Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 32

August 5, 2013

Volume 52, Issue 32

Pages 8171–8471

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Redox Cofactor from Biological Energy Transduction as Molecularly Tunable Energy-Storage Compound (Angew. Chem. Int. Ed. 32/2013) (page 8171)

      Minah Lee, Jihyun Hong, Dr. Dong-Hwa Seo, Dong Heon Nam, Prof. Ki Tae Nam, Prof. Kisuk Kang and Prof. Chan Beum Park

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201304976

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      The cellular metabolism comprises energy transduction machineries that operate by a series of redox-active components such as flavin molecules to store energy. In their Communication on page 8322 ff., C. B. Park, K. Kang, et al. present a biomimetic approach based on the analogy between energy-storage phenomena of mitochondria and rechargeable lithium batteries to design high-performance energy devices.

    2. You have free access to this content
      Inside Cover: Photodissociation and Dissociative Photoionization Mass Spectrometry of Proteins and Noncovalent Protein–Ligand Complexes (Angew. Chem. Int. Ed. 32/2013) (page 8172)

      Dr. Francis Canon, Dr. Aleksandar R. Milosavljević, Dr. Guillaume van der Rest, Dr. Matthieu Réfrégiers, Dr. Laurent Nahon, Dr. Pascale Sarni-Manchado, Dr. Véronique Cheynier and Dr. Alexandre Giuliani

      Article first published online: 26 JUL 2013 | DOI: 10.1002/anie.201305979

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      Identification of the noncovalent binding sites of an intrinsically disordered protein is a challenge. In their Communication on page 8377 ff., A. Giuliani and co-workers use synchrotron radiation coupled to mass spectrometry to perform photo-fragmentation of a human intrinsically disordered protein. The interaction of the protein with tannins is involved in the perception of astringency upon drinking tea or red wine. The method maintains the noncovalent bonds, allowing the identification of the protein tannin binding site.

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      Inside Back Cover: Stepwise-Resolved Thermodynamics of Hydrophobic Self-Assembly (Angew. Chem. Int. Ed. 32/2013) (page 8473)

      Alina Grego, Prof. Achim Müller and Prof. Ira A. Weinstock

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201304906

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      Unprecedented insight into hydrophobic self-assembly can be obtained using a new type of experiment described by A. Grego, A. Müller, and I. A. Weinstock in their Communication on page 8358 ff. The method allows study of the stepwise growth of structurally defined organic aggregates within a water-soluble porous metal-oxide nanocapsule. Different hydrophobic effects drive sequential growth steps, leading to the formation of a beautiful micelle-like assembly with a practically water-free central cavity.

    4. You have free access to this content
      Back Cover: Synthesis, Structure and Gas-Phase Reactivity of a Silver Hydride Complex [Ag3{(PPh2)2CH2}33-H)(μ3-Cl)]BF4 (Angew. Chem. Int. Ed. 32/2013) (page 8474)

      Athanasios Zavras, Dr. George N. Khairallah, Timothy U. Connell, Prof. Jonathan M. White, Dr. Alison J. Edwards, Dr. Paul S. Donnelly and Prof. Richard A. J. O'Hair

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201304983

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      Mass Spectrometry Man saves the day! Traveling from his home on planet Gas Phase, he used his ESI-MS powers to provide G. N. Khairallah, P. S. Donnelly, R. A. J. O'Hair, and co-workers with vital information for their Communication on page 8391 ff. MS Man's powers revealed the formation of novel silver hydride nanocluster cations in silver salts reduced by sodium borohydride in the presence of a bis(phosphino) ligand, and led the way to the condensed-phase synthesis, isolation, and characterization of [Ag3{(Ph2P)2CH2}33-H)(μ3-Cl)]BF4⋅0.5 CHCl3.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 32/2013 (pages 8175–8190)

      Article first published online: 2 AUG 2013 | DOI: 10.1002/anie.201390032

  3. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. You have free access to this content
      Corrigendum: Biomimetic Surface Engineering of Lanthanide-Doped Upconversion Nanoparticles as Versatile Bioprobes (page 8190)

      Dr. Le-Le Li, Dr. Ruobing Zhang, Dr. Leilei Yin, Kezhi Zheng, Prof. Dr. Weiping Qin, Prof. Dr. Paul R. Selvin and Prof. Dr. Yi Lu

      Article first published online: 2 AUG 2013 | DOI: 10.1002/anie.201305509

      This article corrects:

      Biomimetic Surface Engineering of Lanthanide-Doped Upconversion Nanoparticles as Versatile Bioprobes1

      Vol. 51, Issue 25, 6121–6125, Article first published online: 8 MAY 2012

  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. C. Oliver Kappe (page 8198)

      Article first published online: 12 MAR 2013 | DOI: 10.1002/anie.201300854

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      “My favorite quote is ‘when the going gets tough, the tough get going’. My favorite time of day is early morning …” This and more about C. Oliver Kappe can be found on page 8198.

  6. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. Structural Methods in Molecular Inorganic Chemistry. By D. W. H. Rankin, Norbert Mitzel and Carole Morrison. (pages 8200–8201)

      Florian Kraus

      Article first published online: 2 JUL 2013 | DOI: 10.1002/anie.201304990

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      John Wiley & Sons, Hoboken, 2013. 498 pp., hardcover, € 137.00.—ISBN 978-0470972793

  8. Correspondence

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. Quantum Mechanics (1)

      Correct Interpretation of How Tunneling Proceeds at Low Temperatures in the Proton Transfer Reactions Involving Thiotropolone: A Comment (pages 8204–8205)

      Dr. Antonio Fernández-Ramos

      Article first published online: 5 JUL 2013 | DOI: 10.1002/anie.201303206

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      The correct interpretation is provided of how tunneling proceeds at low temperatures in the proton transfer Reactions (1) and (3) involving thiotropolone and tropolone (see the Arrhenius plots). It is also shown that the variational transition-state theory calculations carried out by Jose and Datta (Angew. Chem.­ 2012, 124, 9523; Angew. Chem. Int. Ed.­ 2012, 51, 9389), as well as their conclusions regarding these two processes are erroneous.

    2. Quantum Mechanics (2)

      Pronounced Tunneling Effect of Proton Transfer in Thiotropolone at Room Temperature: A Reply (pages 8206–8207)

      Prof. Dr. Ayan Datta

      Article first published online: 10 JUL 2013 | DOI: 10.1002/anie.201304556

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      Quantum mechanical calculations can provide insight into the role of tunneling in many reactions. At room temperature a pronounced tunneling effect of proton transfer is found for thiotropolone (see picture).

  9. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. Flexible Minerals

      Bio-Inspired Materials Science at Its Best—Flexible Mesocrystals of Calcite (pages 8208–8209)

      Dr. Denis Gebauer

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201303933

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      Minerals are the benchmark of hard and brittle materials. Self-assembled calcitic spicules were recently obtained utilizing a protein from silica biomineralization, silicatein-α. The synthetic spicules show remarkable material properties including extreme flexibility. Breakthroughs in bio-inspired materials science are highlighted. Will it be possible to obtain similar composites with truly artificial organic constituents?

    2. Activity-Based Protein Probes

      Propargyl Amides as Irreversible Inhibitors of Cysteine Proteases—A Lesson on the Biological Reactivity of Alkynes (pages 8210–8212)

      Dr. Christoph Arkona and Prof. Dr. Jörg Rademann

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201303544

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      Are aliphatic alkynes truly bioorthogonal? In an attempt to prepare clickable ubiquitin derivatives bearing a C-terminal propargyl amide, two groups have now independently discovered propargylamides to be irreversible inhibitors of cysteine proteases. The unexpected findings demonstrate the unexpected reactivity of alkynes in protein-templated reactions and introduce a novel class of activity-based protein probes.

  10. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. Fluorine

      Introduction of Fluorine and Fluorine-Containing Functional Groups (pages 8214–8264)

      Dr. Theresa Liang, Constanze N. Neumann and Prof. Tobias Ritter

      Article first published online: 19 JUL 2013 | DOI: 10.1002/anie.201206566

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      Although known for more than 100 years, fluorination still remains a challenge today. Recent advances, to a large extent enabled by catalysis, have resulted in more efficient methods to introduce fluorine and fluorine-containing functional groups into functionalized molecules. This Review focuses on new strategies for fluorination, with a brief introduction to conventional fluorination, so that the modern methods can be put into perspective.

  11. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlights
    11. Review
    12. Communications
    1. Self-Assembling Fibers

      Supramolecular Self-Assembly of N-Acetyl-Capped β-Peptides Leads to Nano- to Macroscale Fiber Formation (pages 8266–8270)

      Dr. Mark P. Del Borgo, Dr. Adam I. Mechler, Dr. Daouda Traore, Dr. Craig Forsyth, Assoc.Prof. Jacqueline A. Wilce, Prof. Matthew C. J. Wilce, Prof. Marie-Isabel Aguilar and Prof. Patrick Perlmutter

      Article first published online: 19 JUN 2013 | DOI: 10.1002/anie.201303175

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      From little things big things grow: 14-Helical N-acetyl β3-peptides spontaneously self-assemble in a unique head-to-tail fashion to form fibers from solution. The fiber size can be controlled from the nano- to the macroscale. The inherent flexibility in design and ease of synthesis provide powerful new avenues for the development of novel bio- and nanomaterials by supramolecular self-assembly.

    2. Natural Products

      Nitro versus Hydroxamate in Siderophores of Pathogenic Bacteria: Effect of Missing Hydroxylamine Protection in Malleobactin Biosynthesis (pages 8271–8275)

      Jakob Franke, Dr. Keishi Ishida, Dr. Mie Ishida-Ito and Prof. Dr. Christian Hertweck

      Article first published online: 2 JUL 2013 | DOI: 10.1002/anie.201303196

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      The elusive structure of malleobactin, a virulence factor of pathogens belonging to the Burkholderia mallei family, was finally unveiled by genetic and chemical analyses. The novel nitro-substituted siderophore is derived from an unusual, unprotected hydroxylamine, which undergoes spontaneous oxidation, as shown by in vitro assays and detection of analogues featuring hydroxylamino, nitroso, and azoxide groups.

    3. Photovoltaics

      Photovoltaic Wire with High Efficiency Attached onto and Detached from a Substrate Using a Magnetic Field (pages 8276–8280)

      Hao Sun, Zhibin Yang, Xuli Chen, Longbin Qiu, Xiao You, Peining Chen and Prof. Huisheng Peng

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201303216

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      Post-it wire: Novel photovoltaic wires which can be easily attached onto a substrate by a magnetic field and then detached from the substrate after their use have been developed with a record energy conversion efficiency of 8.03 % (see picture; CNT=carbon nanotube). The photovoltaic wire is also lightweight, flexible, and can be interwoven.

    4. NMR Spectroscopy

      Ultrafast Scanning of Exchangeable Sites by NMR Spectroscopy (pages 8281–8284)

      Dr. Xiang Xu, Dr. Jae-Seung Lee and Prof. Alexej Jerschow

      Article first published online: 27 JUN 2013 | DOI: 10.1002/anie.201303255

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      Development of NMR methods: A fast method is reported to obtain Z-spectra for studying magnetization transfer and chemical exchange saturation transfer phenomena in homogeneous systems. The method exploits gradient fields to irradiate a given system and to acquire the z polarization of water protons simultaneously at many frequency offsets (see picture).

    5. Supramolecular Chemistry

      Supramolecular Photosensitizers with Enhanced Antibacterial Efficiency (pages 8285–8289)

      Kai Liu, Yiliu Liu, Yuxing Yao, Huanxiang Yuan, Prof. Shu Wang, Prof. Zhiqiang Wang and Prof. Xi Zhang

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201303387

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      Photodynamic therapy: A novel supramolecular photosensitizer is efficiently fabricated based on a strong host–guest interaction, which shows an enhanced singlet oxygen generation ability of the porphyrin units and has thus a greatly improved antibacterial efficiency (see picture). The supramolecular photosensitizer is an adaptive system with switchable photophysical properties.

    6. Metal–Organic Frameworks

      Highly Hydrophobic Isoreticular Porous Metal–Organic Frameworks for the Capture of Harmful Volatile Organic Compounds (pages 8290–8294)

      Natalia M. Padial, Dr. Elsa Quartapelle Procopio, Carmen Montoro, Elena López, Prof. J. Enrique Oltra, Dr. Valentina Colombo, Dr. Angelo Maspero, Prof. Norberto Masciocchi, Dr. Simona Galli, Dr. Irena Senkovska, Prof. Stefan Kaskel, Dr. Elisa Barea and Prof. Jorge A. R. Navarro

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201303484

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      Tunable hydrophobicity: Efficient air filters for the protection against chemical warfare agents might be achieved by surface functionalization of the pores in robust metal–organic frameworks (MOFs) with fluoroalkyl residues and the precise control of their pore size (see picture). These MOFs capture harmful volatile organic compounds even under extremely moist conditions (80 % relative humidity).

    7. Protein Engineering

      Functional Antibody CDR3 Fusion Proteins with Enhanced Pharmacological Properties (pages 8295–8298)

      Dr. Yong Zhang, Dr. Danling Wang, Dr. Lorenzo de Lichtervelde, Sophie B. Sun, Dr. Vaughn V. Smider, Dr. Peter G. Schultz and Dr. Feng Wang

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201303656

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      Real staying power: A subset of bovine antibodies (blue, see scheme) feature an ultralong CDR3 loop that forms an antiparallel β-sheet stalk, terminating in a folded, disulfide cross-linked knob domain. Fusion of a polypeptide (red) into this unique CDR3 motif provides a novel strategy for generating polypeptide therapeutics with enhanced pharmacokinetics and pharmacodynamics.

    8. Asymmetric Catalysis

      Enantioselective Cyanoethoxycarbonylation of Isatins Promoted by a Lewis Base–Brønsted Acid Cooperative Catalyst (pages 8299–8303)

      Yoshihiro Ogura, Prof. Dr. Matsujiro Akakura, Prof. Dr. Akira Sakakura and Prof. Dr. Kazuaki Ishihara

      Article first published online: 3 JUL 2013 | DOI: 10.1002/anie.201303572

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      Teaming up to make it happen: In the title reaction, the Lewis basic site of the catalyst activated ethyl cyanoformate, and the deep and flexible Brønsted acidic cavity stabilized and selectively recognized the key reaction intermediate to promote asymmetric acylation (see scheme).

    9. Nanoparticles

      Light-Triggered Self-Assembly of Gold Nanoparticles Based on Photoisomerization of Spirothiopyran (pages 8304–8308)

      Dr. Yasuhiro Shiraishi, Kazuya Tanaka, Eri Shirakawa, Dr. Yoshitsune Sugano, Dr. Satoshi Ichikawa, Dr. Shunsuke Tanaka and Prof. Takayuki Hirai

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201302430

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      Give it some stick: UV irradiation of spirothiopyran in an aqueous solution of gold nanoparticles (AuNPs) gives AuNP aggregates. The aggregate size is tuned by the photoirradiation time and the aggregation is facilitated by the covalent binding of photoisomerized spirothiopyran to the surface of the AuNPs. This binding decreases the electrostatic repulsion between the AuNPs.

    10. Natural Products

      Total Synthesis of (−)-Melotenine A (pages 8309–8311)

      Senzhi Zhao, Gopal Sirasani, Dr. Shivaiah Vaddypally, Dr. Michael J. Zdilla and Dr. Rodrigo B. Andrade

      Article first published online: 19 JUN 2013 | DOI: 10.1002/anie.201302517

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      'Melo' out: A concise asymmetric synthesis of (−)-melotenine A has been accomplished in fourteen steps and 1 % overall yield from commercial N-tosylindole-3-carboxaldehyde. Key steps include a Piers annulation, an intermolecular vinylogous aldol reaction, and a novel one-pot sequence to prepare the ABCE tetracycle. Boc=tert-butoxycarbonyl, Ts=4-toluenesulfonyl.

    11. Molecular Machines

      You have full text access to this OnlineOpen article
      The Archaeal Exosome: Identification and Quantification of Site-Specific Motions That Correlate with Cap and RNA Binding (pages 8312–8316)

      Maxime J. C. Audin, Georg Dorn, Simon A. Fromm, Kerstin Reiss, Stefan Schütz, Matthias K. Vorländer and Dr. Remco Sprangers

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201302811

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      Big and unexpectedly flexible: The 173 kDa exosome core is unexpectedly dynamic in solution. The kinetic and thermodynamic properties connected with the identified exchange process were quantified. Both cap protein and RNA substrate binding significantly alter the identified motions, suggesting that these interactions occur through conformational selection.

    12. Optochemical Sensing

      A Versatile Fiber-Optic Fluorescence Sensor Based on Molecularly Imprinted Microstructures Polymerized in Situ (pages 8317–8321)

      Xuan-Anh Ton, Dr. Bernadette Tse Sum Bui, Dr. Marina Resmini, Dr. Paolo Bonomi, Ihab Dika, Dr. Olivier Soppera and Prof. Karsten Haupt

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201301045

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      Seeing molecules: A method using laser-induced photopolymerization was developed to generate highly selective fiber optic sensors in a few seconds that are based on molecularly imprinted polymer (MIP) microtips. The fluorescence detection signal was enhanced using gold nanoparticles. The sensor also detects nonfluorescent analytes when a fluorescent signaling monomer is incorporated into the MIP.

    13. Biomimetics

      Redox Cofactor from Biological Energy Transduction as Molecularly Tunable Energy-Storage Compound (pages 8322–8328)

      Minah Lee, Jihyun Hong, Dr. Dong-Hwa Seo, Dong Heon Nam, Prof. Ki Tae Nam, Prof. Kisuk Kang and Prof. Chan Beum Park

      Article first published online: 19 JUN 2013 | DOI: 10.1002/anie.201301850

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      Flavin Battery: Flavins are used as a molecularly tunable cathode material that reversibly reacts with two lithium ions and two electrons per formula unit. Combined ex situ analyses and DFT calculations reveal that the redox reaction occurs using two successive single-electron transfer steps at nitrogen atoms of the diazabutadiene motif (see picture).

    14. Protein Structure

      Hofmeister Salts Recover a Misfolded Multiprotein Complex for Subsequent Structural Measurements in the Gas Phase (pages 8329–8332)

      Linjie Han and Prof. Dr. Brandon T. Ruotolo

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201301893

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      A misfolded protein complex (see picture, red tetramer), which exists both in solution and in the gas phase, can be recovered back to a native-like structure (blue) by the addition of salts prior to desorption/ionization into the gas phase using nano-electrospray ionization.

    15. Synthetic Methods

      Domino Cycloaddition Organocascades of Dendralenes (pages 8333–8336)

      Nicholas J. Green, Dr. Andrew L. Lawrence, Dr. Gomotsang Bojase, Dr. Anthony C. Willis, Prof. Michael N. Paddon-Row and Prof. Michael S. Sherburn

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201302185

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      Hooray Horeau! Highly enantioselective organocatalyzed Diels–Alder reaction cascades are disclosed for the first time. The reaction enables the efficient and rapid construction of enantiopure polycycles from simple achiral, acyclic polyenes.

    16. Cancer Cells

      Efficient Isolation and Accurate In Situ Analysis of Circulating Tumor Cells Using Detachable Beads and a High-Pore-Density Filter (pages 8337–8340)

      Hun Joo Lee, Dr. Jin Ho Oh, Jin Mi Oh, Jong-Myeon Park, Dr. Jeong-Gun Lee, Dr. Minseok S. Kim, Dr. Yeon Jeong Kim, Dr. Hyun Ju Kang, Prof. Joon Jeong, Prof. Seung Il Kim, Dr. Soo Suk Lee, Prof. Jeong-Woo Choi and Dr. Nam Huh

      Article first published online: 3 JUL 2013 | DOI: 10.1002/anie.201302278

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      Analysis of cancer cells: A new technique isolates rare circulating tumor cells (CTCs) and analyzes their protein expression by the use of detachable beads and high-pore-density filters. This technique shows significantly improved efficiency in the isolation of rare CTCs from peripheral blood and enables accurate measurement of in situ protein-expression levels.

    17. Organic Photovoltaics

      High-Molecular-Weight Regular Alternating Diketopyrrolopyrrole-based Terpolymers for Efficient Organic Solar Cells (pages 8341–8344)

      Koen H. Hendriks, Gaël H. L. Heintges, Dr. Veronique S. Gevaerts, Dr. Martijn M. Wienk and Prof. René A. J. Janssen

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201302319

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      A regular alternating terpolymer design strategy is used to create a semiconducting polymer with tailored energy levels and optical band gap. Combined with a modified synthetic procedure for the polymerization reaction, high-molecular-weight polymers of the terpolymer as well as the parent co-polymers were obtained with high efficiencies (up to 8.0 %) in organic solar cells when combined with [70]PCBM.

    18. Natural Product Synthesis

      Biomimetic Dehydrogenative Diels–Alder Cycloadditions: Total Syntheses of Brosimones A and B (pages 8345–8348)

      Chao Qi, Huan Cong, Katharine J. Cahill, Peter Müller, Prof. Dr. Richard P. Johnson and Prof. Dr. John A. Porco Jr.

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201302847

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      Passing (H2) gas: Concise syntheses of the natural products brosimones A and B have been achieved using sequential dehydrogenative Diels–Alder (DHDA) cycloadditions. The syntheses employ either Pt/C-cyclopentene or DDQ to effect dehydrogenation of prenylchalcone substrates in combination with silver nanoparticles to promote subsequent Diels–Alder cycloadditions.

    19. Fuel-Cell Catalysts

      A Highly Active and Support-Free Oxygen Reduction Catalyst Prepared from Ultrahigh-Surface-Area Porous Polyporphyrin (pages 8349–8353)

      Dr. Shengwen Yuan, Dr. Jiang-Lan Shui, Lauren Grabstanowicz, Chen Chen, Sean Commet, Briana Reprogle, Prof. Dr. Tao Xu, Prof. Dr. Luping Yu and Dr. Di-Jia Liu

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201302924

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      An electrocatalyst for the oxygen reduction reaction that is free of precious metals was prepared by thermal activation of an ultrahigh-surface-area porous polyporphyrin. The PEM fuel cells made with such catalyst demonstrated excellent current and power densities.

    20. Polyamorphism

      Pressure-Induced Polyamorphism and Formation of ‘Aragonitic’ Amorphous Calcium Carbonate (pages 8354–8357)

      Dr. Alejandro Fernandez-Martinez, Dr. Bora Kalkan, Dr. Simon M. Clark and Dr. Glenn A. Waychunas

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201302974

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      Pressed for time: Amorphous calcium carbonate (ACC) undergoes a reversible amorphous–amorphous phase transition at 10 GPa, adopting an aragonite-like local order. This result suggests a mechanism by which Mg2+—a cation with smaller ionic radius than Ca2+—modifies the local order of ACC to an aragonite-like order by helping to decrease the molar volume of the amorphous phase.

    21. Supramolecular Chemistry

      Stepwise-Resolved Thermodynamics of Hydrophobic Self-Assembly (pages 8358–8362)

      Alina Grego, Prof. Achim Müller and Prof. Ira A. Weinstock

      Article first published online: 13 JUN 2013 | DOI: 10.1002/anie.201303083

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      Unprecedented information concerning how the relative roles of different hydrophobic effects evolve during multistep hydrophobic assembly processes is provided by using a unique type of experiment to resolve the underlying energetics of individual growth steps in the formation of a structurally well-defined micelle-like organic aggregate of n-butyrate ions within a porous inorganic-oxide nanocapsule.

    22. Li–Se Batteries

      An Advanced Selenium–Carbon Cathode for Rechargeable Lithium–Selenium Batteries (pages 8363–8367)

      Chun-Peng Yang, Sen Xin, Dr. Ya-Xia Yin, Huan Ye, Juan Zhang and Prof. Yu-Guo Guo

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201303147

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      Selenium has been confined in the form of cyclic Se8 molecules within ordered mesoporous carbon for use as a cathode material in Li–Se batteries. An ex situ study of the Se cathode reveals conversion from cyclic Se8 molecules into chain-like Sen molecules upon cycling. This effectively eliminates the shuttle effect of Se, resulting in superior electrochemical performance in terms of volumetric capacity density and cycling stability.

    23. Pd Nanosheets

      Shape-Controlled Synthesis of Surface-Clean Ultrathin Palladium Nanosheets by Simply Mixing a Dinuclear PdI Carbonyl Chloride Complex with H2O (pages 8368–8372)

      Dr. Huan Li, Guangxu Chen, Huayan Yang, Xingli Wang, Jinghong Liang, Pengxin Liu, Mei Chen and Prof. Nanfeng Zheng

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201303772

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      Simple shape control: Ultrathin Pd nanosheets are readily fabricated by simply mixing [Pd2(μ-CO)2Cl4]2− with H2O at ambient temperature. The as-prepared Pd nanosheets are surface clean and serve as an excellent platform to evaluate the effect of organic capping agents on the catalytic and electrocatalytic properties of Pd nanocrystals.

    24. Tailored 2D Pores

      Tailoring Surface-Confined Nanopores with Photoresponsive Groups (pages 8373–8376)

      Dr. Kazukuni Tahara, Koji Inukai, Dr. Jinne Adisoejoso, Hiroyuki Yamaga, Dr. Tatyana Balandina, Dr. Matthew O. Blunt, Prof. Steven De Feyter and Prof. Dr. Yoshito Tobe

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201303745

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      Opening light: Two-dimensional pores are formed by the self-assembly of azobenzene-functionalized triangular building blocks on graphite at the liquid–solid interface. These pores can selectively host a guest molecule. The pore size can be reversibly changed by irradiation at different wavelength which changes the number of guest molecules that are adsorbed (see scheme).

    25. Mass Spectrometry of Proteins

      Photodissociation and Dissociative Photoionization Mass Spectrometry of Proteins and Noncovalent Protein–Ligand Complexes (pages 8377–8381)

      Dr. Francis Canon, Dr. Aleksandar R. Milosavljević, Dr. Guillaume van der Rest, Dr. Matthieu Réfrégiers, Dr. Laurent Nahon, Dr. Pascale Sarni-Manchado, Dr. Véronique Cheynier and Dr. Alexandre Giuliani

      Article first published online: 19 JUL 2013 | DOI: 10.1002/anie.201304046

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      Weight of evidence: Using synchrotron radiation, photo-fragmentation of an intrinsically disordered protein is probed and compared with classical tandem mass-spectrometry activation techniques. It provides excellent sequence coverage allowing the identification of the protein noncovalent binding sites.

    26. Iron Catalysis

      Iron-Catalyzed Hydrogenation for the In Situ Regeneration of an NAD(P)H Model: Biomimetic Reduction of α-Keto-/α-Iminoesters (pages 8382–8386)

      Dr. Liang-Qiu Lu, Dr. Yuehui Li, Dr. Kathrin Junge and Prof. Dr. Matthias Beller

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201301972

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      Two irons for a smoother finish: An NAD(P)H model was regenerated readily in situ by iron-catalyzed reduction with molecular hydrogen. The subsequent biomimetic reduction of α-keto-/ α-iminoesters proceeded smoothly in the presence of an iron-based Lewis acid (LA) to provide α-hydroxyesters and amino acid esters in good to excellent yields (see scheme; NAD(P)+=nicotinamide adenine dinucleotide (phosphate), TM=transition metal).

    27. Drug Design

      Pyrimido[4,5-d]pyrimidin-4(1H)-one Derivatives as Selective Inhibitors of EGFR Threonine790 to Methionine790 (T790M) Mutants (pages 8387–8390)

      Tianfeng Xu, Lianwen Zhang, Shilin Xu, Dr. Chao-Yie Yang, Jinfeng Luo, Fang Ding, Xiaoyun Lu, Yingxue Liu, Zhengchao Tu, Shiliang Li, Prof. Duanqing Pei, Qian Cai, Prof. Honglin Li, Xiaomei Ren, Prof. Shaomeng Wang and Prof. Ke Ding

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201302313

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      Catching the mutants: Pyrimido[4,5-d]pyrimidin-4(1H)-one derivatives (see example) were identified as specific inhibitors of EGFRT790M mutants. The compounds bound with T790M or L858R/T790M mutants with significantly lower Kd values than that with EGFRWT. They also selectively inhibited EGFR signal transduction and proliferation of NSCLC cells harboring EGFRL858R/T790M mutation, but were significantly less potent to cells with EGFRWT.

    28. Silver Hydrides

      Synthesis, Structure and Gas-Phase Reactivity of a Silver Hydride Complex [Ag3{(PPh2)2CH2}33-H)(μ3-Cl)]BF4 (pages 8391–8394)

      Athanasios Zavras, Dr. George N. Khairallah, Timothy U. Connell, Prof. Jonathan M. White, Dr. Alison J. Edwards, Dr. Paul S. Donnelly and Prof. Richard A. J. O'Hair

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201302436

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      Mass spectrometry shows the way! MS analysis of silver salts treated with sodium borohydride in the presence of a bis(phosphino) ligand revealed the formation of novel silver hydride nanocluster cations instead of all silver nanocluster cations. This serendipitous discovery prompted the condensed-phase synthesis, isolation, and characterization of [Ag3{(Ph2P)2CH2}33-H)(μ3-Cl)]BF4⋅0.5 CHCl3.

    29. Cross-Metathesis

      Catalytic Z-Selective Cross-Metathesis with Secondary Silyl- and Benzyl-Protected Allylic Ethers: Mechanistic Aspects and Applications to Natural Product Synthesis (pages 8395–8400)

      Tyler J. Mann, Dr. Alexander W. H. Speed, Prof. Richard R. Schrock and Prof. Amir H. Hoveyda

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201302538

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      Get me a­ Z(olefin): Efficient catalytic cross-metathesis reactions that afford Z-disubstituted allylic silyl or benzyl ethers are reported (see scheme, MAP=monoalkoxide pyrrolide). The approach, in combination with catalytic cross-coupling, provides a general entry to otherwise difficult-to-access alkyne-containing Z olefins.

    30. Drug Design

      Design, Syntheses, and SAR Studies of Carbocyclic Analogues of Sergliflozin as Potent Sodium-Dependent Glucose Cotransporter 2 Inhibitors (pages 8401–8405)

      Prof. Dr. Tony K. M. Shing, Wai-Lung Ng, Judy Y.-W. Chan and Prof. Dr. Clara B.-S. Lau

      Article first published online: 19 JUN 2013 | DOI: 10.1002/anie.201302543

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      Combating diabetes: A small-molecule carbohydrate mimic, pseudo-sergliflozin, was synthesized effectively by a regio- and stereoselective allylic substitution reaction. It was found to be a potent and selective inhibitor of a transporter protein—sodium-dependent glucose cotransporter 2 (SGLT2)—which is responsible for glucose reabsorption in the human body. It could be a lead compound for further development into an antidiabetic agent.

    31. Polar Magnetic Oxides

      Polar and Magnetic Mn2FeMO6 (M=Nb, Ta) with LiNbO3-type Structure: High-Pressure Synthesis (pages 8406–8410)

      Dr. Man-Rong Li, Dr. David Walker, Maria Retuerto, Tapati Sarkar, Dr. Joke Hadermann, Dr. Peter W. Stephens, Dr. Mark Croft, Alexander Ignatov, Dr. Christoph P. Grams, Joachim Hemberger, Dr. Israel Nowik, Dr. P. Shiv Halasyamani, T. Thao Tran, Dr. Swarnakamal Mukherjee, Dr. Tanusri Saha Dasgupta and Martha Greenblatt

      Article first published online: 27 JUN 2013 | DOI: 10.1002/anie.201302775

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      Polar LiNbO3-type magnetic oxides have been extended, for the first time, to the A2BB′O6 family. Mn2+2Fe3+M5+O6 (M=Nb, Ta), synthesized at high pressure, adopt a polar structure, as demonstrated by electron diffraction and the second harmonic generation effect, and they have interesting magnetic properties.

    32. Multicomponent Reactions

      α-Boryl Isocyanides Enable Facile Preparation of Bioactive Boropeptides (pages 8411–8415)

      Adam Zajdlik, Dr. Zezhou Wang, Jennifer L. Hickey, Dr. Ahmed Aman, Dr. Aaron D. Schimmer and Prof. Dr. Andrei K. Yudin

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201302818

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      Entry to bioactive boropeptides: MIDA-containing α-boryl isocyanides are isolable molecules which allow one-step access to boroalkyl-functionalized heterocycles as well as biologically active boropeptides through a multicomponent approach. Among these derivatives are 6-boromorpholinones, novel borocycles with nanomolar IC50 values for 20S proteasome inhibition. MIDA=N-methyliminodiacetyl.

    33. Asymmetric Hydrogenation

      Synthesis of Chiral Aliphatic Amines through Asymmetric Hydrogenation (pages 8416–8419)

      Tang-Lin Liu, Prof. Dr. Chun-Jiang Wang and Prof. Dr. Xumu Zhang

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201302943

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      The direct route: A Rhodium-catalyzed asymmetric hydrogenation method for the efficient synthesis of a broad range of chiral allylic amines and aliphatic amines from readily available materials was developed. A chiral Z-allylic amine was obtained for the first time through a Rhodium–DuanPhos-catalyzed asymmetric hydrogenation. TMS=Trimethylsilyl, cod=cyclooctadiene, TON=turnover number.

    34. Cross-Coupling

      Heterogeneous-Gold-Catalyzed Acceptorless Cross-Dehydrogenative Coupling of Hydrosilanes and Isocyanic Acid Generated in situ from Urea (pages 8420–8423)

      Kento Taniguchi, Shintaro Itagaki, Dr. Kazuya Yamaguchi and Prof. Dr. Noritaka Mizuno

      Article first published online: 24 JUN 2013 | DOI: 10.1002/anie.201303132

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      Support structure: In the presence of gold nanoparticles supported on alumina (Au/Al2O3), various hydrosilanes can be converted into the corresponding silyl isocyanates using urea as an isocyanate source. The observed catalysis is truly heterogeneous, and the retrieved Au/Al2O3 catalyst can be reused several times without any loss of its high catalytic performance.

    35. Multicomponent Cycloadditions

      Stereoselective Nickel-Catalyzed [2+2+2] Cycloadditions and Alkenylative Cyclizations of Ene-Allenes and Alkenes (pages 8424–8427)

      Njamkou N. Noucti and Prof. Erik J. Alexanian

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201303211

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      [2+2+2]=4 (stereocenters)? Nickel-catalyzed multicomponent cycloadditions and alkenylative cyclizations involving two alkenes and one allene are described. The [2+2+2] cycloaddition provides rapid access to stereochemically complex, cis-fused hydrindanes. By exchanging P(o-tol)3 for PBu3 as ligand, the reaction pathway can be diverted to an alkenylative cyclization process.

    36. Transfer Hydrogenation

      Regio- and Diastereoselective C[BOND]C Coupling of α-Olefins and Styrenes to 3-Hydroxy-2-oxindoles by Ru-Catalyzed Hydrohydroxyalkylation (pages 8428–8431)

      Eiji Yamaguchi, Jeffrey Mowat, Tom Luong and Michael J. Krische

      Article first published online: 5 JUL 2013 | DOI: 10.1002/anie.201303552

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      The direct approach: Ruthenium(0)-catalyzed hydrohydroxyalkylation of α-olefins and styrenes with 3-hydroxy-2-oxindoles forms branched products of C[BOND]C coupling with high levels of diastereocontrol. A mechanism involving diene–olefin oxidative coupling and a subsequent carboxylic acid co-catalyzed transfer hydrogenolysis of the resulting oxaruthenacycle intermediate is postulated.

    37. Alkylation

      Alkyl Transfer from C[BOND]C Cleavage (pages 8432–8436)

      Guangxun Li, Rong Chen, Lei Wu, Qingquan Fu, Prof. Dr. Xiaomei Zhang and Prof. Dr. Zhuo Tang

      Article first published online: 27 JUN 2013 | DOI: 10.1002/anie.201303696

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      Hydrogenation was only the beginning: Hantzsch esters have now been used to transfer alkyl groups to imines under mild catalytic conditions to provide a variety of amines (see scheme). Benzyl, secondary alkyl, and tertiary alkyl groups containing ether, ester, and hydroxy functionalities were transferred successfully. The use of Hantzsch esters as alkylation reagents offers a practical and complementary alternative to organometallic processes.

    38. Alkene Insertion

      Reversible Insertion of Unactivated Alkenes into Silicon(II)–Tin Bonds (pages 8437–8440)

      Dr. Ricardo Rodriguez, Dr. Yohan Contie, Dr. David Gau, Dr. Nathalie Saffon-Merceron, Dr. Karinne Miqueu, Dr. Jean-Marc Sotiropoulos, Dr. Antoine Baceiredo and Dr. Tsuyoshi Kato

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201303705

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      Insertion without assertion: Alkenes reacted reversibly under mild conditions (25–85 °C) with phosphine–silylene complexes containing a SiII[BOND]Sn bond to give alkyl silylene complexes (see scheme). Theoretical studies indicated that the insertion reaction proceeds through oxidative addition and migratory insertion in a two-step process and thus revealed that silicon(II)–phosphine complexes can behave like transition-metal complexes.

    39. Glycosylation

      Bismuth(V)-Mediated Thioglycoside Activation (pages 8441–8445)

      Manibarsha Goswami, Dr. Arkady Ellern and Prof. Nicola L. B. Pohl

      Article first published online: 27 JUN 2013 | DOI: 10.1002/anie.201304099

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      A straightforward method utilizing a bismuth(V) compound was developed for the activation of thiopropylglycosides for coupling to various acceptors; good to excellent yields were obtained without applying additional additives/co-promoters. The method does not require low temperatures, is applicable to a wide variety of carbohydrates, and tolerates different functional groups including alkenes.

    40. Hydrogen Peroxide Synthesis

      Safe Direct Synthesis of High Purity H2O2 through a H2/O2 Plasma Reaction (pages 8446–8449)

      Yanhui Yi, Juncheng Zhou, Prof. Hongchen Guo, Jianli Zhao, Ji Su, Li Wang, Xiangsheng Wang and Weimin Gong

      Article first published online: 26 JUN 2013 | DOI: 10.1002/anie.201304134

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      Plasma makes it safer: A gaseous H2/O2 plasma reaction has been developed for the safe direct synthesis of H2O2. Low electron density favors the generation of H2O2 by a chain termination path. This plasma method is promising for the direct synthesis of neutral, high concentration (ca. 60 wt %), and high purity (electronic grade) H2O2.

    41. Asymmetric Catalysis

      Catalytic Enantioselective Iodoetherification of Oximes (pages 8450–8453)

      Chandra Bhushan Tripathi and Prof. Dr. Santanu Mukherjee

      Article first published online: 3 JUL 2013 | DOI: 10.1002/anie.201304173

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      Organocatalysis: The first catalytic enantioselective iodoetherification of oximes is developed using commercially available N-iodosuccinimide. In the presence of a dihydrocinchonidine-derived thiourea (10 mol %), β,γ-unsaturated oximes undergo facile iodoetherification to produce Δ2-isoxazolines containing a quaternary stereogenic center generally in high yield with good to excellent enantioselectivity.

    42. Asymmetric Hydrogenation

      Ruthenium–NHC-Catalyzed Asymmetric Hydrogenation of Flavones and Chromones: General Access to Enantiomerically Enriched Flavanones, Flavanols, Chromanones, and Chromanols (pages 8454–8458)

      Dr. Dongbing Zhao, Bernhard Beiring and Prof. Dr. Frank Glorius

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201302573

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      Two to four! Readily available flavones and chromones were efficiently converted into four valuable chiral classes of O-heterocycles—flavanones, chromanones, flavanols, and chromanols—by means of an enantioselective Ru/NHC-catalyzed hydrogenation process (see scheme; NHC=N-heterocyclic carbene, PCC=pyridinium chlorochromate).

    43. Aromatic Hydroxylation

      Regioselective o-Hydroxylation of Monosubstituted Benzenes by P450 BM3 (pages 8459–8462)

      Alexander Dennig, Nina Lülsdorf, Dr. Haifeng Liu and Prof. Dr. Ulrich Schwaneberg

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201303986

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      Dream come true: A new monooxygenase catalyst shows excellent activity for the hydroxylation of halogenated benzenes, anisole, and toluene with almost complete ortho regioselectivity (see scheme; R=F, Cl, Br, I, CH3, OCH3). The substrates were hydroxylated at room temperature in water without cosolvent using molecular oxygen as oxidant.

    44. Reaction Control in Proteins

      Directed Manipulation of a Flavoprotein Photocycle (pages 8463–8466)

      Dr. Heike Staudt, Dr. Michael Georg Hoesl, Prof. Dr. Andreas Dreuw, Sascha Serdjukow, Prof. Dr. Dieter Oesterhelt, Prof. Dr. Nediljko Budisa, Prof. Dr. Josef Wachtveitl and Prof. Dr. Martin Grininger

      Article first published online: 1 JUL 2013 | DOI: 10.1002/anie.201302334

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      Tamed electrons: To manipulate a protein photocycle in a directed manner, the flavoprotein dodecin was endoscopically modified at its key amino acid tryptophan with substituents carefully selected by their structural and electronic influence. The approach is ideal in the precision of rational protein engineering, and allows correlating tryptophan ionization potentials and electron transfer rates in a Marcus model.

    45. Asymmetric Catalysis

      Titanium Salalen Catalysts Based on cis-1,2-Diaminocyclohexane: Enantioselective Epoxidation of Terminal Non-Conjugated Olefins with H2O2 (pages 8467–8471)

      Prof. Dr. Albrecht Berkessel, Dr. Thomas Günther, Qifang Wang and Dr. Jörg-M. Neudörfl

      Article first published online: 3 JUL 2013 | DOI: 10.1002/anie.201210198

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      Help for the neglected: Terminal, non-conjugated olefins, such as 1-octene, are difficult to epoxidize asymmetrically. Ti salalen complexes based on cis-1,2-diaminocyclohexane catalyze this demanding reaction giving high yields and enantioselectivities (up to 95 % ee), with H2O2 as the oxidant. The X-ray structures of the μ-oxo and peroxo complexes shed light on the coordination behavior of this novel class of ligands.

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