Angewandte Chemie International Edition

Cover image for Vol. 55 Issue 27

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, ChemPlusChem, Zeitschrift für Chemie

  1. Communications

    1. Vibrational Spectroscopy

      Toward Extreme Biophysics: Deciphering the Infrared Response of Biomolecular Solutions at High Pressures

      Sho Imoto, Patrick Kibies, Christopher Rosin, Roland Winter, Stefan M. Kast and Dominik Marx

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201602757

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      Squeeze it out of them: Trimethylamine N-oxide (TMAO) is known to stabilize protein structures at extreme pressures, possibly through hydrogen bonding. A combination of FTIR spectroscopy and computer simulation has now been used to connect pressure-induced changes in the IR spectrum of TMAO (see picture) to a locally enhanced hydrogen-bonding network at high compression. The insight gained should be transferable to biomolecules in their native solvent.

    2. Electrocatalysis

      Highly Efficient, Selective, and Stable CO2 Electroreduction on a Hexagonal Zn Catalyst

      Da Hye Won, Hyeyoung Shin, Jaekang Koh, Jaehoon Chung, Hee Sang Lee, Prof. Hyungjun Kim and Prof. Seong Ihl Woo

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201602888

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      CO2 conversion: A design strategy for efficient carbon dioxide reduction is suggested using a well-synthesized hierarchical hexagonal Zn catalyst which shows highly selective and, more importantly, stable performance towards carbon monoxide production (see picture). The manipulation of the Zn crystal structure and its facet ratio (101)/(002) can be used as a key control factor for product selectivity.

    3. NMR Spectroscopy

      Selective Protein Hyperpolarization in Cell Lysates Using Targeted Dynamic Nuclear Polarization

      Thibault Viennet, Dr. Aldino Viegas, Arne Kuepper, Sabine Arens, Prof. Dr. Vladimir Gelev, Prof. Dr. Ognyan Petrov, Prof. Dr. Tom N. Grossmann, Prof. Dr. Henrike Heise and Dr. Manuel Etzkorn

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201603205

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      Directing polarization: By using a biradical-labeled ligand, dynamic nuclear polarization (DNP) can be efficiently and very specifically directed to a target protein. This behavior allows to filter out the signal of the target protein from a large backround (see picture), enabling a selective solid-state NMR characterization in increasingly native environments such as found in crude cell lysates.

    4. Hydrogen Bonding

      Hydrogen-Bond Cooperativity in Formamide2–Water: A Model for Water-Mediated Interactions

      Prof. Susana Blanco, Pablo Pinacho and Prof. Juan Carlos López

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201603319

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      Isolated formamide2–water can be taken as a simple model for water-mediated interactions and amide self-association. The structure and the electric field gradient determined at the nitrogen nuclei measured from the rotational spectrum reveal the subtle inductive effects that polarize the amide group and alter the C=O and N−C distances of formamide.

    5. Heterocycles

      Transition-Metal-Free Regioselective Alkylation of Pyridine N-Oxides Using 1,1-Diborylalkanes as Alkylating Reagents

      Woohyun Jo, Junghoon Kim, Seoyoung Choi and Prof. Dr. Seung Hwan Cho

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201603329

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      Going to the source: The transition-metal-free alkylation of pyridine N-oxides using 1,1-diborylalkanes as alkyl sources proceeds efficiently for a wide range of pyridine N-oxides and 1,1-diborylalkanes with excellent regioselectivity, thus affording C2-alkylated pyridines in good yields.

    6. Protein Engineering

      Accelerating the Association of the Most Stable Protein–Ligand Complex by more than Two Orders of Magnitude

      Dr. Christoph Giese, Jonathan Eras, Anne Kern, Dr. Martin A. Schärer, Dr. Guido Capitani and Prof. Rudi Glockshuber

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201603652

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      Accelerated binding of the protein FimGt to its natural peptide ligand DsF was achieved by rational design of FimGt and DsF variants with enhanced electrostatic interactions. Binding was accelerated by two orders of magnitude without structural perturbation of the complex. The most stable and fastest associating complex (see picture, shown in green) showed a dissociation constant of 8.8×10−22m (wild-type complex shown in gray).

    7. Molecular Recognition | Hot Paper

      Unidirectional Threading into a Bowl-Shaped Macrocyclic Trimer of Boron–Dipyrrin Complexes through Multipoint Recognition

      Dr. Takashi Nakamura, Gento Yamaguchi and Prof. Dr. Tatsuya Nabeshima

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201603821

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      Going in to bowl: A bowl-shaped macrocyclic trimer of a boron–dipyrrin complex has been synthesized in which six polarized B−F bonds are directed towards the center of the macrocycle for strong recognition. Cationic ammonium guests are strongly captured from the convex side of the macrocycle by hydrogen bonding, Coulomb forces, and C−H⋅⋅⋅π interactions and thread unidirectionally through the complex.

    8. Cycloaddition

      Cy-SaBOX/Copper(II)-Catalyzed Highly Diastereo- and Enantioselective Synthesis of Bicyclic N,O Acetals

      Qiong-Jie Liu, Dr. Lijia Wang, Qi-Kai Kang, Prof. Dr. X. Peter Zhang and Prof. Dr. Yong Tang

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201603911

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      N,O skeletons: A protocol for the enantioselective construction of useful and important bicyclic N,O-acetal skeletons is described. Excellent yields and excellent stereoselectivities were obtained for a broad scope of substrates, and even with only a 1 mol % catalyst loading on gram scale.

  2. Obituaries

    1. Fritz Stern (19262016)

      Prof. Dr. Gerhard Ertl and Prof. Dr. Bretislav Friedrich

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201605519

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      The German-born American historian Fritz Stern passed away on May 18, 2016 in New York. Stern dedicated his life's work to the study of European, particularly German, cultural history. Well aware that Germany's rise to preeminence during the 19th century was rooted in its scientific-technological culture, Fritz Stern created a portrait gallery of key protagonists of that “age of genius” which included Fritz Haber, his godfather.

  3. Communications

    1. Radical Coupling

      Monofluoroalkenylation of Dimethylamino Compounds through Radical–Radical Cross-Coupling

      Dr. Jin Xie, Dr. Jintao Yu, Dr. Matthias Rudolph, Dr. Frank Rominger and Prof. Dr. A. Stephen K. Hashmi

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201602347

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      Privileged products: A α-C(sp3)−H monofluoroalkenylation of unactivated tertiary amines through a mild, efficient, and redox-neutral route delivers privileged tetrasubstituted monofluoroalkenes under photoredox catalysis through the radical–radical cross- coupling of α-aminoalkyl radicals with monofluoroalkenyl radicals. This method enables the challenging late-stage monofluoroalkenylation of complex molecules.

    2. ALD Precursors

      You have full text access to this OnlineOpen article
      Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines

      Dr. Sang Bok Kim, Chuanxi Yang, Dr. Tamara Powers, Dr. Luke M. Davis, Xiabing Lou and Prof. Dr. Roy G. Gordon

      Version of Record online: 28 JUN 2016 | DOI: 10.1002/anie.201602406

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      Fling the window open: Dimeric amidinate complexes 1 were obtained as volatile white crystals from a redox reaction between Ca metal and amidine ligands (see scheme). The vapor of the formamidinate complex was used for the synthesis of conformal and uniform polycrystalline CaS films by ALD. With this complex, the ALD window was considerably wider and lower in temperature (150–280 °C) than that observed with the most commonly used ALD precursor.

    3. Nanoparticles

      Luminescent Gold Nanoparticles with Size-Independent Emission

      Dr. Jinbin Liu, Paul N. Duchesne, Dr. Mengxiao Yu, Xingya Jiang, Xuhui Ning, Rodrigo D. Vinluan III, Prof. Dr. Peng Zhang and Prof. Dr. Jie Zheng

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201602795

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      Size-independent emission has been widely observed for ultrasmall thiolated gold nanoparticles (AuNPs). Herein, the emission wavelength of thiolated AuNPs is found to depend on the surface coverage and local binding geometry of the thiolate ligands (glutathione) on the AuNP; AuNPs with different surface coverages emit at different wavelengths in spite of their identical size (ca. 2.5 nm).

    4. Enzyme Catalysis

      Hydrostatic Pressure Studies Distinguish Global from Local Protein Motions in C−H Activation by Soybean Lipoxygenase-1

      Dr. Shenshen Hu, Jérôme Cattin-Ortolá, Dr. Jeffrey W. Munos and Prof. Dr. Judith P. Klinman

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201603592

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      Under pressure: The effect of hydrostatic pressure (P) on the steady-state rate constants, substrate kinetic isotope effects, and the temperature dependency of these parameters enables isotope-dependent, local protein motions to be distinguished from the more global, isotope-independent conformational landscape in the primary C−H activation step of the enzyme soybean lipoxygenase-1 (structure shown, active site circled).

  4. Highlights

    1. Polycycles

      A Stable π-Conjugated Singlet Biradical

      Dr. Felix Hinkel, Dr. Jan Freudenberg and Prof. Uwe H. F. Bunz

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201605490

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      A large polycyclic hydrocarbon with a singlet biradical ground state has been obtained by the combined effects of topology and electron-accepting aromatic substituents, which stabilize its open-shell singlet state.

  5. Communications

    1. Metal-Oxide Films | Hot Paper

      Tuning the Reactivity of Ultrathin Oxides: NO Adsorption on Monolayer FeO(111)

      Dr. Lindsay R. Merte, Dr. Christopher J. Heard, Dr. Feng Zhang, Dr. Juhee Choi, Mikhail Shipilin, Dr. Johan Gustafson, Prof. Jason F. Weaver, Prof. Henrik Grönbeck and Prof. Edvin Lundgren

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201601647

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      Tailored chemisorption: Supported oxide monolayers exhibit novel chemical properties that can be exploited for applications in catalysis. Drastic differences in adsorption of NO on supported FeO monolayers are observed, depending on the metal substrate. These differences are found to result from steric blocking, which is due to substrate-induced buckling of the FeO films.

    2. Luminescence Sensors

      Coordinatively Unsaturated Lanthanide(III) Helicates: Luminescence Sensors for Adenosine Monophosphate in Aqueous Media

      Jashobanta Sahoo, Rajendran Arunachalam, Dr. Palani S. Subramanian, Dr. Eringathodi Suresh, Dr. Arto Valkonen, Prof. Dr. Kari Rissanen and Prof. Dr. Markus Albrecht

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201604093

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      One AMP is enough: A coordinatively unsaturated double-stranded dinuclear europium(III) helicate shows adenosine monophosphate (AMP)-specific luminescence response even in the presence of highly charged adenosine di- or triphosphate (ADP or ATP).

    3. Cross-Coupling

      Direct Access to α,α-Difluoroacylated Arenes by Palladium-Catalyzed Carbonylation of (Hetero)Aryl Boronic Acid Derivatives

      Thomas L. Andersen, Mette W. Frederiksen, Katrine Domino and Prof. Dr. Troels Skrydstrup

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201604152

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      Yielding to pressure: The title reaction produces aryl α,α-difluoro-β-ketoamides and -esters from readily available difluorinated carboxylic acid derivatives by employing gaseous carbon monoxide. The method features low CO pressures and high functional-group tolerance. The fluorinated products can be transformed into a variety fluoroalkylated structures.

    4. Enantioselectivity

      Construction of Chiral Tri- and Tetra-Arylmethanes Bearing Quaternary Carbon Centers: Copper-Catalyzed Enantioselective Propargylation of Indoles with Propargylic Esters

      Kouhei Tsuchida, Yasushi Senda, Dr. Kazunari Nakajima and Prof. Dr. Yoshiaki Nishibayashi

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201604182

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      All-star all-carbon: The title reaction leads to the enantioselective construction of an all-carbon quaternary stereocenter. The subsequent derivatization of terminal alkyne moiety, into aromatic rings, is useful for the construction of chiral all-carbon substituted tri- and tetra-arylmethanes. The one-pot procedure demonstrated herein provides a successful example of the enantioselective preparation of a tetraarylmethane.

    5. Metal–Organic Frameworks | Hot Paper

      Flexible Zirconium Metal-Organic Frameworks as Bioinspired Switchable Catalysts

      Shuai Yuan, Lanfang Zou, Dr. Haixia Li, Ying-Pin Chen, Dr. Junsheng Qin, Dr. Qiang Zhang, Dr. Weigang Lu, Prof. Dr. Michael B. Hall and Prof. Dr. Hong-Cai Zhou

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201604313

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      An open and shut case: The inherent cavities and dynamic behavior of flexible MOFs, bear a close resemblance to regulatory enzymes. Switchable activation and deactivation of their catalytic properties occurs on pore opening and closing by solvation/solvent removal.

  6. Highlights

    1. Imaging

      Imaging Bioorthogonal Groups in Their Ultrastructural Context with Electron Microscopy

      Daphne M. van Elsland and Sander I. van Kasteren

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201604672

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      Spitting image: Herein a recent paper on the imaging of bioorthogonal groups using three-dimensional electron microscopy is discussed. The work has demonstrated electron microscopy imaging as a technique suitable for gaining structural information on bioorthogonal groups in their cellular context.

  7. Communications

    1. Platinum Clusters

      Monomeric Chini-Type Triplatinum Clusters Featuring Dianionic and Radical-Anionic π*-Systems

      Brandon R. Barnett, Prof. Arnold L. Rheingold and Prof. Joshua S. Figueroa

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201604903

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      Unstacking the deck: The dianionic “Chini clusters” consist of stacked triangulo-Pt3(CO)6 units, but the parent species [Pt3(CO)6]2− has eluded structural characterization. Sterically demanding m-terphenyl isocyanides (CNArDipp2) allow for isolation of isolobal K2[Pt3(μ-CO)3(CNArDipp2)3] as well as the corresponding monoanionic radical. The highest occupied orbital in both is primarily CO/CNR π*, which results in ligand-based redox non-innocence.

  8. Cover Pictures

    1. You have free access to this content
      Dizinc Lactide Polymerization Catalysts: Hyperactivity by Control of Ligand Conformation and Metallic Cooperativity

      Arnaud Thevenon, Dr. Charles Romain, Michael S. Bennington, Dr. Andrew J. P. White, Hannah J. Davidson, Prof. Sally Brooker and Prof. Charlotte K. Williams

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201605383

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      The hyperactivity of dizinc catalysts used for the ring-opening polymerization (ROP) of racemic lactide (LA) was studied. In their Communication (DOI: 10.1002/anie.201602930), S. Brooker, C. K. Williams et al. show that “folded” macrocyclic catalysts have high turnover frequencies (60 000 h−1), up to 5500 times those of their “planar” analogues in the conversion of lactide (from corn) into polylactide (PLA). The catalysts also perform well under immortal conditions.

  9. Communications

    1. Shape-Selective Catalysis

      Encapsulating Palladium Nanoparticles Inside Mesoporous MFI Zeolite Nanocrystals for Shape-Selective Catalysis

      Tian-Lu Cui, Wen-Yu Ke, Wen-Bei Zhang, Hong-Hui Wang, Prof. Dr. Xin-Hao Li and Prof. Dr. Jie-Sheng Chen

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201602429

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      Shape-selective reactions over a palladium nanoparticle (Pd NP) based catalyst were achieved by integrating Pd NPs inside mesoporous silicalite-1 nanocrystals. The unique micro- and mesoporous structure of the zeolite nanocrystals endowed Pd NPs both high stability and excellent shape-selectivity for organic synthesis.

    2. Organocatalysis

      Catalytic Asymmetric Synthesis of Dihydropyrido[1,2-a]indoles from Nitrones and Allenoates

      Wiktoria H. Pace, Dr. Dong-Liang Mo, Tyler W. Reidl, Dr. Donald J. Wink and Prof. Laura L. Anderson

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201602568

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      Take your partners, join the dance: Chiral squaramide catalysts promote the asymmetric synthesis of dihydropyridoindoles from simple, non-indole reagents. In this complex cascade process, the catalyst appears to interact with reactive intermediates to control both regio- and enantioselectivity. A subsequent epimerization step increases the diastereomeric ratio of the products, while retaining high enantiomeric purity.

    3. Phase Transitions

      Phase Transition of a Structure II Cubic Clathrate Hydrate to a Tetragonal Form

      Dr. Satoshi Takeya, Dr. Hiroshi Fujihisa, Dr. Hiroshi Yamawaki, Dr. Yoshito Gotoh, Prof. Ryo Ohmura, Dr. Saman Alavi and Dr. John A. Ripmeester

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201602733

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      Changing phases: The thermally induced cubic–tetragonal phase transition of sII clathrate hydrate containing 2-propanol causes volume expansion. This transition is most likely related to the restriction of the motion of 2-propanol within the host water cage.

    4. Biophysics

      You have full text access to this OnlineOpen article
      Electrostatics and Intrinsic Disorder Drive Translocon Binding of the SRP Receptor FtsY

      Dr. Nils-Alexander Lakomek, Dr. Albena Draycheva, Dr. Thomas Bornemann and Prof. Dr. Wolfgang Wintermeyer

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201602905

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      Integral membrane proteins in bacteria are co-translationally targeted to the translocon for membrane insertion via the signal recognition particle (SRP) pathway. The SRP receptor FtsY and its N-terminal A domain, which is lacking in any structural model of FtsY, were studied using NMR and fluorescence spectroscopy. Translocon targeting and binding of FtsY is driven by electrostatic interactions of the intrinsically disordered A domain.

    5. Plant Glycobiology

      Metabolic Labeling and Imaging of N-Linked Glycans in Arabidopsis Thaliana

      Yuntao Zhu, Jie Wu and Prof. Xing Chen

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201603032

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      Glycan imaging in plants: N-linked glycosylation is metabolically labeled with an azide-functionalized sugar reporter, which enables click-labeling and fluorescence imaging of N-glycans in Arabidopsis thaliana.

    6. Natural Product Synthesis

      Total Synthesis of Nosiheptide

      Dipl.-Chem. K. Philip Wojtas, Dr. Matthias Riedrich, Dr. Jin-Yong Lu, Dr. Philipp Winter, M. Sc. Thomas Winkler, M. Sc. Sophia Walter and Prof. Dr. Hans-Dieter Arndt

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201603140

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      Each ring is different: A total synthesis of the bismacrocyclic thiopetide antibiotic nosiheptide was achieved through the assembly of a fully functionalized linear precursor, followed by consecutive macrocyclizations. Key to success were the late-stage formation of a dehydroalanine residue and finely tuned deprotection of the hydroxypyridine core. The synthesis product was identical to the natural material in terms of structure and function.

    7. Protein Dynamics

      Kinetics of the Antibody Recognition Site in the Third IgG-Binding Domain of Protein G

      Supriya Pratihar, Prof. Dr. T. Michael Sabo, Dr. David Ban, Dr. R. Bryn Fenwick, Dr. Stefan Becker, Prof. Dr. Xavier Salvatella, Prof. Dr. Christian Griesinger and Prof. Dr. Donghan Lee

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201603501

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      A link is made between ground-state conformational inter-conversion and molecular recognition. High-power relaxation dispersion measurements at super-cooled temperatures, together with an ensemble representation of the third IgG-binding domain of protein G derived from residual dipolar couplings, point to a role for supra-inline image dynamics in molecular recognition.

    8. Coordination Cages

      A Mixed-Ligand Approach for a Gigantic and Hollow Heterometallic Cage {Ni64RE96} for Gas Separation and Magnetic Cooling Applications

      Wei-Peng Chen, Pei-Qin Liao, Youzhu Yu, Prof. Dr. Zhiping Zheng, Prof. Dr. Xiao-Ming Chen and Prof. Dr. Yan-Zhen Zheng

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201603907

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      The highest-nuclearity transition-metal–rare-earth heterometallic coordination cages {Ni64RE96} (RE=Gd, Dy, and Y) with a cuboidal porous structure have been synthesized by using a mixed-ligand approach to control the hydrolysis of the metal ions. These giant cluster complexes exhibit high selectivity for CO2 over CH4 or N2 at ambient temperature and large magnetocaloric effect at ultralow temperatures.

    9. Asymmetric Phosphine Catalysis

      Engaging Allene-Derived Zwitterions in an Unprecedented Mode of Asymmetric [3+2]-Annulation Reaction

      Dr. Muthukumar G. Sankar, Dr. Miguel Garcia-Castro, Christopher Golz, Prof. Dr. Carsten Strohmann and Dr. Kamal Kumar

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201603936

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      Taming a zwitterion: Chiral phosphine (R)- or (S)-SITCP generates a zwitterion from α-substituted allene ester that can engage the isatine derived ketimines in an unprecedented mode of [3+2] annulation reaction. This provides a facile asymmetric access to 3,2′-pyrrolidinyl spirooxindoles.

    10. Water Splitting | Hot Paper

      Spatially Separated Photosystem II and a Silicon Photoelectrochemical Cell for Overall Water Splitting: A Natural–Artificial Photosynthetic Hybrid

      Dr. Wangyin Wang, Hong Wang, Qingjun Zhu, Dr. Wei Qin, Dr. Guangye Han, Prof. Dr. Jian-Ren Shen, Prof. Dr. Xu Zong and Prof. Dr. Can Li

      Version of Record online: 27 JUN 2016 | DOI: 10.1002/anie.201604091

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      A hybrid natural–artificial photosynthetic platform was constructed by wiring photosystem II and a silicon photoelectrochemical cell based on a photocatalytic–photoelectrochemical Z-scheme design. The hybrid platform combined the strengths of natural and artificial platforms and achieved unassisted and spatially separated production of H2 and O2 from water splitting under solar irradiation.

  10. Reviews

    1. Nucleotide Excision Repair

      Mechanisms of DNA Repair by Photolyase and Excision Nuclease (Nobel Lecture)

      Prof. Aziz Sancar

      Version of Record online: 23 JUN 2016 | DOI: 10.1002/anie.201601524

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      Ultraviolet light damages DNA by converting two adjacent thymines into a thymine dimer which is potentially mutagenic, carcinogenic, or lethal to the organism. This damage is repaired by photolyase and the nucleotide excision repair system in E. coli by nucleotide excision repair in humans. The work leading to these results is presented by A. Sancar in his Nobel lecture.

  11. Communications

    1. Peptide Coatings | Hot Paper

      Easy Access toward Functional Patterns on Cellulose Paper by Combining Laser Printing and Material-Specific Peptide Adsorption

      Steffi Große, Dr. Patrick Wilke and Prof. Hans G. Börner

      Version of Record online: 23 JUN 2016 | DOI: 10.1002/anie.201601603

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      Stick to print: Selective coating of laser-printed patterns was achieved by material-specific adhesion of peptides to cellulose or toner. The peptide sequences were obtained using phage display. Functionalization of the immobilized peptides was realized by selective modification of tyrosine residues present on the printed-pattern coatings, offering new ways towards low-cost printed devices.

    2. Sustainable Chemistry

      Importance of Micropore–Mesopore Interfaces in Carbon Dioxide Capture by Carbon-Based Materials

      Dr. Gema Durá, Dr. Vitaliy L. Budarin, Dr. José A. Castro-Osma, Dr. Peter S. Shuttleworth, Sophie C. Z. Quek, Prof. James H. Clark and Prof. Michael North

      Version of Record online: 23 JUN 2016 | DOI: 10.1002/anie.201602226

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      The impact of mesoporosity: Mesoporous carbon materials (Starbons®) derived from waste biomass show an enhanced carbon dioxide capture capacity and an enhanced selectivity for carbon dioxide compared to microporous activated carbon. This effect is due to the presence of micropore–mesopore interfaces.

    3. Solar-Energy Conversion | Very Important Paper

      Light-Driven Electron Accumulation in a Molecular Pentad

      Margherita Orazietti, Dr. Martin Kuss-Petermann, Prof. Dr. Peter Hamm and Prof. Dr. Oliver S. Wenger

      Version of Record online: 23 JUN 2016 | DOI: 10.1002/anie.201604030

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      No sacrifice at all: Long-lived (τ=870 ns) electron accumulation has been achieved in a molecular pentad without the use of sacrificial reagents. This is an important proof-of-concept for solar-energy conversion and multi-electron photoredox chemistry.

    4. Biosynthesis | Very Important Paper

      Leader Peptide-Free In Vitro Reconstitution of Microviridin Biosynthesis Enables Design of Synthetic Protease-Targeted Libraries

      Emmanuel Reyna-González, Bianca Schmid, Dr. Daniel Petras, Prof. Dr. Roderich D. Süssmuth and Prof. Dr. Elke Dittmann

      Version of Record online: 23 JUN 2016 | DOI: 10.1002/anie.201604345

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      Natural products: A chemo-enzymatic one-pot synthesis approach was developed for tricyclic microviridins comprising lactone as well as lactam rings. The method was used to design and screen protease-targeted libraries derived from short synthetic oligopeptides.

    5. Multicomponent Reactions

      Copper-Catalyzed Formal [2+2+1] Heteroannulation of Alkenes, Alkylnitriles, and Water: Method Development and Application to a Total Synthesis of (±)-Sacidumlignan D

      Tu M. Ha, Dr. Claire Chatalova-Sazepin, Dr. Qian Wang and Prof. Dr. Jieping Zhu

      Version of Record online: 23 JUN 2016 | DOI: 10.1002/anie.201604528

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      Water connections: The title reaction affords γ-butyrolactones with the creation of three chemical bonds and a quaternary carbon center. The domino process involves an unprecedented copper-catalyzed hydroxy-cyanoalkylation of alkenes. A total synthesis of (±)-sacidumlignan D was accomplished featuring this heteroannulation as a key step.

  12. Meeting Reviews

    1. Conference Report

      Structures, Reactions, and Mechanisms: Stereochemistry in the Broadest Sense at the 51st Bürgenstock Conference

      Dr. Ivana Fleischer

      Version of Record online: 23 JUN 2016 | DOI: 10.1002/anie.201605274

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      Tradition and innovation: The 51st Bürgenstock Conference on Stereochemistry took place from May 1–6, 2016 and offered its usual mixture of impressive science and superb discussions in a wonderful atmosphere. In the Meeting Review, Ivana Fleischer outlines the program.

  13. Author Profiles

    1. Xiaogang Liu

      Version of Record online: 23 JUN 2016 | DOI: 10.1002/anie.201605390

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      I can never resist seafood and fresh fruits. My favorite quote is “Nothing is impossible, the word itself says ‘I'm possible’!” (Audrey Hepburn).

  14. Communications

    1. Carbon–Fluorine Bond Activation

      Asymmetric Desymmetrization via Metal-Free C−F Bond Activation: Synthesis of 3,5-Diaryl-5-fluoromethyloxazolidin-2-ones with Quaternary Carbon Centers

      Junki Tanaka, Satoru Suzuki, Etsuko Tokunaga, Prof. Dr. Günter Haufe and Prof. Dr. Norio Shibata

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201603210

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      ortho Effect: Non-activated Csp3−F bonds can be cleaved selectively in the novel desymmetrization of 1,3-difluorides. The combination of a cinchona alkaloid based chiral ammonium bifluoride catalyst and N,O-bis(trimethylsilyl)acetamide facilitated the efficient, catalyzed asymmetric Csp3−F bond cleavage. The steric ortho effect plays an important role in the asymmetric induction.

    2. Algal Blooms

      Investigating the Toxicity of the Aeruginosin Chlorosulfopeptides by Chemical Synthesis

      Manuel Scherer, Dominik Bezold and Prof. Dr. Karl Gademann

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201602755

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      Toxic brew: Four chlorosulfopeptide congeners that are thought to be responsible for the adverse effects of algal blooms were prepared by chemical synthesis. The roles of the chloride and sulfate groups were then established by toxicity assays with the crustacean Thamnocephalus platyurus.

  15. Reviews

    1. 2D Nanomaterials

      Solution-Processed Two-Dimensional MoS2 Nanosheets: Preparation, Hybridization, and Applications

      Xiao Zhang, Zhuangchai Lai, Chaoliang Tan and Prof. Hua Zhang

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201509933

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      Sheets ahead: Solution-based methods offer an effective route for the preparation of MoS2 nanosheets. With the an emphasis on applications, the synthetic strategies and methods for functionalization and hybridization are discussed.

    2. Annulation

      Metal-Catalyzed Annulations through Activation and Cleavage of C−H Bonds

      Prof. Moisés Gulías and Prof. José Luis Mascareñas

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201511567

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      Formel notice: Recent years have witnessed an upsurge in annulations based on C−H activation that can be formally considered as cycloaddition processes. These transformations are particularly appealing from a synthetic perspective because they allow the conversion of readily available substrates into highly valuable cyclic products in a rapid and sustainable manner.

    3. Homogeneous Catalysis

      The Cation–π Interaction in Small-Molecule Catalysis

      C. Rose Kennedy, Dr. Song Lin and Prof. Dr. Eric N. Jacobsen

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201600547

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      Positive effects: This Review discusses the burgeoning role of the cation–π interaction in the small-molecule catalysis of organic and organometallic reactions. An extensive survey of the state-of-the-art research emphasizes how unexpected discoveries and systematic mechanistic studies have begun to enable rational applications of the cation–π interaction in catalyst design.

  16. Communications

    1. Stretchable Supercapacitors

      Highly Stretchable Supercapacitors Based on Aligned Carbon Nanotube/Molybdenum Disulfide Composites

      Dr. Tian Lv, Yao Yao, Ning Li and Prof. Tao Chen

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201603356

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      At full stretch: Using highly aligned CNT/MoS2 composites, stretchable all-solid-state supercapacitors are prepared that sustain their electrochemical performance after being stretched by 240 %. They also exhibited excellent cycling stability after 10 000 charge–discharge cycles.

    2. Flexible Supercapacitors

      Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors

      Wanwan Li, Fengxian Gao, Xiaoqian Wang, Dr. Ning Zhang and Prof. Dr. Mingming Ma

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201603417

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      For whom the gel toils: Inspired by the dynamic network structure of animal dermis, a strong and robust conductive hydrogel is prepared by supramolecular assembly of polyaniline and polyvinyl alcohol. Flexible solid-state supercapacitors based on the hydrogel show excellent capacitance and energy density and outstanding mechanical robustness.

    3. Noncovalent Interactions

      Glucose–Nucleobase Pseudo Base Pairs: Biomolecular Interactions within DNA

      Dr. Empar Vengut-Climent, Dr. Irene Gómez-Pinto, Dr. Ricardo Lucas, Dr. Pablo Peñalver, Dr. Anna Aviñó, Dr. Célia Fonseca Guerra, Prof. Dr. F. Matthias Bickelhaupt, Prof. Ramón Eritja, Prof. Carlos González and Dr. Juan C. Morales

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201603510

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      New lego pieces: The formation of a glucose–nucleobase pseudo base pair is proposed as a new type of biomolecular interaction. When formed within a DNA double helix the high-resolution structure shows only a minor distortion. These DNA duplexes are less stable than natural ones, but glucose shows preference for binding purine nucleobases. Moreover, quantum chemical calculations indicate that glucose–purine pairs are as stable as a natural T–A pair.

    4. Frustrated Lewis Pairs

      Coupling of Carbon Monoxide with Nitrogen Monoxide at a Frustrated Lewis Pair Template

      Dr. Ke-Yin Ye, Dr. Gerald Kehr, Dr. Constantin G. Daniliuc, Dr. Lei Liu, Prof. Dr. Stefan Grimme and Prof. Dr. Gerhard Erker

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201603760

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      Couples and pairs: Coupling of carbon monoxide with nitrogen monoxide was achieved at a frustrated Lewis pair template. This unique reaction uses hydride as an auxiliary, which reductively activates carbon monoxide at the frustrated Lewis pair. The CO/NO coupling reaction then takes place through a pathway involving a radical reaction in which the hydrogen atom auxiliary is eventually removed again.

    5. Polymerization

      CdSe Nanoplatelets: Living Polymers

      Dr. Santanu Jana, Dr. Patrick Davidson and Dr. Benjamin Abécassis

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201603880

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      It's alive! A method to controllably assemble CdSe nanoplatelets into micron-long polymer-like threads is reported. Threads of a given length could be further grown through addition of supplementary nanoparticles, giving these structures living polymer characteristics.

    6. Magnetic Resonance Imaging

      Quantitative, In Situ Visualization of Metal-Ion Dissolution and Transport Using 1H Magnetic Resonance Imaging

      Dr. Joshua M. Bray, Prof. Alison J. Davenport, Prof. Karl S. Ryder and Dr. Melanie M. Britton

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201604310

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      Insights into corrosion processes: Magnetic resonance imaging is used to quanititatively map the distribution of copper(II) ions during the electrodissolution of metallic copper (see picture). The method is non-invasive and can be applied in situ, in three dimensions, and in real time. The dissolution of Cu2+ ions is shown to be non-uniform across the anode.

  17. Highlights

    1. Computational Chemistry

      Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy

      Prof. C. Richard A. Catlow

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201603930

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      Ex Machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources.

  18. News

  19. Cover Pictures

    1. You have free access to this content
      Metal-Catalyzed Annulations through Activation and Cleavage of C−H Bonds

      Dr. Moisés Gulías and Prof. José Luis Mascareñas

      Version of Record online: 22 JUN 2016 | DOI: 10.1002/anie.201604288

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      Hitherto considered inert C−H bonds can react in formal annulation reactions using metal-catalyzed activation, which allows the conversion of readily available substrates into highly valuable cyclic products in a rapid and sustainable manner. In their Review (DOI: 10.1002/anie.201511567), M. Gulías and J. L. Mascareñas make a classification of these powerful synthetic transformations on the basis of the mechanism and consideration of the number of atoms involved in the annulation.

  20. News

  21. Communications

    1. Theranostic Nanoparticles

      Cell-Penetrating Poly(disulfide)-Assisted Intracellular Delivery of Mesoporous Silica Nanoparticles for Inhibition of miR-21 Function and Detection of Subsequent Therapeutic Effects

      Dr. Changmin Yu, Linghui Qian, Dr. Jingyan Ge, Jiaqi Fu, Dr. Peiyan Yuan, Samantha C. L. Yao and Prof. Dr. Shao Q. Yao

      Version of Record online: 21 JUN 2016 | DOI: 10.1002/anie.201602188

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      Combine and detect: Mesoporous silica nanoparticles are coated with cell-penetrating poly(disulfide)s and a fluorogenic apoptosis-detecting peptide. The result is a theranostic drug delivery system for endocytosis-independent delivery/controlled release of combination drugs for the inhibition of endogenous miR-21 with simultaneous detection of subsequent drug effects by two-photon fluorescence microscopy.

    2. Porphyrinoids

      A Directly Fused Subporphyrin Dimer with a Wavelike Structure

      Yasuhiro Okuda, Dr. Eiji Tsurumaki, Juwon Oh, Dr. Jooyoung Sung, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Version of Record online: 21 JUN 2016 | DOI: 10.1002/anie.201603759

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      Link up: [Ni(cod)2]-mediated intramolecular reductive coupling of a ββ′ linked meso,meso′-dibromosubporphyrin dimer gave the anti-isomer of a fused subporphyrin dimer. The new dimer displays a wavelike coplanar structure, a perturbed and red-shifted absorption spectrum, reversible redox behaviors with a decreased electrochemical HOMO–LUMO band gap, and a shortened S1-state lifetime owing to the effective conjugation through fusion.

    3. Nanocrystals | Very Important Paper

      Excavated Cubic Platinum–Tin Alloy Nanocrystals Constructed from Ultrathin Nanosheets with Enhanced Electrocatalytic Activity

      Qiaoli Chen, Yanan Yang, Zhenming Cao, Dr. Qin Kuang, Guifen Du, Dr. Yaqi Jiang, Prof. Zhaoxiong Xie and Prof. Lansun Zheng

      Version of Record online: 21 JUN 2016 | DOI: 10.1002/anie.201602592

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      Excavated cubic Pt–Sn alloy nanocrystals with {110} facets were constructed by the assembly of ultrathin nanosheets by co-reduction in the presence of a surfactant. These nanocrystals have a very high surface area and displayed superior electrocatalytic activity towards methanol oxidation.

    4. Hydrogels

      Non-Osmotic Hydrogels: A Rational Strategy for Safely Degradable Hydrogels

      Dr. Hiroyuki Kamata, Dr. Keiichiro Kushiro, Prof. Madoka Takai, Prof. Ung-il Chung and Prof. Takamasa Sakai

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201602610

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      Degradation without swelling: Hydrogels with an optimal polymer–solvent interaction parameter were synthesized to achieve non-osmotic conditions. The resultant non-osmotic hydrogels displayed the capability to retain their original shape (see picture) and degrade without accompanying significant morphological changes under physiological conditions.

    5. Peptide Catalysts

      Allosterically Regulated Phosphatase Activity from Peptide–PNA Conjugates Folded Through Hybridization

      Takuya Machida, Dr. Som Dutt and Prof. Nicolas Winssinger

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201602751

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      A library of peptides that are constrained in a hairpin loop by flanking peptide nucleic acids upon hybridization were synthesized. A screen for phosphatase activity led to the discovery of a catalyst with >25-fold rate acceleration over the linear peptide. The hybridization-enforced folding of the peptide is decisive for the activity.

    6. C(sp3)−H Fluorination

      The Uranyl Cation as a Visible-Light Photocatalyst for C(sp3)−H Fluorination

      Julian G. West, T. Aaron Bedell and Prof. Erik J. Sorensen

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201603149

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      U can do it: The uranyl cation (UO22+) is able to effect the catalytic fluorination of unactivated C(sp3)−H bonds under visible-light irradiation. Uranyl nitrate is highlighted as a convenient molecular C−H abstraction catalyst, which exhibits selectivity that is distinct from previously reported catalytic systems. NFSI: N-fluorobenzenesulfonimide.

    7. Sustainable Chemistry

      Solvent Extraction: Structure of the Liquid–Liquid Interface Containing a Diamide Ligand

      Dr. Ernesto Scoppola, Dr. Erik B. Watkins, Dr. Richard A. Campbell, Dr. Oleg Konovalov, Dr. Luc Girard, Prof. Jean-Francois Dufrêche, Dr. Geoffroy Ferru, Dr. Giovanna Fragneto and Dr. Olivier Diat

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201603395

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      Liquid interfaces: For a full understanding of the ion transfer during solvent extraction knowledge about the extractant and ion distributions across the water–oil interface is necessary. The extractant and ion distributions at the water–oil interface were studied by X-ray and neutron reflectivity measurements for two different diamide extractants (see picture).

    8. Enantioselectivity

      Enantio- and Diastereoselective 1,2-Additions to α-Ketoesters with Diborylmethane and Substituted 1,1-Diborylalkanes

      Stephanie A. Murray, Jacob C. Green, Sanita B. Tailor and Prof. Simon J. Meek

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201603465

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      Catalytic enantioselective synthesis of boronate-substituted tertiary alcohols is possible through the title reaction. The reactions are catalyzed by chiral phosphine/copper(I) complexes and produce β-hydroxyboronates containing up to two contiguous stereogenic centers. The utility of the organoboron products is demonstrated through several chemoselective functionalizations. pin=pinacolato, TMS=trimethylsilyl.

    9. Photoredox Reactions

      Picomole-Scale Real-Time Photoreaction Screening: Discovery of the Visible-Light-Promoted Dehydrogenation of Tetrahydroquinolines under Ambient Conditions

      Dr. Suming Chen, Dr. Qiongqiong Wan and Prof. Dr. Abraham K. Badu-Tawiah

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201603530

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      The here and now of it: A picomole-scale, real-time platform based on mass spectrometry for the screening of photoredox reactions enabled the discovery of an accelerated photocatalytic transformation of tetrahydroquinolines into quinolines under ambient conditions (see scheme). The screening platform also has the advantage that key mechanistic information can be derived from captured intermediates.

    10. Hydrogenation

      C-Propargylation Overrides O-Propargylation in Reactions of Propargyl Chloride with Primary Alcohols: Rhodium-Catalyzed Transfer Hydrogenation

      Dr. Tao Liang, Dr. Sang Kook Woo and Prof. Michael J. Krische

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201603575

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      A path less travelled: The canonical SN2 behavior displayed by alcohols and activated alkyl halides in basic media (O-alkylation) is superseded by a pathway leading to carbinol C-alkylation under the conditions of rhodium-catalyzed transfer hydrogenation. Racemic and asymmetric propargylations are described.

    11. Redox Chemistry

      Redox-Active-Ligand-Mediated Formation of an Acyclic Trinuclear Ruthenium Complex with Bridging Nitrido Ligands

      Dr. Bidraha Bagh, Daniël L. J. Broere, Dr. Maxime A. Siegler and Dr. Ir. Jarl Ivar van der Vlugt

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201603659

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      Three strikes aN2d you′re out! The spontaneous azide decomposition on mononuclear ruthenium complexes bearing a redox-active aminophenol-derived tridentate NNO ligand selectively generates a rare trinuclear complex with an unsymmetric Ru=N−Ru−N=Ru skeleton, proposedly by oxidative nitride coupling. DFT and experimental data support a pivotal role for the NNO ligand. The bridging bis(nitrido) complex is reactive towards H2 and hydrogen-atom donor species.

    12. Hydrogen Production | Very Important Paper

      Boosting Photocatalytic Hydrogen Production of a Metal–Organic Framework Decorated with Platinum Nanoparticles: The Platinum Location Matters

      Juan-Ding Xiao, Qichao Shang, Prof. Dr. Yujie Xiong, Prof. Dr. Qun Zhang, Prof. Dr. Yi Luo, Prof. Dr. Shu-Hong Yu and Prof. Dr. Hai-Long Jiang

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201603990

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      Location, location, location: Platinum nanoparticles (PtNPs) are incorporated inside or supported on a metal–organic framework (MOF), UiO-66-NH2, giving Pt@UiO-66-NH2 and Pt/UiO-66-NH2, respectively. Having the Pt NPs inside the MOF greatly shortens the electron–transport distance, which favors the electron–hole separation and thereby yields the highest photocatalytic efficiency for H2 production.

  22. Editorials

    1. You have free access to this content
      The Active Field of Nuclear and Radiochemistry: Not Just Nuclear Power

      Prof. Dr. Clemens Walther

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201604045

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      “ … The number of universities teaching nuclear and radiochemistry has decreased, not least as radiochemistry is erroneously linked to the use of nuclear power … Radiochemistry is essential for a variety of fields, including radiopharmaceuticals, as well as the management of radioactive waste … we are facing a lack of specialists in the area of radiation protection …” Read more in the Editorial by Clemens Walther.

  23. Communications

    1. Nanominerals | Very Important Paper

      Fast-Geomimicking using Chemistry in Supercritical Water

      Dr. Angela Dumas, Marie Claverie, Dr. Cédric Slostowski, Guillaume Aubert, Cristel Careme, Dr. Christophe Le Roux, Dr. Pierre Micoud, Prof. François Martin and Dr. Cyril Aymonier

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201604096

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      Small talc: The supercritical hydrothermal flow synthesis is a new method to produce model nanominerals, such as nano-talc, in just a few tens of seconds. As well as having different spectroscopic signals to natural talc, the nano-talc has new properties, such as its hydrophilic character, making it the first fluid talc filler for new applications.

  24. Cover Pictures

    1. You have free access to this content
      Integrin-Targeting Knottin Peptide–Drug Conjugates Are Potent Inhibitors of Tumor Cell Proliferation

      Nick Cox, James R. Kintzing, Mark Smith, Gerald A. Grant and Prof. Jennifer R. Cochran

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201605483

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      A knottin miniprotein first isolated from the seeds of the squirting cucumber has been engineered to bind selectively to tumor-associated integrin receptors. In their Communication (DOI: 10,1002/anie.201603488), N. Cox and co-workers describe a knottin–gemcitabine conjugate that is over 40-times smaller than an antibody–drug conjugate. This approach for targeted drug delivery offers an alternative strategy for the treatment of resistant tumors, such as brain or pancreatic cancer. Cover picture: Ellen Loshbough.

    2. You have free access to this content
      Single C−F Bond Cleavage of Trifluoromethylarenes with an ortho-Silyl Group

      Dr. Suguru Yoshida, Ken Shimomori, Youngchan Kim and Prof. Dr. Takamitsu Hosoya

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201605487

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      Like the fall of an impregnable castle, a challenging single C−F bond activation of trifluoromethylarenes with an ortho-hydrosilyl group was achieved by T. Hosoya, S. Yoshida, and co-workers through the activation of the hydrosilyl group with a trityl cation in the presence of various nucleophiles as they describe in their Communication (DOI: 10.1002/anie.201604776). Further derivatization of the resulting fluorosilylarenes afforded various difluoromethylated arenes.

    3. You have free access to this content
      Site-Selective Tertiary Alkyl–Fluorine Bond Formation from α-Bromoamides Using a Copper/CsF Catalyst System

      Prof. Dr. Takashi Nishikata, Syo Ishida and Ryo Fujimoto

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201605488

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      A copper catalyst enables the site-selective fluorination of α-bromoamides with multiple brominated centers with CsF. In their Communication (DOI: 10.1002/anie.201603426), T. Nishikata et al. show that CuF2 is generated in situ as the key fluorinating reagent, which reacts with the tertiary alkyl radicals that are generated from the reaction of the α-bromoamide and the CuI salt. As the products contain reactive bonds for further functionalization, this approach provides access to a wide range of fluorinated building blocks.

    4. You have free access to this content
      The Nanoparticle Size Effect in Graphene Cutting: A “Pac-Man” Mechanism

      Zongyang Qiu, Prof. Li Song, Prof. Jin Zhao, Prof. Zhenyu Li and Prof. Jinlong Yang

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201605489

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      A “Pac-Man” mechanism is revealed for the metal-nanoparticle-catalyzed cutting of graphene by employing a multiscale simulation approach. Z. Li et al. report in their Communication (DOI: 10.1002/anie.201602541) that although the overall cutting rate is proportional to the surface area of the nanoparticle, the rate-limiting step of graphene cutting is actually at the graphene–metal interface. Such an apparent inconsistency turns out to be a result of the distinct etching behaviors at zigzag and armchair edge sites.

    5. You have free access to this content
      Ferrocenyl Quinone Methide–Thiol Adducts as New Antiproliferative Agents: Synthesis, Metabolic Formation from Ferrociphenols, and Oxidative Transformation

      Dr. Yong Wang, Dr. Marie-Aude Richard, Dr. Siden Top, Dr. Patrick M. Dansette, Dr. Pascal Pigeon, Dr. Anne Vessières, Dr. Daniel Mansuy and Prof. Gérard Jaouen

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/anie.201605536

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      An elaborate metabolic choreography: In their Communication (DOI: 10.1002/anie.201603931), G. Jaouen and co-workers detail the metabolic activation of ferrociphenols by liver microsomes, leading to quinone methides that subsequently react with thiols, such as glutathione, to give thiol adducts. The behavior of these organometallic adducts in an oxidative environment resembling in vivo conditions may explain their antiproliferative activity against cancer cells.

  25. Communications

    1. Multicomponent Reactions | Hot Paper

      Insertion of Isocyanides into N−Si Bonds: Multicomponent Reactions with Azines Leading to Potent Antiparasitic Compounds

      Kranti G. Kishore, Ouldouz Ghashghaei, Dr. Carolina Estarellas, M. Mar Mestre, Cristina Monturiol, Dr. Nicola Kielland, Prof. John M. Kelly, Dr. Amanda Fortes Francisco, Shiromani Jayawardhana, Prof. Diego Muñoz-Torrero, Prof. Belén Pérez, Prof. F. Javier Luque, Prof. Rocío Gámez-Montaño and Prof. Rodolfo Lavilla

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201604109

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      Insert here! Multicomponent reactions (MCRs) with isoquinolines and other azines that proceed through the insertion of an isocyanide into a N−Si bond are described. This novel activation mode enables a variety of transformations to take place with high selectivity under mild reaction conditions. Some of the products showed in vitro activity against the causative agents of trypanosomiasis. TMS=trimethylsilyl.

    2. Synthetic Methods

      Palladium Catalysis Enables Benzylation of α,α-Difluoroketone Enolates

      Ming-Hsiu Yang, Jordan R. Hunt, Dr. Niusha Sharifi and Prof. Dr. Ryan A. Altman

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201604149

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      Alkylation reactions of α,α-difluoroketone enolates with sp3-based electrophiles have been underdeveloped because of intrinsically weak nucleophilicity and chemoselective formation associated with this enolate. Reported herein is a palladium-catalyzed decarboxylative benzylation of α,α-difluoroketone enolates, in which the external α,α-difluoroenolate, formed in situ, underwent reductive elimination from a palladium(II) intermediate to generate the key C(α)−C(sp3) bond.

    3. Kinetic Resolution

      Palladium-Catalyzed Chemo- and Enantioselective C−O Bond Cleavage of α-Acyloxy Ketones by Hydrogenolysis

      Dr. Jianzhong Chen, Dr. Zhenfeng Zhang, Dr. Delong Liu and Prof. Wanbin Zhang

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201603590

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      A break of C−O: A chemoselective C−O bond cleavage of the ester alkyl side-chain of α-acyloxy ketones by a palladium-catalyzed hydrogenolysis is reported. Furthermore, an enantioselective C−O bond cleavage was successfully applied to the kinetic resolution of some acyloins with up to 99 % ee. The example (S/C=6000) represents by far the highest catalytic efficiency for a palladium-catalyzed homogeneous hydrogenation.

    4. Synthetic Methods

      Direct Difluoromethylation of Alcohols with an Electrophilic Difluoromethylated Sulfonium Ylide

      Jiansheng Zhu, Yafei Liu and Prof. Dr. Qilong Shen

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201603166

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      A general method for the formation alkyl difluoromethylethers from the reaction of an alcohol with an electrophilic difluoromethylating reagent (1 a) is reported. The reaction conditions are mild and a variety of functional groups are compatible.

    5. Drug Bioconjugates

      N-Heterocyclic Carbene–Gold(I) Complexes Conjugated to a Leukemia-Specific DNA Aptamer for Targeted Drug Delivery

      Weijia Niu, Xigao Chen, Weihong Tan and Adam S. Veige

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201602702

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      Apt to enter cancer cells: N-Heterocyclic carbene (NHC)–gold(I) complexes were conjugated to the CCRF-CEM leukemia-specific aptamer sgc8c as a strategy for the selective targeting of cancer cells. Cell-viability assays in combination with other techniques indicated that the NHC–AuI–aptamer conjugate (see structure) was more cytotoxic than the NHC–gold complex alone and targeted CCRF-CEM leukemia cells selectively.

    6. Molecular Devices | Hot Paper

      Alcohol-Mediated Resistance-Switching Behavior in Metal–Organic Framework-Based Electronic Devices

      Dr. Yaqing Liu, Dr. Hong Wang, Dr. Wenxiong Shi, Dr. Weina Zhang, Dr. Jiancan Yu, Bevita K. Chandran, Chenlong Cui, Bowen Zhu, Zhiyuan Liu, Dr. Bin Li, Cai Xu, Zhiling Xu, Prof. Shuzhou Li, Prof. Wei Huang, Prof. Fengwei Huo and Prof. Xiaodong Chen

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201602499

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      A MOF never forgets: Alcohol-mediated memory devices with reliable resistance-switching properties were realized in metal–organic framework (MOF) films. The memory behavior can be controlled by the intermolecular interactions among the guest molecules adsorbed in MOF crystals to achieve multilevel information storage.

    7. Carbon Dioxide Reduction

      Efficient Reduction of CO2 into Formic Acid on a Lead or Tin Electrode using an Ionic Liquid Catholyte Mixture

      Dr. Qinggong Zhu, Dr. Jun Ma, Xinchen Kang, Xiaofu Sun, Prof. Huizhen Liu, Jiayin Hu, Prof. Zhimin Liu and Prof. Buxing Han

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201601974

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      Just a splash: Addition of a small amount of water to an ionic liquid/acetonitrile electrolyte mixture enhanced the efficiency of the electrochemical reduction of CO2 into formic acid significantly using a Pb or Sn electrode. The partial current density for HCOOH was as high as 37.6 mA cm−2 at a Faradaic efficiency of 91.6 %.

    8. Mass Spectrometry

      You have full text access to this OnlineOpen article
      Impact of Deuteration on the Assembly Kinetics of Transthyretin Monitored by Native Mass Spectrometry and Implications for Amyloidoses

      Ai Woon Yee, Martine Moulin, Nina Breteau, Dr. Michael Haertlein, Dr. Edward P. Mitchell, Dr. Jonathan B. Cooper, Dr. Elisabetta Boeri Erba and Prof. V. Trevor Forsyth

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201602747

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      Amyloid formation: While deuteration shows no major impact on the transthyretin (TTR) crystal structure, the labeling affects protein kinetics significantly. This behavior is reflected in differing levels of TTR subunit exchange and also in the rate of amyloid formation. Deuteration effects are comparable to effects observed in the case of aggressive TTR.

    9. Gas Separation | Hot Paper

      A Highly Permeable Aligned Montmorillonite Mixed-Matrix Membrane for CO2 Separation

      Dr. Zhihua Qiao, Dr. Song Zhao, Prof. Dr. Jixiao Wang, Prof. Dr. Shichang Wang, Prof. Dr. Zhi Wang and Prof. Dr. Michael D. Guiver

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201603211

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      A mixed-matrix membrane consisting of aligned montmorillonite (AMT) and polysulfone was prepared for CO2 separation. The MT interlayer gaps were aligned with polyvinylamineacid chains that had been grafted onto the surface of the hydroxylated polysulfone substrate. The high-speed transport channels in AMT result in high CO2 permeance and mixed-gas permselectivity.

    10. Double Perovskites

      Double Double Cation Order in the High-Pressure Perovskites MnRMnSbO6

      Elena Solana-Madruga, Dr. Ángel M. Arévalo-López, Dr. Antonio J. Dos Santos-García, Dr. Esteban Urones-Garrote, Dr. David Ávila-Brande, Prof. Regino Sáez-Puche and Prof. J. Paul Attfield

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201603526

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      Cations called to order: A double double perovskite type structure is reported in the MnRMnSbO6 compound series (R=La, Pr, Nd, Sm). The structure has Mn2+ and R3+ cations ordered in columns on perovskite A sites, while Mn2+ and Sb5+ ions have rock salt order on the B sites. The MnRMnSbO6 double double perovskites are ferrimagnetic at low temperatures with additional spin-reorientation transitions.

    11. C−F Activation | Hot Paper

      Single C−F Bond Cleavage of Trifluoromethylarenes with an ortho-Silyl Group

      Dr. Suguru Yoshida, Ken Shimomori, Youngchan Kim and Prof. Dr. Takamitsu Hosoya

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201604776

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      One of the three: The transformation of a single C−F bond of trifluoromethylarenes bearing an ortho-hydrosilyl group is described. The activation of the hydrosilyl group with a trityl cation in the presence of nucleophiles enabled selective C−F bond functionalization, for example, by allylation, carboxylation, or chlorination. Further derivatization of the resulting fluorosilylarenes afforded various difluoromethylated arenes.

  26. Reviews

    1. Lignin Valorisation

      You have full text access to this OnlineOpen article
      Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis

      Dr. Roberto Rinaldi, Dr. Robin Jastrzebski, Dr. Matthew T. Clough, Prof. Dr. John Ralph, Marco Kennema, Dr. Pieter C. A. Bruijnincx and Prof. Dr. Bert M. Weckhuysen

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201510351

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      Seeing the wood for the trees: Lignin is an abundant biopolymer with a high carbon content and high aromaticity. A critical analysis of “upstream” and “downstream” elements of lignin valorisation is given, including bioengineering, biorefining and catalysis.

  27. Communications

    1. Synthetic Receptors

      You have full text access to this OnlineOpen article
      Platform Synthetic Lectins for Divalent Carbohydrate Recognition in Water

      Tom S. Carter, Dr. Tiddo J. Mooibroek, Patrick F. N. Stewart, Prof. Matthew P. Crump, Dr. M. Carmen Galan and Prof. Anthony P. Davis

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201603082

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      Be my guests: Carbohydrate receptors featuring two equivalent binding sites were designed to target facially amphiphilic substrates. A version with anionic side chains favors aminosugars, whereas a cationic variant binds the biologically important α-sialyl unit (as shown).

    2. Polycycle Synthesis

      Highly Efficient Formal [2+2+2] Strategy for the Rapid Construction of Polycyclic Spiroindolines: A Concise Synthesis of 11-Demethoxy-16-epi-myrtoidine

      Dr. Jun Zhu, Yu-Jing Cheng, Xiao-Kang Kuang, Dr. Lijia Wang, Dr. Zhong-Bo Zheng and Prof. Dr. Yong Tang

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/anie.201603991

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      Going full cycle: Upon treatment with the catalyst InCl3 (5 mol %), tryptamine-derived enamides reacted readily with methylene malonate to provide rapid, gram-scale access to versatile tetracyclic spiroindolines with excellent diastereoselectivity (see scheme). This strategy offers a concise approach to alkaloids isolated from Strychnos myrtoides, as demonstrated by a short synthesis of 11-demethoxy-16-epi-myrtoidine.

    3. Inorganic Radicals

      Exergonic and Spontaneous Production of Radicals through Beryllium Bonds

      M. Sc. Oriana Brea, Prof. Dr. Ibon Alkorta, Prof. Dr. Otilia Mó, Prof. Dr. Manuel Yáñez, Prof. Dr. José Elguero and Prof. Dr. Inés Corral

      Version of Record online: 16 JUN 2016 | DOI: 10.1002/anie.201603690

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      Be radical: The formation of a beryllium bond between a beryllium derivative and a Lewis base induces a reorganization of the electron density that results in the exergonic and spontaneous homolytic dissociation of the base. The effect of the BeX2 attachment is twofold: it activates the covalent bond of the base and greatly stabilizes the radicals formed (see picture: Be light green, X white, F green, R black).

    4. Antiperovskites

      Metal Vacancy Ordering in an Antiperovskite Resulting in Two Modifications of Fe2SeO

      Dr. Martin Valldor, Taylor Wright, Prof. Dr. Andrew Fitch and Dr. Yurii Prots

      Version of Record online: 16 JUN 2016 | DOI: 10.1002/anie.201603920

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      Two variants: Metal vacancy ordering in an antiperovskite results in two modifications of Fe2SeO, which are pseudo-tetragonal and chiral, polar, non-centrosymmetric, and trigonal, respectively. Both modifications have similarities with ionic conductors. As the compounds seem to be insulating, the Fe is present as divalent high-spin ions because of weak crystal fields.

    5. Heterocycle Synthesis

      Gold(I)-Catalyzed N-Desulfonylative Amination versus N-to-O 1,5-Sulfonyl Migration: A Versatile Approach to 1-Azabicycloalkanes

      Solène Miaskiewicz, Boris Gaillard, Dr. Nicolas Kern, Prof. Dr. Jean-Marc Weibel, Prof. Dr. Patrick Pale and Dr. Aurélien Blanc

      Version of Record online: 16 JUN 2016 | DOI: 10.1002/anie.201604329

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      Worth their weight in gold: The great value of sulfonamides in gold catalysis is highlighted by two hydroamination reactions that occur by migration or cleavage of sulfonyl group (see scheme). These unprecedented gold-promoted sulfonyl-transfer reactions open the way to appealing synthetic applications of these robust nitrogen-protecting groups, as demonstrated by the formation of versatile azabicycles.

  28. Cover Pictures

    1. You have free access to this content
      Fast-Geomimicking using Chemistry in Supercritical Water

      Angela Dumas, Marie Claverie, Cédric Slostowski, Guillaume Aubert, Cristel Careme, Christophe Le Roux, Pierre Micoud, François Martin and Cyril Aymonier

      Version of Record online: 16 JUN 2016 | DOI: 10.1002/anie.201605535

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      Geomimicking is an innovative process inspired by the mineral world to produce new advanced materials. In nature, talc results from the hydrothermal alteration of bedrock over millions of years. In their Communication (DOI: 10.1002/anie.201604096), F. Martin, C. Aymonier et al. show that by geomimicking, synthetic talc is obtained in only 20 s using a continuous supercritical fluids reactor (SCF). Synthetic nano-sized talc exhibits new crystal-chemistry signals and new properties, such as a hydrophilic character, opening the way to new applications.

  29. Reviews

    1. Metal Carbenes

      New Approaches to the Synthesis of Metal Carbenes

      Dr. Minqiang Jia and Prof. Shengming Ma

      Version of Record online: 16 JUN 2016 | DOI: 10.1002/anie.201508119

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      Metal carbenes without diazo compounds? In the past, diazo compounds were most commonly used for the generation of metal carbenes under metal catalysis. With concerns over safety and large-scale syntheses, many other substrates are now available as surrogates for this purpose, and their applications are summarized in this Review.

  30. Minireviews

    1. Drug Delivery

      Controlling the Stealth Effect of Nanocarriers through Understanding the Protein Corona

      Dr. Susanne Schöttler, Prof. Dr. Katharina Landfester and Prof. Dr. Volker Mailänder

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/anie.201602233

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      Stealth shield: The use of nanocarriers in medical applications is complicated by the formation of a protein corona on the nanocarrier surface. This can influence interaction with cell membranes, and makes it difficult to predict cellular interactions, biodistribution, and toxicity. This Minireview provides an overview of what we know about the protein corona of nanocarriers, with a focus on surface functionalization to reduce unspecific uptake—termed the stealth effect.

  31. Communications

    1. DNA Nanotechnology

      Computer-Aided Production of Scaffolded DNA Nanostructures from Flat Sheet Meshes

      Erik Benson, Abdulmelik Mohammed, Dr. Alessandro Bosco, Dr. Ana I. Teixeira, Prof. Pekka Orponen and Dr. Björn Högberg

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/anie.201602446

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      Flat-sheet DNA nanostructures: Using algorithmic tools, DNA nanostructures were designed from 2D meshes with varying internal geometries. Using this method, structures with complex internal and external features were prepared that self-assemble under physiological salt concentrations and have larger surface areas compared to classic DNA origami flat-sheet designs.

    2. Flow Reactions

      Continuous-Flow Synthesis and Derivatization of Aziridines through Palladium-Catalyzed C(sp3)−H Activation

      Jacek Zakrzewski, Adam P. Smalley, Dr. Mikhail A. Kabeshov, Prof. Matthew J. Gaunt and Prof. Alexei A. Lapkin

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/anie.201602483

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      Keep up with the flow! A predictive mechanistic model was developed and used to design a flow process for C−H activation. The resulting continuous-flow synthesis of aziridines through palladium-catalyzed C(sp3)−H activation was combined with ring opening of the aziridine in flow to give highly functionalized aliphatic amines in a consecutive process involving the capture and release of the aziridine intermediate (see scheme).

    3. P4 Functionalization

      Direct Synthesis of Phospholyl Lithium from White Phosphorus

      Dr. Ling Xu, Yue Chi, Shanshan Du, Prof. Dr. Wen-Xiong Zhang and Prof. Dr. Zhenfeng Xi

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/anie.201602790

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      Pull it together: Phospholyl lithium derivatives were synthesized directly from P4 and 1,4-dilithio-1,3-butadienes with excellent efficiency. DFT calculations indicate that the mechanism of this reaction differs from the well-known stepwise cleavage of P−P bonds in P4 activation. Instead, a cooperative nucleophilic attack of two Cinline image −Li bonds on P4 is preferred.

    4. Drug Delivery | Very Important Paper

      Integrin-Targeting Knottin Peptide–Drug Conjugates Are Potent Inhibitors of Tumor Cell Proliferation

      Nick Cox, James R. Kintzing, Mark Smith, Gerald A. Grant and Prof. Jennifer R. Cochran

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/anie.201603488

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      Tied up in knottins: Tumor-targeted knottin peptide-drug conjugates (KDC) are significantly smaller than antibody–drug conjugates, allowing for facile synthesis and conjugation. A KDC bearing the nucleoside gemcitabine is internalized by an integrin-mediated mechanism, releases its payload intracellularly, and is shown to be a highly potent inhibitor of several malignant cell lines.

    5. Polymers

      Molecular Engineering of Conjugated Polybenzothiadiazoles for Enhanced Hydrogen Production by Photosynthesis

      Can Yang, Beatriz Chiyin Ma, Linzhu Zhang, Dr. Sen Lin, Saman Ghasimi, Prof. Katharina Landfester, Dr. Kai A. I. Zhang and Prof. Xinchen Wang

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/anie.201603532

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      Bring to light: Conjugated polybenzothiadiazoles were introduced as a new family of organic photocatalysts for H2 evolution from water in the presence of electron donors with visible-light irradiation. The molecular engineering of the electron-withdrawing benzothiadiazole unit on the phenyl unit allows the construction of either one- or three-dimensional polybenzothiadiazoles, and the effect of the structure on the photocatalytic H2 evolution activity was investigated.

    6. C−H Bond Activation | Hot Paper

      Highly Stereoselective Cobalt(III)-Catalyzed Three-Component C−H Bond Addition Cascade

      Jeffrey A. Boerth, Joshua R. Hummel and Prof. Dr. Jonathan A. Ellman

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/anie.201603831

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      Essential bond connections: A highly stereoselective three-component C(sp2)−H bond addition across alkene and polarized π-bonds is reported. Catalysis by CoIII was much more effective than by RhIII, providing products in good yield and with high diastereoselectivity for a broad range of aldehydes. The first asymmetric reactions employing CoIII-catalyzed C−H functionalization are also reported for three-component C−H bond addition cascades with N-tert- butanesulfinyl imines.