Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 19

May 7, 2012

Volume 51, Issue 19

Pages 4493–4752

  1. Cover Picture

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    5. Back Cover
    6. Graphical Abstract
    7. Flashback
    8. Corrigendum
    9. News
    10. Author Profile
    11. News
    12. Obituary
    13. Book Review
    14. Highlights
    15. Review
    16. Communications
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    1. Cover Picture: Liquid-Phase Deposition of Freestanding Copper Foils and Supported Copper Thin Films and Their Structuring into Conducting Line Patterns (Angew. Chem. Int. Ed. 19/2012) (page 4493)

      Niklaus Kränzlin, Stefan Ellenbroek, Dr. Desirée Durán-Martín and Prof. Markus Niederberger

      Article first published online: 13 APR 2012 | DOI: 10.1002/anie.201202069

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      The liquid-phase preparation of copper, either as freestanding submicrometer-thin foil or supported on a substrate, is presented by M. Niederberger et al. in their Communication on page 4743 ff. A solution of copper acetylacetonate initially forms a mirror on the reaction container wall, which then delaminates. When the copper is supported on a flexible substrate, such as Kapton, it can be structured into conduction line patterns.

  2. Inside Cover

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    6. Graphical Abstract
    7. Flashback
    8. Corrigendum
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    10. Author Profile
    11. News
    12. Obituary
    13. Book Review
    14. Highlights
    15. Review
    16. Communications
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    1. Inside Cover: A Strong Bio-Inspired Layered PNIPAM–Clay Nanocomposite Hydrogel (Angew. Chem. Int. Ed. 19/2012) (page 4494)

      Dr. Jianfeng Wang, Dr. Ling Lin, Prof. Qunfeng Cheng and Prof. Lei Jiang

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201202063

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      Inspired from natural nacre a transparent, layered nanocomposite hydrogel was fabricated from poly(N-isopropylacrylamide) and clay. This hydrogel shows excellent mechanical properties and a hierarchical microstructure. In their Communication on page 4676 ff., Q. Cheng et al. introduce a concept for the preparation of wet-chemical high-performance materials that can be used for applications, such as tissue-engineering, sensors, artificial muscles, and underwater antifouling materials.

  3. Inside Back Cover

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    8. Corrigendum
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    12. Obituary
    13. Book Review
    14. Highlights
    15. Review
    16. Communications
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    1. Inside Back Cover: Crystal Structures of the Hydration States of Pigment Red 57:1 (Angew. Chem. Int. Ed. 19/2012) (page 4753)

      Sándor L. Bekö, Sonja M. Hammer and Prof. Dr. Martin U. Schmidt

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201202062

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      Like most journals and newspapers worldwide Angewandte Chemie International Edition is printed with Pigment Red 57:1. M. U. Schmidt et al. report in their Communication on page 4735 ff. that the actual shade of red depends on the hydration state and thus may change with the weather conditions. The crystal structures of the pigment in various hydration states have been solved by X-ray powder diffraction.

  4. Back Cover

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    6. Graphical Abstract
    7. Flashback
    8. Corrigendum
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    10. Author Profile
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    12. Obituary
    13. Book Review
    14. Highlights
    15. Review
    16. Communications
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    1. Back Cover: Sensitive and High-Throughput Isolation of Rare Cells from Peripheral Blood with Ensemble-Decision Aliquot Ranking (Angew. Chem. Int. Ed. 19/2012) (page 4754)

      Perry G. Schiro, Mengxia Zhao, Jason S. Kuo, Karen M. Koehler, Prof. Daniel E. Sabath and Prof. Daniel T. Chiu

      Article first published online: 2 MAR 2012 | DOI: 10.1002/anie.201201432

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      A blood sample was broken up into nanoliter volumes, and subsequently each aliquot was ranked based on whether or not a rare cell was present in the ensemble of cells within the aliquot. This approach is called ensemble decision aliquot ranking (eDAR). In their Communication on page 4618 ff., D. T. Chiu et al. show that the eDAR technique is well-suited for the enrichment of rare cells, such as circulating tumor cells.

  5. Graphical Abstract

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    14. Highlights
    15. Review
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    1. Graphical Abstract: Angew. Chem. Int. Ed. 19/2012 (pages 4497–4511)

      Article first published online: 3 MAY 2012 | DOI: 10.1002/anie.201290034

    2. Graphical Abstract: Angew. Chem. Int. Ed. 19/2012 (pages 4497–4511)

      Article first published online: 19 AUG 2013 | DOI: 10.1002/anie.201390035

  6. Flashback

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    1. 50 Years Ago... (page 4508)

      Article first published online: 3 MAY 2012 | DOI: 10.1002/anie.201202311

  7. Corrigendum

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    15. Review
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    1. You have free access to this content
      Corrigendum: Characterization of Vinylgold Intermediates: Gold-Mediated Cyclization of Acetylenic Amides (page 4511)

      Dr. Olga A. Egorova, Hyewon Seo, Yonghwi Kim, Dr. Dohyun Moon, Prof. Young Min Rhee and Prof. Kyo Han Ahn

      Article first published online: 25 APR 2012 | DOI: 10.1002/anie.201201329

      This article corrects:

      Characterization of Vinylgold Intermediates: Gold-Mediated Cyclization of Acetylenic Amides1

      Vol. 50, Issue 48, 11446–11450, Article first published online: 5 OCT 2011

  8. News

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    13. Book Review
    14. Highlights
    15. Review
    16. Communications
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  9. Author Profile

    1. Top of page
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    6. Graphical Abstract
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    8. Corrigendum
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    1. Max Malacria (pages 4518–4519)

      Article first published online: 21 MAR 2012 | DOI: 10.1002/anie.201200571

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      “What I appreciate most about my friends is loyalty and frankness. The greatest scientific advance of the last decade was published at the very beginning of the 21st century: the first draft sequence and analysis of the human genome …” This and more about Max Malacria can be found on page 4518.

  10. News

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  11. Obituary

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    1. Richard Bader (1931–2012) (pages 4521–4522)

      Paul W. Ayers and Gernot Frenking

      Article first published online: 18 APR 2012 | DOI: 10.1002/anie.201201794

  12. Book Review

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    1. Beyond the Finite. The Sublime in Art and Science. Edited by Roald Hoffmann and Iain Boyd Whyte. (pages 4523–4524)

      John Meurig Thomas

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201942

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      Oxford University Press, New York, 2011. 208 pp., hardcover, $ 24.95.—ISBN 978-0199737697

  13. Highlights

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    1. Silylium Ions

      “Tamed” Silylium Ions: Versatile in Catalysis (pages 4526–4528)

      Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Article first published online: 15 MAR 2012 | DOI: 10.1002/anie.201108320

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      Cations for all seasons: Silylium cations, because of their high Lewis acidity, are suitable for catalysis like almost no other class of reactive cations. Starting from a new, elegant synthetic route to triarylsilylium ions and their application in hydrogen activation, the general potential of silylium ions in synthesis is discussed.

    2. Nitrogen Fixation

      New Insights into the Biological and Synthetic Fixation of Nitrogen (pages 4529–4531)

      M. Sc. Markus G. Scheibel and Prof. Dr. Sven Schneider

      Article first published online: 12 MAR 2012 | DOI: 10.1002/anie.201200175

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      The fixation with fixation: Microorganisms have converted atmospheric nitrogen into ammonia for millions of years under ambient conditions, whereas the Haber–Bosch process requires high pressures and temperatures. Some recent studies on the biological and synthetic generation of ammonia should contribute to a better understanding of the mechanism of this reaction, which remains one of the most challenging goals for catalysis.

    3. Asymmetric Fluorination

      A New Approach towards the Asymmetric Fluorination of Alkenes Using Anionic Phase-Transfer Catalysts (pages 4532–4534)

      Dr. Ulrich Hennecke

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201200831

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      Chiral anions can do it: Asymmetric phase-transfer catalysis is no longer limited to cationic catalysts. Lipophilic BINOL phosphate anions are superior catalysts for the asymmetric electrophilic fluorination of alkenes under phase-transfer conditions (see picture). Now complex fluorinated compounds can be synthesized selectively from simple alkene starting materials.

  14. Review

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    1. Natural Product Synthesis

      The Chemistry of the Polycyclic Polyprenylated Acylphloroglucinols (pages 4536–4561)

      Dr. Jean-Alexandre Richard, Dr. Rebecca H. Pouwer and Prof. Dr. David Y.-K. Chen

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201103873

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      Recently completed total syntheses and the ingenious synthetic approaches developed for the construction of the biologically significant polycyclic polyprenylated acylphloroglucinols (PPAPs) are presented in this Review. The state-of-the-art synthetic methods and strategies, current limitations, as well as the outlook for this field are highlighted.

  15. Communications

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    1. Stacking Interactions

      Oligothiophene Cruciform with a Germanium Spiro Center: A Promising Material for Organic Photovoltaics (pages 4562–4567)

      Dr. Iain A. Wright, Dr. Alexander L. Kanibolotsky, Joseph Cameron, Dr. Tell Tuttle, Prof. Dr. Peter J. Skabara, Dr. Simon J. Coles, Calvyn T. Howells, Stuart A. J. Thomson, Dr. Salvatore Gambino and Prof. Dr. Ifor D. W. Samuel

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201109074

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      X marks the spot! A fascinating packing motif is observed in a novel cruciform oligothiophene containing a Ge (violet; see picture) spiro center. Long-range interchain interactions between molecules and strong electronic coherence between orthogonal chains within the molecules are present. Such ordering is advantageous for bulk charge transport, as demonstrated by high short-circuit currents in bulk heterojunction organic solar cells.

    2. Synthetic Methods

      Pseudoephenamine: A Practical Chiral Auxiliary for Asymmetric Synthesis (pages 4568–4571)

      Marvin R. Morales, Kevin T. Mellem and Prof. Andrew G. Myers

      Article first published online: 27 MAR 2012 | DOI: 10.1002/anie.201200370

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      Unrestricted: Pseudoephenamine is introduced as a versatile chiral auxiliary and an alternative to pseudoephedrine in asymmetric synthesis. It is free from regulatory restrictions and leads to remarkable stereocontrol in alkylation reactions, especially in those that form quaternary carbon centers. Amides derived from pseudoephenamine exhibit a high propensity to be crystalline substances, and provide sharp, well-defined signals in NMR spectra.

    3. Alkaloid Synthesis

      A Concise and Versatile Double-Cyclization Strategy for the Highly Stereoselective Synthesis and Arylative Dimerization of Aspidosperma Alkaloids (pages 4572–4576)

      Jonathan William Medley and Prof. Dr. Mohammad Movassaghi

      Article first published online: 12 MAR 2012 | DOI: 10.1002/anie.201200387

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      Building cycles: A strategy for the concise, stereoselective synthesis of aspidosperma alkaloids and related structures via a common putative diiminium ion intermediate is reported. The approach enables the dimerization of aspidosperma-type structures at the sterically hindered C2 position. The intermediate is prepared in one step from the shown lactam through an electrophilic double-cyclization cascade (see scheme; Tf=trifluoromethanesulfonyl).

    4. C[BOND]CF3 Bond Formation

      Copper-Catalyzed Trifluoromethylation of Allylsilanes (pages 4577–4580)

      Ryo Shimizu, Dr. Hiromichi Egami, Dr. Yoshitaka Hamashima and Prof. Dr. Mikiko Sodeoka

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201201095

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      CF3 on Cmath image: Trifluoromethylation of allylsilane derivatives was accomplished through the use of CuI and Togni's reagent (1) under mild conditions. The reaction of allylsilanes without a substituent in the 2-position gave vinylsilane derivatives, while 2-substituted allylsilanes afforded desilylated products. The utility of the products was demonstrated through their further transformation.

    5. Organofluorine Chemistry

      Catalytic Asymmetric Mono-Fluorination of α-Keto Esters: Synthesis of Optically Active β-Fluoro-α-Hydroxy and β-Fluoro-α-Amino Acid Derivatives (pages 4581–4585)

      Dr. Shoko Suzuki, Dr. Yuki Kitamura, Dr. Sylvain Lectard, Dr. Yoshitaka Hamashima and Prof. Dr. Mikiko Sodeoka

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201201303

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      Enantioselective mono-fluorination of α-keto esters was achieved using a mildly basic palladium μ-hydroxo complex as catalyst. Subsequent one-pot reduction afforded optically active β-fluoro-α-hydroxy esters. These compounds were then converted into β-fluoro-α-amino esters, which are potentially useful in medicinal chemistry research.

    6. Carbohydrate Recognition

      High-Affinity Disaccharide Binding by Tricyclic Synthetic Lectins (pages 4586–4590)

      Bunyarithi Sookcharoenpinyo, Dr. Emmanuel Klein, Dr. Yann Ferrand, Dr. D. Barney Walker, Dr. Peter R. Brotherhood, Dr. Chenfeng Ke, Dr. Matthew P. Crump and Prof. Anthony P. Davis

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201200447

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      Stay flexible: Rigid preorganization is not always the best approach to molecular recognition. Unlike previous synthetic lectins, new receptors (see picture) were synthesized that possess conformational freedom which allows hydrophobically driven collapse of the cavity. Nonetheless, they bind their carbohydrate targets in water with ground-breaking affinities (up to 4500 M−1 for methyl cellobioside, R=Me) and selectivities.

    7. Peptide Conformations

      Peptide Bond Tautomerization Induced by Divalent Metal Ions: Characterization of the Iminol Configuration (pages 4591–4593)

      Prof. Robert C. Dunbar, Dr. Jeffrey D. Steill, Prof. Nicolas C. Polfer, Dr. Giel Berden and Prof. Jos Oomens

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200437

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      Rearranged: The attachment of gas-phase divalent metal ions that bind as strongly as Mg2+ and transition-metal ions to the dipeptide PhePhe results in displacement of the amide proton by the newly characterized iminol tautomerization rearrangment. More weakly coordinating ions bind in the known charge-solvation mode. Infrared multiple-photon dissociation spectroscopy using the free-electron laser clearly shows the tautomeric transition.

    8. Aryl–Aryl Coupling

      Facile Bucky-Bowl Synthesis by Regiospecific Cove-Region Closure by HF Elimination (pages 4594–4597)

      K. Yu. Amsharov, M. A. Kabdulov and Prof. Dr. Martin Jansen

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200516

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      Building bowls: An effective intramolecular aryl–aryl coupling is the key step in rational fullerene synthesis and in synthesis of extended buckybowl structures. Such a process can be embodied very efficiently through quantitative HF elimination on active Al2O3. The process is characterized by an unprecedentedly high chemoselectivity and regiospecificity.

    9. Polyoxometalates

      Hybrid Assemblies of Eu-Containing Polyoxometalates and Hydrophilic Block Copolymers with Enhanced Emission in Aqueous Solution (pages 4598–4602)

      Prof. Jie Zhang, Yang Liu, Yang Li, Hongxiang Zhao and Prof. Xinhua Wan

      Article first published online: 27 MAR 2012 | DOI: 10.1002/anie.201107481

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      Core–shell nanostructures of a photoluminescent Eu-containing polyoxometalate (Eu-POM) with double-hydrophilic neutral–cationic block copolymer PEO114-b-PDMAEMA16 in aqueous solution were fabricated by self-assembly driven by electrostatic interactions (see scheme; neutral block blue, cationic block red). The emission of Eu-POM, which depends on the charge ratio of the Eu-POM/copolymer system, is enhanced up to 20-fold by complexation with the cationic PDMAEMA block.

    10. Radiopharmaceuticals

      Synthesis of [18F]BODIPY: Bifunctional Reporter for Hybrid Optical/Positron Emission Tomography Imaging (pages 4603–4606)

      Dr. J. Adam Hendricks, Dr. Edmund J. Keliher, Dongpeng Wan, Dr. Scott A. Hilderbrand, Prof. Ralph Weissleder and Prof. Ralph Mazitschek

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201107957

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      The best of both worlds: BODIPY-based imaging probes can be tracelessly transformed into hybrid PET/fluorescence imaging reagents by direct 19F/18F exchange without the need for redesign. This approach has the potential to accelerate not only the development of imaging agents, but perhaps also the screening of therapeutic molecules.

    11. MicroRNA Detection

      Target-Cell-Specific Delivery, Imaging, and Detection of Intracellular MicroRNA with a Multifunctional SnO2 Nanoprobe (pages 4607–4612)

      Dr. Haifeng Dong, Prof. Jianping Lei, Prof. Huangxian Ju, Dr. Feng Zhi, Dr. Hua Wang, Dr. Wenjie Guo, Zhu Zhu and Prof. Feng Yan

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201108302

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      Right on target: A multifunctional nanoprobe is designed for target-cell-specific imaging and in situ detection of intracellular miRNA. The nanoprobe is prepared by functionalizing SnO2 nanoparticles with both folic acid (FA), a target-cell-specific moiety to recognize folate receptors overexpressed on cancer cells, and a gene probe to inhibit or recognize intracellular miRNA levels (see scheme).

    12. Nanoparticles

      Probing Bioinspired Transport of Nanoparticles into Polymersomes (pages 4613–4617)

      Karmena Jaskiewicz, Antje Larsen, Dr. Ingo Lieberwirth, Dr. Kaloian Koynov, Prof. Wolfgang Meier, Prof. George Fytas, Dr. Anja Kroeger and Prof. Katharina Landfester

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201108421

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      Transmembrane transport: A combination of photon and fluorescence correlation spectroscopies is used to study the internalization of nanoparticles into a minimal model system based on poly(dimethylsiloxane)-block-poly(2-methyloxazoline) vesicles (see picture). These techniques provide information about the kinetics and dynamics of this transport process in real time.

    13. Tumor Cells

      Sensitive and High-Throughput Isolation of Rare Cells from Peripheral Blood with Ensemble-Decision Aliquot Ranking (pages 4618–4622)

      Perry G. Schiro, Mengxia Zhao, Jason S. Kuo, Karen M. Koehler, Prof. Daniel E. Sabath and Prof. Daniel T. Chiu

      Article first published online: 22 FEB 2012 | DOI: 10.1002/anie.201108695

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      Enrichment of cells: An approach called ensemble-decision aliquot ranking (eDAR) for isolating rare cells from peripheral blood is described. The eDAR process has a recovery of over 93 % (number of runs n=9) with a zero false positive rate (n=8) and provides direct easy access to individual isolated live cells for downstream single-cell manipulation and analysis (CTCs=circulating tumor cells).

    14. Cofactors

      Regulation of Redox Potential of a Pterin Derivative Bound to a Ruthenium(II) Complex by Intermolecular Hydrogen Bonding with Nucleobases (pages 4623–4627)

      Yuji Inui, Dr. Soushi Miyazaki, Dr. Kei Ohkubo, Prof. Dr. Shunichi Fukuzumi and Prof. Dr. Takahiko Kojima

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201108827

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      Potential control: A RuII-bound pterin forms a stable hydrogen-bonding adduct with a guanine derivative through three-point recognition. A large positive shift of the reduction potential of the pterin ligand up to +320 mV is observed (see picture). For the thymine derivative, the mode of hydrogen bonding is altered. Regulation of redox potentials of a pterin coenzyme by noncovalent interaction is demonstrated.

    15. Gene Synthesis

      RNA-Mediated Gene Assembly from DNA Arrays (pages 4628–4632)

      Dr. Cheng-Hsien Wu, Dr. Matthew R. Lockett and Prof. Lloyd M. Smith

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201109058

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      Gene Genie: RNA-mediated gene assembly is possible in a single day from oligonucleotide sequences on a DNA array. A T7 promoter is appended to each surface-bound oligonucleotide and many RNA copies of each are then produced with T7 RNA polymerase (see Figure). These RNA molecules self-assemble into the desired full-length transcript by hybridization and ligation, which is then converted into double-stranded DNA by reverse transcriptase polymerase chain reaction.

    16. Cluster Compounds

      The Importance of Being Exchanged: [GdIII4MII8(OH)8(L)8(O2CR)8]4+ Clusters for Magnetic Refrigeration (pages 4633–4636)

      Dr. Thomas N. Hooper, Prof. Jürgen Schnack, Dr. Stergios Piligkos, Dr. Marco Evangelisti and Prof. Euan K. Brechin

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200072

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      Playing it cool: Almost all of the constituent parts of the complex [LnIII4MII8(OH)8(L)8(O2CR)8]X4, namely the lanthanide ions Ln3+, the transition-metal ions M2+, the bridging ligand L, the carboxylates, and the counterions X can be exchanged, thus allowing a thorough understanding of the individual contributions to the magnetocaloric effect. Example in picture: Gd purple, Cu green, O red, N blue.

    17. Small-Molecule Inhibitors

      Structure-Based Macrocyclization Yields Hepatitis C Virus NS5B Inhibitors with Improved Binding Affinities and Pharmacokinetic Properties (pages 4637–4640)

      Dr. Maxwell D. Cummings, Dr. Tse-I Lin, Lili Hu, Dr. Abdellah Tahri, David McGowan, Dr. Katie Amssoms, Stefaan Last, Dr. Benoit Devogelaere, Marie-Claude Rouan, Dr. Leen Vijgen, Dr. Jan Martin Berke, Pascale Dehertogh, Els Fransen, Erna Cleiren, Liesbet van der Helm, Dr. Gregory Fanning, Dr. Kristof Van Emelen, Prof. Dr. Origène Nyanguile, Dr. Kenny Simmen, Dr. Pierre Raboisson and Dr. Sandrine Vendeville

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201200110

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      The concept of drug-likeness distills the physicochemical properties of small-molecule drugs to a set of rules. Macrocyclic drugs are known to break these rules. A structure-based macrocyclization strategy was applied to design new hepatitis C virus NS5B inhibitors with improved pharmacokinetic properties, exemplifying a rational strategy for overcoming the confines of standard “drug-like chemical space”.

    18. Oxygen Reduction Reaction

      The Effect of Size on the Oxygen Electroreduction Activity of Mass-Selected Platinum Nanoparticles (pages 4641–4643)

      Dr. Francisco J. Perez-Alonso, Dr. David N. McCarthy, Anders Nierhoff, Dr. Patricia Hernandez-Fernandez, Christian Strebel, Dr. Ifan E. L. Stephens, Prof. Jane H. Nielsen and Prof. Ib Chorkendorff

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201200586

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      A matter of size: The particle size effect on the activity of the oxygen reduction reaction of size-selected platinum clusters was studied. The ORR activity decreased with decreasing Pt nanoparticle size, corresponding to a decrease in the fraction of terraces on the surfaces of the Pt nanoparticles (jk=kinetic current density, see picture).

    19. Liquid-Crystalline Polymers

      Photoinduced Deformation of Crosslinked Liquid-Crystalline Polymer Film Oriented by a Highly Aligned Carbon Nanotube Sheet (pages 4644–4647)

      Wei Wang, Xuemei Sun, Wei Wu, Prof. Huisheng Peng and Prof. Yanlei Yu

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201200723

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      Bending over backwards: A highly aligned carbon nanotube sheet orients crosslinked liquid-crystalline polymer through a simple melting process (see picture). The resulting composite film can be rapidly bent and unbent by alternate irradiation with UV and visible light. The film also exhibits excellent mechanical and electrical properties due to the incorporation of aligned CNTs.

    20. Photoinitiator Synthesis

      Phosphorous-Functionalized Bis(acyl)phosphane Oxides for Surface Modification (pages 4648–4652)

      Dipl.-Chem. Alex Huber, Dr. Andreas Kuschel, Dr. Timo Ott, Dr. Gustavo Santiso-Quinones, Dr. Daniel Stein, Dr. Judith Bräuer, Dr. Reinhard Kissner, Dr. Frank Krumeich, Dr. Hartmut Schönberg, Prof. Dr. Joëlle Levalois-Grützmacher and Prof. Dr. Hansjörg Grützmacher

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201026

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      Got a light? An efficient method for the synthesis of phosphorus-functionalized bis(acyl)phosphaneoxides (BAPOs) was developed, which allows the preparation of photoactive polymers or grafting of these photoinitiators to various surfaces. Irradiation in the presence of polymerizable monomers leads to coatings that can be deposited imagewise.

    21. Polymer–Lipid Complexes

      Detergent-Free Formation and Physicochemical Characterization of Nanosized Lipid–Polymer Complexes: Lipodisq (pages 4653–4657)

      Dr. Marcella C. Orwick, Dr. Peter J. Judge, Jan Procek, Dr. Ljubica Lindholm, Andrea Graziadei, Prof. Andreas Engel, Prof. Gerhard Gröbner and Prof. Anthony Watts

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201201355

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      Lipodisq particles are polymer–lipid complexes formed by detergent-free methods. Lipodisq particles containing dimyristoylphosphatidylcholine (DMPC) are characterized by increased lipid ordering compared to a DMPC dispersion. The styrene and maleic acid groups of the polymer interact with the DMPC lipid chains in bilayers, as well as lipid headgroups in the Lipodisq periphery (see picture).

    22. Self-Assembled Monolayers

      The Rate of Charge Tunneling through Self-Assembled Monolayers Is Insensitive to Many Functional Group Substitutions (pages 4658–4661)

      Dr. Hyo Jae Yoon, Dr. Nathan D. Shapiro, Dr. Kyeng Min Park, Dr. Martin M. Thuo, Dr. Siowling Soh and Prof. George M. Whitesides

      Article first published online: 13 APR 2012 | DOI: 10.1002/anie.201201448

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      Insensitivity: A series of molecules containing a common head group and body as well as structurally varied tail groups (-R) has been used in junctions with the structure Ag/S(CH2)4CONH(CH2)2R//Ga2O3/EGaIn to study the rates of charge transport by tunneling. Changing the structure of R over a range of common aliphatic, aromatic, and heteroaromatic organic groups was found to not significantly influence the rate of tunneling (see plots; the dashed lines represent calibration standards).

    23. Homogeneous Catalysis

      A Highly Active Protonated Tetranuclear Peroxotungstate for Oxidation with Hydrogen Peroxide (pages 4662–4665)

      Ryo Ishimoto, Dr. Keigo Kamata and Prof. Dr. Noritaka Mizuno

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201049

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      Acid assists: The reaction of [{WO(O2)2}2(μ-O)]2− with 0.5 equivalents of HNO3 gave a tetranuclear peroxotungstate (1; see picture) that has a dramatically enhanced activity for the epoxidation of cyclooctene with H2O2 compared to various peroxotungstates. The 1-catalyzed system was applicable to the selective oxidation of various kinds of substrates with 1.0–1.5 equivalents of H2O2.

    24. Aerobic Oxidation

      Room-Temperature Copper-Catalyzed Oxidation of Electron-Deficient Arenes and Heteroarenes Using Air (pages 4666–4670)

      Qiang Liu, Pan Wu, Yuhong Yang, Ziqi Zeng, Jie Liu, Hong Yi and Prof. Aiwen Lei

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200750

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      No pressure: The oxidation of aromatic C[BOND]H bonds at room temperature was realized through a copper-catalyzed “oxygenase-type” oxidation of arenes and heteroarenes in the presence of air (see scheme). The reaction involves an oxygen-atom transfer from O2 in the air onto the substrates.

    25. Si[BOND]H Bond Activation

      Radical Activation of Si[BOND]H Bonds by Organozinc and Silylzinc Reagents: Synthesis of Geminal Dizinciosilanes and Zinciolithiosilanes (pages 4671–4675)

      Dr. Roman Dobrovetsky, Yosi Kratish, Dr. Boris Tumanskii, Dr. Mark Botoshansky, Dr. Dmitry Bravo-Zhivotovskii and Prof. Yitzhak Apeloig

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200126

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      Si[BOND]H bonds can be activated by organozinc and silylzinc compounds in the presence of minute amounts of radical initiators such as tBu2Hg or AIBN, yielding zinciosilanes in good yields (see scheme). Activation of dihydridosilanes leads to geminal dizinciosilanes. Zincio-bridged disilyllithium compounds, which have three (1) and four metal–silicon bonds, were also synthesized.

    26. Bio-Inspired Hydrogels

      A Strong Bio-Inspired Layered PNIPAM–Clay Nanocomposite Hydrogel (pages 4676–4680)

      Dr. Jianfeng Wang, Dr. Ling Lin, Prof. Qunfeng Cheng and Prof. Lei Jiang

      Article first published online: 6 MAR 2012 | DOI: 10.1002/anie.201200267

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      Inspired by nacre, a layered poly(N-isopropylacrylamide)–clay nanocomposite hydrogel was successfully fabricated by combination of vacuum-filtration self-assembly and photo-initiated in situ polymerization. This bio-inspired layered nanocomposite hydrogel shows excellent mechanical properties, which can rival some biological soft tissues (see picture).

    27. Gold Catalysis

      Gold-Catalyzed Carbene Transfer to Alkynes: Access to 2,4-Disubstituted Furans (pages 4681–4684)

      Søren Kramer and Prof. Dr. Troels Skrydstrup

      Article first published online: 23 APR 2012 | DOI: 10.1002/anie.201200307

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      Furans of gold: The first example of a gold-catalyzed intermolecular addition of carbon ylides to terminal alkynes is reported (see scheme; DCE=dichloroethane, Tf=trifluoromethanesulfonyl). Subsequent intramolecular trapping of the generated gold carbene completes a formal [3+2] cycloaddition, which represents a novel synthesis of 2,4-disubstituted furans.

    28. Direct Aldol Reaction

      Base-Catalyzed Direct Aldolization of α-Alkyl-α-Hydroxy Trialkyl Phosphonoacetates (pages 4685–4689)

      Michael T. Corbett, Dr. Daisuke Uraguchi, Prof. Dr. Takashi Ooi and Prof. Dr. Jeffrey S. Johnson

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200559

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      Pass the P: Catalytic direct aldol addition of α-hydroxy trialkyl phosphonacetates to aldehydes affords α-hydroxy-β-phosphonyloxy ester products (see scheme). The fully substituted glycolate enolate intermediate is generated in situ under mild conditions by a [1,2] phosphonate–phosphate rearrangement. High enantioselectivity and dramatic enhancement of reaction diastereocontrol is realized by the application of chiral iminophosphorane catalysts.

    29. Nanostructures

      Tuning Complex Shapes in Platinum Nanoparticles: From Cubic Dendrites to Fivefold Stars (pages 4690–4694)

      Dr. Lise-Marie Lacroix, Dr. Christophe Gatel, Dr. Raul Arenal, Dr. Cécile Garcia, Dr. Sébastien Lachaize, Dr. Thomas Blon, Dr. Bénédicte Warot-Fonrose, Prof. Etienne Snoeck, Prof. Bruno Chaudret and Prof. Guillaume Viau

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201107425

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      A platinum star performance: Quasi-single-crystalline Pt nanoparticles with peculiar morphologies—cubic dendrites, planar tripods, and fivefold stars—were synthesized in high yield. Shape selectivity was achieved by finely tuning the growth kinetics under a dihydrogen atmosphere.

    30. Biomimetic Synthesis

      In Silico Inspired Total Synthesis of (−)-Dolabriferol (pages 4695–4697)

      Russell H. Currie and Dr. Jonathan M. Goodman

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201109080

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      Going retro: The diazabicycloundecane-induced retro-Claisen rearrangement of a linear precursor serves as the key step to form the hindered ester of the polypropionate dolabriferol (1, see scheme, PMB=p-methoxybenzyl, PMP=p-methoxyphenyl, TES=triethylsilyl). The rearrangement is thought to mimic the biosynthetic formation of 1.

    31. C[BOND]H Bond Functionalization

      Mild and Efficient C2-Alkenylation of Indoles with Alkynes Catalyzed by a Cobalt Complex (pages 4698–4701)

      Zhenhua Ding and Prof. Naohiko Yoshikai

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200019

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      Direct alkenylation of the C2-position of indoles bearing an easily removable N-pyrimidyl group with alkynes has been achieved by using a cobalt catalyst complexed with a phosphine–pyridine bidentate ligand. This reaction has wide substrate scope and is highly efficient and stereoselective at room temperature. The alkenylated indoles serve as useful platforms for further synthetic transformations (some products of these transformations are shown in the scheme).

    32. C[BOND]H Bond Activation

      Synergistic Effect on the Photoactivation of the Methane C[BOND]H Bond over Ga3+-Modified ETS-10 (pages 4702–4706)

      Lu Li, Yi-Yu Cai, Prof. Guo-Dong Li, Xiao-Yue Mu, Prof. Kai-Xue Wang and Prof. Jie-Sheng Chen

      Article first published online: 23 APR 2012 | DOI: 10.1002/anie.201200045

      Thumbnail image of graphical abstract

      Breaking down methane: A Ga3+-modified microporous titanosilicate (ETS-10) exhibits distinct photoactivity for the cleavage of the methane C[BOND]H bond at room temperature. The highly enhanced activity is attributed to the synergistic effect of gallium-induced C[BOND]H bond polarization and a titania-based photoredox process.

    33. Solid-State Structures

      An Unprecedented AB2 Tetrahedra Network Structure Type in a High-Pressure Phase of Phosphorus Oxonitride (PON) (pages 4707–4709)

      Dominik Baumann, Dr. Stefan J. Sedlmaier and Prof. Dr. Wolfgang Schnick

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201200811

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      Restructuring: An unprecedented framework structure made up of tetrahedra has been discovered in a novel high-pressure polymorph of the phosphorus oxonitride PON by treating a single-source precursor at 12 GPa and 1250 °C. It is the first polymorph of PON that does not crystallize in a structure type known from SiO2.

    34. Cross-Coupling

      A Bulky Biaryl Phosphine Ligand Allows for Palladium-Catalyzed Amidation of Five-Membered Heterocycles as Electrophiles (pages 4710–4713)

      Mingjuan Su and Prof. Dr. Stephen L. Buchwald

      Article first published online: 30 MAR 2012 | DOI: 10.1002/anie.201201244

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      The incredible bulk: The first palladium-catalyzed amidation of five-membered heterocyclic bromides with multiple heteroatoms was achieved using the Pd/1 catalyst system. N-Arylated imidazoles, pyrazoles, thiazoles, pyrroles, and thiophenes were synthesized in moderate to excellent yield. Experimental results and DFT calculations point to the need for an electron-rich and sterically demanding biaryl phosphine ligand to promote these difficult reactions.

    35. Carbon Dioxide Capture

      Phosphorus as a Lewis Acid: CO2 Sequestration with Amidophosphoranes (pages 4714–4717)

      Dr. Lindsay J. Hounjet, Christopher B. Caputo and Prof. Dr. Douglas W. Stephan

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201201422

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      CO2 snapper: Compounds containing both acidic and basic P,N functionalities have been prepared. Of these, two amidophosphoranes containing highly reactive P[BOND]N bonds within four-membered rings react rapidly with CO2, resulting in relief of ring strain. These compounds demonstrate the utility of phosphorus as a Lewis acid for small-molecule activation.

    36. Acyl Azides

      Experimental and Theoretical Studies on the Synthesis, Spectroscopic Data, and Reactions of Formyl Azide (pages 4718–4721)

      Prof. Dr. Klaus Banert, Christian Berndt, Dr. Manfred Hagedorn, Hailiang Liu, Tony Anacker, Prof. Dr. Joachim Friedrich and Prof. Dr. Guntram Rauhut

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201200029

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      Small is beautiful: spectroscopic proof or any other indication for the existence of formyl azide (HC(O)N3) has until now been lacking. Although it liberates dinitrogen much more rapidly than homologous acyl azides, it has been prepared for the first time by four different methods (see scheme).

    37. Multicomponent Reactions

      A Catalytic Multicomponent Approach for the Stereoselective Synthesis of cis-4,5-Disubstituted Pyrrolidinones and Tetrahydro-3H-pyrrolo[3,2-c]quinolines (pages 4722–4725)

      M. Sc. Sudipta Roy and Prof. Dr. Oliver Reiser

      Article first published online: 27 MAR 2012 | DOI: 10.1002/anie.201107831

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      Ménage à trois: In a three-component reaction, furancarbaldehydes 1, anilines 2, and the monocyclopropanated pyrrole 3 can be assembled highly stereoselectively to give cis-4,5-disubstituted pyrrolidinones (see scheme; Boc=tert-butoxycarbonyl). The products are lead structures for pharmaceutically important compounds.

    38. Synthetic Methods

      Synthesis of Macroheterocycles through Intramolecular Oxidative Coupling of Furanoid β-Ketoesters (pages 4726–4730)

      Prof. Dr. K. C. Nicolaou, Christopher R. H. Hale, Christian Ebner, Dr. Christian Nilewski, Christopher F. Ahles and Derek Rhoades

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201201538

      Thumbnail image of graphical abstract

      It's all in the CAN: Cerium ammonium nitrate (CAN) promotes the oxidative radical cyclization of furan β-ketoesters to form macrocycles of varying ring sizes. The reaction is tolerant of unsaturation, oxygenation, and nitrogen and oxygen heterocycles in the carbon backbone tether.

    39. Surface Chemistry

      The Surface Science Approach for Understanding Reactions on Oxide Powders: The Importance of IR Spectroscopy (pages 4731–4734)

      Dr. Mingchun Xu, Dr. Heshmat Noei, Dr. Karin Fink, Prof. Dr. Martin Muhler, Dr. Yuemin Wang and Prof. Dr. Christof Wöll

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201200585

      Thumbnail image of graphical abstract

      Chemistry at defects: The concentration of defect sites at rutile TiO2 (r-TiO2) surfaces of both single crystals and powder particles was determined by UHV-FTIR spectroscopy using CO as a probe molecule (see picture). The potential of this novel approach is demonstrated by unraveling the mechanism of reductive coupling of formaldehyde to give ethylene.

    40. Organic Pigments

      Crystal Structures of the Hydration States of Pigment Red 57:1 (pages 4735–4738)

      Sándor L. Bekö, Sonja M. Hammer and Prof. Dr. Martin U. Schmidt

      Article first published online: 29 MAR 2012 | DOI: 10.1002/anie.201109082

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      The Red carrying the news around the world: Most newspapers and journals worldwide (including Angewandte Chemie) are printed with Pigment Red 57:1. The crystal structures of this pigment in various hydration states have now been determined by X-ray powder diffraction.

    41. Radical Chemistry

      Catalytic, Atom-Economical Radical Arylation of Epoxides (pages 4739–4742)

      Prof. Dr. Andreas Gansäuer, Maike Behlendorf, Daniel von Laufenberg, André Fleckhaus, Christian Kube, Dr. Dhandapani V. Sadasivam and Prof. Robert A. Flowers II

      Article first published online: 27 MAR 2012 | DOI: 10.1002/anie.201200431

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      A slow electron waltz: Catalysis in single-electron steps with radicals as intermediates is essential for an atom-economical arylation of epoxides with a proton-coupled electron transfer as a key step. Stabilization of the catalyst is essential for low catalyst loading, as demonstrated by reaction-progress kinetic analysis, cyclic voltammetry, and calculations.

    42. Electroless Deposition

      Liquid-Phase Deposition of Freestanding Copper Foils and Supported Copper Thin Films and Their Structuring into Conducting Line Patterns (pages 4743–4746)

      Niklaus Kränzlin, Stefan Ellenbroek, Dr. Desirée Durán-Martín and Prof. Markus Niederberger

      Article first published online: 5 APR 2012 | DOI: 10.1002/anie.201200428

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      Metal foils: A simple electroless liquid-phase deposition technique gives access to freestanding copper foils and supported copper thin films. The films can be easily structured into conducting line patterns for electronics applications (see picture).

    43. Knot Structures

      NMR-Based Structure Determination of an Intertwined Coordination Cage Resembling a Double Trefoil Knot (pages 4747–4750)

      David M. Engelhard, Sabrina Freye, Kristof Grohe, Dr. Michael John and Prof.Dr. Guido H. Clever

      Article first published online: 4 APR 2012 | DOI: 10.1002/anie.201200611

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      A knot that ties itself! The entanglement of six ligands coordinated to three PdII ions results in the quantitative formation of a walnut-shaped supramolecular cage. Each of the two hemispheres resembles a trefoil knot. The solution-state structure was elucidated using a combination of NMR experiments and calculated model structures. The final structure was selected from several models by topological analyses and encapsulation of chiral camphorsulfonate ions.

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      Article first published online: 3 MAY 2012 | DOI: 10.1002/anie.201290035

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