dr. Jérémy Cure, Dr. Kilian Piettre, Dr. Yannick Coppel, Dr. Eric Beche, Dr. Jérôme Esvan, Vincent Collière, Dr. Bruno Chaudret and Dr. Pierre Fau

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201509715

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      Wet Mn deposition: The deposition of high-purity manganese oxide layers on a silica surface was achieved by Solution Layer Deposition: a solution chemistry route to form functional oxides layers. The mechanism taking place on the surface was determined by coupling 29Si MAS NMR, XPS, and HRTEM analyses.

    9. Biomimetic Oxidation

      Hydroxylation versus Halogenation of Aliphatic C−H Bonds by a Dioxygen-Derived Iron–Oxygen Oxidant: Functional Mimicking of Iron Halogenases

      Sayanti Chatterjee and Dr. Tapan Kanti Paine

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201509914

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      An oxidative copycat: An iron(II)–benzilate complex of a facial N3 ligand promoted the oxidative halogenation of aliphatic C−H bonds in the presence of a protic acid and a halide. An iron(IV)–oxo–halide species is proposed as the active oxidant in this biomimetic process (see scheme).

    10. NHC Catalysis

      Enantioselective N-Heterocyclic Carbene Catalysis by the Umpolung of α,β-Unsaturated Ketones

      Yuji Nakano and Prof. Dr. David W. Lupton

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510106

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      One for addition: 1,4-Addition of N-heterocyclic carbenes (NHCs) into conjugate acceptors followed by tautomerization provides the β-azolium ylide. This intermediate provides access to a range of enantioenriched 2-aryl propionates. The reaction was possible using electron-rich N-substituted triazolium catalysts in the presence of hexafluoroisopropanol (HFIP).

    11. Pincer Ligands

      A Cobalt(I) Pincer Complex with an η2-Caryl−H Agostic Bond: Facile C−H Bond Cleavage through Deprotonation, Radical Abstraction, and Oxidative Addition

      Sathiyamoorthy Murugesan, Dr. Berthold Stöger, Dr. Ernst Pittenauer, Prof. Dr. Günter Allmaier, Prof. Dr. Luis F. Veiros and Prof. Dr. Karl Kirchner

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510145

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      Protonation of [Co(PCPNMe-iPr)(CO)2] yields the CoI pincer complex [Co(ϰ3P,CH,P-P(CH)PNMe-iPr)(CO)2]+ featuring an η2-Caryl-H agostic bond. This bond can be cleaved easily by deprotonation, radical abstraction with oxygen or TEMPO to afford the paramagnetic CoII PCP complex [Co(PCPNMe-iPr)(CO)2]+, or by CNtBu promoted oxidative addition to give CoIII PCP hydride complexes.

    12. Polynuclear Complexes

      A Bis(Diphosphanyl N-Heterocyclic Carbene) Gold Complex: A Synthon for Luminescent Rigid AuAg2 Arrays and Au5 and Cu6 Double Arrays

      Pengfei Ai, Dr. Matteo Mauro, Prof. Luisa De Cola, Dr. Andreas A. Danopoulos and Dr. Pierre Braunstein

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510150

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      Crossing paths: A mononuclear bis(NHC)/AuI (NHC=N-heterocyclic carbene) cationic complex with a rigid bis(phosphane)-functionalized NHC ligand (PCNHCP) provides access to unique Au, Au/Ag, and Cu arrays. These arrays display metallophilicity-based photoluminescence.

    13. Photoswitching | Hot Paper

      Giant Amplification of Photoswitching by a Few Photons in Fluorescent Photochromic Organic Nanoparticles

      Dr. Jia Su, Prof. Tuyoshi Fukaminato, Dr. Jean-Pierre Placial, Dr. Tsunenobu Onodera, Ryuju Suzuki, Prof. Hidetoshi Oikawa, Arnaud Brosseau, Dr. François Brisset, Dr. Robert Pansu, Prof. Keitaro Nakatani and Dr. Rémi Métivier

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510600

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      Amped up: Fluorescent photochromic organic nanoparticles, showing bright red emission, complete ON–OFF contrast with full reversibility, and excellent fatigue resistance, have been prepared. They exhibit a full fluorescence quenching and recovery under light illumination at very low photochromic conversion levels, leading to a “giant amplification of fluorescence photoswitching”.

    14. Allylic Compounds

      Copper-Catalyzed Borylcupration of Allenylsilanes

      Weiming Yuan, Liu Song and Prof. Dr. Shengming Ma

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510354

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      Do a (dis)favor: A new highly selective copper-catalyzed borylcupration of allenylsilanes for the synthesis of thermodynamically disfavored 3-silylalk-2(Z)-enylboronates was developed. Such stereodefined allylic boronates containing an extra alkenyl silane moiety are useful organodimetallic reagents for organic synthesis.

    15. Biomimetic Hosts

      Synthetic Receptors for the High-Affinity Recognition of O-GlcNAc Derivatives

      Pablo Rios, Tom S. Carter, Dr. Tiddo J. Mooibroek, Prof. Matthew P. Crump, Micke Lisbjerg, Prof. Michael Pittelkow, Nitin T. Supekar, Prof. Geert-Jan Boons and Prof. Anthony P. Davis

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510611

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      Two carbohydrate receptors (see scheme) were prepared directly from a pyrenyl tetraamine and an isophthaloyl derivative. With extended aromatic surfaces linked by polar spacers, they are well suited to binding all-equatorial monosaccharides, showing especially high affinities for β-linked N-acetylglucosamine (GlcNAc).

    16. Lewis Acid Catalysis

      Friedel–Crafts-Type Intermolecular C−H Silylation of Electron-Rich Arenes Initiated by Base-Metal Salts

      Dr. Qin Yin, Dr. Hendrik F. T. Klare and Prof. Dr. Martin Oestreich

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510469

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      So simple: Combining a base-metal salt and NaBArF4 generates a Lewis acid that promotes the C−H silylation of electron-rich arenes with hydrosilanes. The more obvious choice, chlorosilanes, do not participate in this electrophilic aromatic substitution. No base is required to absorb the protons released, so this process resembles a typical Friedel–Crafts reaction. ArF=3,5-bis(trifluoromethyl)phenyl.

    17. Semiconducting Films

      Porous Organic Polymers Films with Tunable Work Functions and Selective Hole and Electron Flows for Energy Conversions

      Dr. Cheng Gu, Ning Huang, Youchun Chen, Huanhuan Zhang, Shitong Zhang, Prof. Fenghong Li, Prof. Yuguang Ma and Prof. Dr. Donglin Jiang

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510723

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      Nanofilters for electrons and holes: Porous organic polymer films were designed to have tunable work functions, and were used to control selective hole and electron flows to achieve high- efficiency energy conversions, including solar cells and light-emitting diodes.

    18. Kinetic Resolution

      Chiral Phosphoric Acid Catalyzed Kinetic Resolution of Indolines Based on a Self-Redox Reaction

      Dr. Kodai Saito and Prof. Dr. Takahiko Akiyama

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510692

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      Asymmetric synthesis of indolines was achieved by oxidative kinetic resolution of the indoline racemate, involving the formation and reduction of iminium intermediate using a chiral phosphoric acid catalyst and salicylaldehyde derivative. This method was applicable to various racemic indolines and the corresponding products were obtained in good yields with excellent enantioselectivities.

    19. Membrane Surfaces

      CuSO4/H2O2-Induced Rapid Deposition of Polydopamine Coatings with High Uniformity and Enhanced Stability

      Chao Zhang, Yang Ou, Wen-Xi Lei, Prof. Dr. Ling-Shu Wan, Prof. Dr. Jian Ji and Prof. Dr. Zhi-Kang Xu

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510724

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      Mussel-inspired surfaces: A facile and robust approach to rapid construction polydopamine (PDA) coatings on various substrates is presented. The CuSO4/H2O2-triggered PDA coatings show high uniformity, enhanced stability, excellent hydrophilicity, antioxidant ability, and antibacterial performance.

    20. Process Development

      Overcoming Phase-Transfer Limitations in the Conversion of Lipophilic Oleo Compounds in Aqueous Media—A Thermomorphic Approach

      M.Sc. Tom Gaide, M.Sc. Jens M. Dreimann, Prof. Dr. Arno Behr and Dr. Andreas J. Vorholt

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510738

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      Bringing cat and dog together: The intelligent selection of solvents facilitates the both the reaction and the recovery of the Rh/SulfoXantphos catalyst. Green solvents (water and 1-butanol) and the use of a renewable feedstock contribute to the development of sustainable processes.

    21. C−H Activation | Hot Paper

      A General Strategy for the Nickel-Catalyzed C−H Alkylation of Anilines

      Zhixiong Ruan, Sebastian Lackner and Prof. Dr. Lutz Ackermann

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510743

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      One for all: An inexpensive nickel catalyst enables the C−H alkylation of pyrimidyl anilines with both primary and secondary alkyl halides. The directing group (DG) could be easily removed in a traceless fashion, and the products contain key structural motifs of important anticancer drugs.

    22. Flow Batteries

      A Highly Ion-Selective Zeolite Flake Layer on Porous Membranes for Flow Battery Applications

      Zhizhang Yuan, Xiangxue Zhu, Prof. Mingrun Li, Wenjing Lu, Prof. Xianfeng Li and Prof. Huamin Zhang

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510849

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      Go with the flow: For the first time, a zeolite-coated membrane that can perfectly separate ions of different sizes was fabricated for use in flow battery applications. See picture; large and small spheres are redox-active and non-reaction ions, respectively.

    23. Ceria Catalysis

      Oxychlorination–Dehydrochlorination Chemistry on Bifunctional Ceria Catalysts for Intensified Vinyl Chloride Production

      Matthias Scharfe, Pedro A. Lira-Parada, Vladimir Paunović, Maximilian Moser, Dr. Amol P. Amrute and Prof. Javier Pérez-Ramírez

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510903

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      One material, two functions: Ceria is used as the catalyst to produce the vinyl chloride monomer (VCM) from C2H4 in one step and in high yield, enabling redox-catalyzed oxychlorination and acid-catalyzed dehydrochlorination on the same material. The bifunctional character of CeO2 intensifies the current two-step process for polyvinyl chloride manufacture and brings great stability advantages with respect to the archetypical CuCl2 oxychlorination catalyst.

    24. Porphyrinoids

      Macrocyclic Transformations from Norrole to Isonorrole and an N-Confused Corrole with a Fused Hexacyclic Ring Triggered by a Pyrrole Substituent

      Miao Li, Pingchun Wei, Dr. Masatoshi Ishida, Xin Li, Mathew Savage, Rui Guo, Prof. Dr. Zhongping Ou, Prof. Dr. Sihai Yang, Prof. Dr. Hiroyuki Furuta and Prof. Dr. Yongshu Xie

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510879

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      Confusing corroles: The pyrrole-substituted corrole isomer norrole underwent an oxidative fusion reaction to afford a unique N-Cmeso-fused isonorrole. The isonorrole was subsequently converted into singly and doubly N-CAr-fused N-confused corroles with unprecedented fused []-tetra- and []hexacyclic structures, respectively.

    25. Metalloid Clusters

      The Largest Metalloid Group 14 Cluster, Ge18[Si(SiMe3)3]6: An Intermediate on the Way to Elemental Germanium

      Dr. Oleksandr Kysliak, Dr. Claudio Schrenk and Prof. Dr. Andreas Schnepf

      Article first published online: 28 JAN 2016 | DOI: 10.1002/anie.201510831

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      Germanium snapshot: The oxidation of [Ge9(Hyp)3] (Hyp=Si(SiMe3)3) with an iron(II) salt leads to Ge18(Hyp)6 (1), the largest metalloid Group 14 cluster that has been structurally characterized to date. 1 can be regarded as a trapped first intermediate of the formation of the elemental phase Ge(cF136), providing first insights into the principles of the formation of elemental germanium from molecular precursors.