Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 5

January 28, 2013

Volume 52, Issue 5

Pages 1335–1594

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. You have free access to this content
      Cover Picture: Complexity from Simplicity: Tricyclic Aziridines from the Rearrangement of Pyrroles by Batch and Flow Photochemistry (Angew. Chem. Int. Ed. 5/2013) (page 1335)

      Katie G. Maskill, Dr. Jonathan P. Knowles, Dr. Luke D. Elliott, Prof. Dr. Roger W. Alder and Prof. Dr. Kevin I. Booker-Milburn

      Article first published online: 16 JAN 2013 | DOI: 10.1002/anie.201210000

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      Complex tricylic aziridines can be prepared from simple pyrroles by UV irradiation. In their Communication on page 1499 ff., K. I. Booker-Milburn and co-workers show that the reaction proceeds by a two-stage photochemical sequence that involves [2+2] cycloaddition and rearrangement, and that the scale of the reaction can be increased using a customized FEP flow reactor.

    2. You have free access to this content
      Inside Cover: IR Spectrum and Structure of a Protonated Disilane: Probing the Si[BOND]H[BOND]Si Proton Bridge (Angew. Chem. Int. Ed. 5/2013) (page 1336)

      Dipl.-Phys. Marco Savoca, Dr. Judith Langer and Prof. Dr. Otto Dopfer

      Article first published online: 16 JAN 2013 | DOI: 10.1002/anie.201210001

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      The IR spectrum of Si2H7+ provides the first spectroscopic characterization of the geometric and electronic structure of this polysilane cation. In their Communication on page 1568 ff., O. Dopfer et al. give direct evidence for a nonlinear Si[BOND]H[BOND]Si proton bridge with a three-center two-electron bond. The IR fingerprint may be used for its identification in silane plasmas, including the interstellar medium (copyright ESO/F. Meynadier, M. Heydari-Malayerie, N. R. Walborn).

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      Inside Back Cover: Perovskite-like Mn2O3: A Path to New Manganites (Angew. Chem. Int. Ed. 5/2013) (page 1595)

      Dr. Sergey V. Ovsyannikov, Prof. Artem M. Abakumov, Dr. Alexander A. Tsirlin, Dr. Walter Schnelle, Dr. Ricardo Egoavil, Prof. Jo Verbeeck, Prof. Gustaaf Van Tendeloo, Dr. Konstantin V. Glazyrin, Dr. Michael Hanfland and Prof. Dr. Leonid Dubrovinsky

      Article first published online: 15 JAN 2013 | DOI: 10.1002/anie.201210136

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      Transformation of Mn2O3 from cubic bixbyite to a distorted perovskite structure by treatment under high-pressure high-temperature conditions is presented in the Communication on page 1494 ff. by S. V. Ovsyannikov et al. Annular bright field scanning transmission electron microscopy (ABF-STEM) imaging demonstrates the positions of the Mn and O atomic columns, indicating a heavily distorted octahedral framework in the perovskite-type Mn2O3.

    4. You have free access to this content
      Back Cover: Rewiring Translation for Elongation Factor Tu-Dependent Selenocysteine Incorporation (Angew. Chem. Int. Ed. 5/2013) (page 1596)

      Caroline Aldag, Markus J. Bröcker, Michael J. Hohn, Laure Prat, Gifty Hammond, Abigail Plummer and Dieter Söll

      Article first published online: 20 JAN 2013 | DOI: 10.1002/anie.201300063

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      Synthetic tRNA for selenoprotein production is described by D. Söll et al. in their Communication on page 1441 ff. The tRNA is a substrate for three E. coli proteins: seryl-tRNA synthetase (SerRS), selenocysteine synthase (SelA) generating Sec-tRNAUTu, and EF-Tu for Sec-tRNAUTu transport to the ribosome, which allows site-specific Sec insertion into proteins. This system has general utility in protein engineering, molecular biology, and disease research.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 5/2013 (pages 1339–1354)

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201390002

  3. Flashback

    1. Top of page
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    3. Graphical Abstract
    4. Flashback
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. 50 Years Ago ... (page 1350)

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201209344

      Angewandte Chemie International Edition was first published in 1962, the mother journal first in 1888. In this monthly flashback, we feature some of the articles that appeared 50 years ago. This look back can open our eyes, stimulate discussion, or even raise a smile.

  4. Corrigendum

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    5. Corrigendum
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    12. Minireview
    13. Review
    14. Communications
    1. You have free access to this content
      Corrigendum: Synthesis of Aromatic α-Aminoesters: Palladium-Catalyzed Long-Range Arylation of Primary Cmath image[BOND]H Bonds (page 1354)

      Sam Aspin, Anne-Sophie Goutierre, Dr. Paolo Larini, Dr. Rodolphe Jazzar and Prof. Dr. Olivier Baudoin

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201208527

      This article corrects:

      Synthesis of Aromatic α-Aminoesters: Palladium-Catalyzed Long-Range Arylation of Primary Cmath image[BOND]H Bonds1

      Vol. 51, Issue 43, 10808–10811, Article first published online: 28 SEP 2012

  5. News

    1. Top of page
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    4. Flashback
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
  6. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Hiroshi Shinokubo (page 1360)

      Article first published online: 8 OCT 2012 | DOI: 10.1002/anie.201207020

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      “My favorite pieces of music are Beethoven's symphonies. If I were not a scientist, I would be a chef in a restaurant …” This and more about Hiroshi Shinokubo can be found on page 1360.

  7. News

    1. Top of page
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    3. Graphical Abstract
    4. Flashback
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
  8. Obituary

    1. Top of page
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    4. Flashback
    5. Corrigendum
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    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Nicholas J. Turro (19382012) (pages 1363–1364)

      Vaidhyanathan Ramamurthy and Jochen Mattay

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201209993

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      Nicholas J. Turro, who was a pioneer of supramolecular photochemistry and spin chemistry, died in November 2012. His research interests ranged from synthetic organic chemistry, colloidal and interface chemistry, chemical physics, magnetic resonance theory, and reaction mechanisms, to materials and biological chemistry.

  9. Book Review

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    12. Minireview
    13. Review
    14. Communications
    1. Organic Chemistry Principles in Context. A Story Telling Historical Approach. By Mark M. Green. (pages 1365–1366)

      Henning Hopf

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201209314

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      ScienceFromAway Publishing, 2012. 476 pp., softcover, $ 25.00.—ISBN 978-0615702711

  10. Highlights

    1. Top of page
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    4. Flashback
    5. Corrigendum
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    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Chemical Biology

      Streamlining Chemical Probe Discovery: Libraries of “Fully Functionalized” Small Molecules for Phenotypic Screening (pages 1368–1370)

      Julian Oeljeklaus, Dr. Farnusch Kaschani and Prof. Dr. Markus Kaiser

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201207306

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      Cross-linked: The concept of phenotypic screening with probes of fully functionalized small molecules (see picture) has recently been introduced. This approach significantly increases the efficiency and success of target identification after the screening campaign.

    2. Carbenes

      Versatile Reactivity of Rhodium–Iminocarbenes Derived from N-Sulfonyl Triazoles (pages 1371–1373)

      Dr. Anton V. Gulevich and Prof. Dr. Vladimir Gevorgyan

      Article first published online: 7 JAN 2013 | DOI: 10.1002/anie.201209338

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      The migrations of different groups to the metal–carbene center of RhII-stabilized iminocarbenes that were derived from N-sulfonyl triazoles are discussed (see scheme). The reactivity of these Rh-iminocabenes can be tuned easily by variation of substituents on the parent triazole.

  11. Minireview

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    12. Minireview
    13. Review
    14. Communications
    1. Anion Transport

      Small-Molecule Lipid-Bilayer Anion Transporters for Biological Applications (pages 1374–1382)

      Nathalie Busschaert and Prof. Dr. Philip A. Gale

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201207535

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      Into the cell: The development of small-molecule lipid-bilayer anion transporters for potential future use in channel replacement therapy for the treatment of cystic fibrosis, and in treating cancer by perturbing chemical gradients within cells, is currently an area of intense interest. This Minireview looks at recent developments in the design of small-molecule transmembrane anion transporters and focuses on the progress so far in employing these compounds in biological systems.

  12. Review

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    13. Review
    14. Communications
    1. Drug Delivery

      Small Targeted Cytotoxics: Current State and Promises from DNA-Encoded Chemical Libraries (pages 1384–1402)

      Nikolaus Krall, Dr. Jörg Scheuermann and Prof. Dario Neri

      Article first published online: 7 JAN 2013 | DOI: 10.1002/anie.201204631

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      On target: Antibodies have emerged as promising vehicles for the targeted delivery of potent cytotoxic agents to sites of disease. This Review surveys how the use of smaller organic molecules can yield targeted constructs with improved properties and how DNA-encoded library technologies will facilitate the discovery of the necessary ligands (see scheme).

  13. Communications

    1. Top of page
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    4. Flashback
    5. Corrigendum
    6. News
    7. Author Profile
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    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Protein Delivery

      Construction of a Photoactivated Insulin Depot (pages 1404–1409)

      Piyush K. Jain, Dipu Karunakaran and Prof. Simon H. Friedman

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201207264

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      Light controlled: A material that allows for insulin to be released in a controlled fashion by using light was prepared. A subcutaneous reservoir of such materials could allow for the non-invasive control of blood sugar. Insulin (blue in picture) was linked to an insoluble resin (green) through a photocleavable linker (red). Native insulin is released following a first-order process in response to pulses of light from an LED.

    2. Raman Spectroscopy

      Reactions of Alkaline Minerals in the Atmosphere (pages 1410–1413)

      Paul Vargas Jentzsch, Valerian Ciobotă, Dr. Petra Rösch and Prof. Dr. Jürgen Popp

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201208319

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      Climate science: When different salts occurring in atmospheric particles combine during a coagulation process and interact with humid air, some reactions can take place and modify the salt composition (see picture). The hygroscopicity of certain salts favors the formation of a liquid H2O film on the solid material. The salts partially dissolve and the ions can react with each other.

    3. Nanoparticle Surface Chemistry

      Spatial Charge Configuration Regulates Nanoparticle Transport and Binding Behavior In Vivo (pages 1414–1419)

      Dr. Hee-Sun Han, John D. Martin, Jungmin Lee, Daniel K. Harris, Prof. Dr. Dai Fukumura, Prof. Dr. Rakesh K. Jain and Prof. Dr. Moungi Bawendi

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201208331

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      Detailed arrangements: A new set of zwitterionic quantum dots were synthesized and used to study the influence of microscopic charge arrangements on the in vivo behavior of nanoparticles. Experiments using cultured cells and live mice demonstrate that the microscopic arrangement of surface charges strongly influences nonspecific binding, clearance behavior, and in vivo transport of nanoparticles.

    4. Computational Chemistry

      Mechanism and Stereocontrol: Enantioselective Addition of Pyrrole to Ketenes Using Planar-Chiral Organocatalysts (pages 1420–1423)

      Ommidala Pattawong, Thomas J. L. Mustard, Ryne C. Johnston and Prof. Paul Ha-Yeon Cheong

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201208417

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      In control: The computational study of the title reaction catalyzed by the planar-chiral 4-(pyrrolidino)pyridine is reported (see scheme). The resting state is a chiral Brønsted acid complex and the rate-determining step involves a chiral base. The catalyst controls the enantioselectivity through a combination of stereoelectronic effects and CH⋅⋅⋅O interactions.

    5. Gold Redox Chemistry

      The Redox Chemistry of Gold with High-Valence Doped Calcium Oxide (pages 1424–1427)

      Dr. Jenni Andersin, Janne Nevalaita, Dr. Karoliina Honkala and Prof. Dr. Hannu Häkkinen

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201208443

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      Red ox power! DFT calculations have been used to analyze the adsorption energy of gold on high-valent doped CaO in terms of iono-covalent, redox, and Coulomb contributions (see picture). Surprisingly, the dominant energy contribution originates from redox processes between the dopant and the adsorbate Au, not from the Coulomb interaction of charged species as currently presumed.

    6. G-Quadruplexes

      You have full text access to this OnlineOpen article
      An Acetylene-Bridged 6,8-Purine Dimer as a Fluorescent Switch-On Probe for Parallel G-Quadruplexes (pages 1428–1431)

      Dr. Mehran Nikan, Dr. Marco Di Antonio, Dr. Keren Abecassis, Dr. Keith McLuckie and Prof. Shankar Balasubramanian

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201207075

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      Lighting up: The systematic design and synthesis of a G-quartet-inspired fluorescence probe (APD), which is made of two acetylene-bridged purines, are reported. The APD lights up in the presence of parallel DNA (e.g. c-MYC) or RNA G-quadruplexes, while it shows no fluorescence enhancement with double-stranded DNA, antiparallel or mixed-type (e.g. h-Telo) G-quadruplexes (see picture). The utility of APD in the preferential staining of G-quadruplexes is also demonstrated.

    7. Microporous Polymers

      Surface Area Control and Photocatalytic Activity of Conjugated Microporous Poly(benzothiadiazole) Networks (pages 1432–1436)

      Dr. Kai Zhang, Dr. Daniel Kopetzki, Prof. Dr. Peter H. Seeberger, Prof. Dr. Markus Antonietti and Dr. Filipe Vilela

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201207163

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      Conjugated microporous polymers (CMPs) with controlled specific surface area have been prepared through Sonogashira–Hagihara cross-coupling reactions in the presence of silica nanoparticles as templating agents. The CMPs act as heterogeneous photosensitizers for producing singlet oxygen in a continuous flow synthesis (see picture).

    8. Protein Engineering

      Complete Oxidation of Methanol in Biobattery Devices Using a Hydrogel Created from Three Modified Dehydrogenases (pages 1437–1440)

      Dr. Yang Hee Kim, Dr. Elliot Campbell, Jiang Yu, Prof. Shelley D. Minteer and Prof. Scott Banta

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201207423

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      Enzyme catalysis: Three dehydrogenases have been engineered to self-assemble into a hydrogel that supports a synthetic metabolic network. The new catalytic biomaterial was used as an anode modification in two enzymatic biobatteries capable of the complete oxidation of methanol to CO2 (see picture).

    9. Rewiring Translation for Elongation Factor Tu-Dependent Selenocysteine Incorporation (pages 1441–1445)

      Caroline Aldag, Markus J. Bröcker, Michael J. Hohn, Laure Prat, Gifty Hammond, Abigail Plummer and Dieter Söll

      Article first published online: 27 NOV 2012 | DOI: 10.1002/anie.201207567

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      Enjoying UTu in concert: A synthetic tRNA (tRNAUTu) was used as a substrate for three E. coli proteins: seryl-tRNA synthetase (SerRS) forming Ser-tRNAUTu, selenocysteine (Sec) synthase (SelA) generating Sec-tRNAUTu, and EF-Tu for Sec-tRNAUTu transport to the ribosome (see scheme). tRNAUTu can be used by the ribosome, thus allowing site-specific Sec insertion into proteins, including formate dehydrogenase H, selenoglutaredoxin, and glutathione peroxidase.

    10. Polycyclic Hydrocarbons

      Self-Assembling Decacyclene Triimides Prepared through a Regioselective Hextuple Friedel–Crafts Carbamylation (pages 1446–1451)

      Toan V. Pho, Francesca M. Toma, Prof. Michael L. Chabinyc and Prof. Fred Wudl

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201207608

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      Molecular electronics: A hextuple Friedel–Crafts carbamylation is reported in the synthesis of the electroactive decacyclene triimides (see picture). These triimides self-assemble into different nanostructures through modification of the alkyl substituents and are promising n-type materials for organic semiconducting devices.

    11. Asymmetric Catalysis

      Highly Enantioselective [3+3] Cycloaddition of Aromatic Azomethine Imines with Cyclopropanes Directed by π–π Stacking Interactions (pages 1452–1456)

      You-Yun Zhou, Jun Li, Lin Ling, Dr. Sai-Hu Liao, Dr. Xiu-Li Sun, Prof. Dr. Yu-Xue Li, Dr. Li-Jia Wang and Prof. Dr. Yong Tang

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201207576

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      Designing armory: The side-arm-modified In-TOX/NiII complex was identified as a highly efficient and stereoselective catalyst for the [3+3] cycloaddition of aromatic azomethine imines with cyclopropanes (see picture). Density functional calculations and control experiments revealed that the directing effect of the side arm through π interactions is crucial to the stereochemical control.

    12. Drug Delivery

      Silicon-Nanowire-Based Nanocarriers with Ultrahigh Drug-Loading Capacity for In Vitro and In Vivo Cancer Therapy (pages 1457–1461)

      Fei Peng, Dr. Yuanyuan Su, Xinpan Wei, Yimei Lu, Yanfeng Zhou, Yiling Zhong, Prof. Shuit-Tong Lee and Prof. Yao He

      Article first published online: 11 DEC 2012 | DOI: 10.1002/anie.201206737

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      A pratical agent for cancer therapy: Silicon nanowires (SiNWs) were employed in the design of high-performance drug nanocarriers. The SiNWs were used as nanovectors for the delivery of an anticancer drug (DOX). SiNWs feature an ultrahigh drug-loading capacity. In vitro and in vivo experiments show that SiNW-based nanocarriers are highly efficacious for cancer therapy (see picture).

    13. RNA Binding

      Small-Molecule-Mediated Cleavage of RNA in Living Cells (pages 1462–1465)

      Dr. Lirui Guan and Prof. Dr. Matthew D. Disney

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201206888

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      Killing the message: An approach to direct the cleavage of RNA targets with small molecules in living cells is described (see scheme). A bifunctional small molecule (purple) that recognizes a specific three nucleotide repeat sequence and cleaves that sequence in response to light was shown to be effective at degrading the myotonic dystrophy type 1 (DM1) extended repeat RNAs, thereby affecting biological functions.

    14. Multiplex DNA Assays

      Absolute and Relative Quantification of Multiplex DNA Assays Based on an Elemental Labeling Strategy (pages 1466–1471)

      Guojun Han, Sichun Zhang, Zhi Xing and Prof. Xinrong Zhang

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201206903

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      Elements and quantification: A nucleic acid assay has been developed, based on an elemental labeling strategy using magnetic microparticles (MMPs), which provides quantification of multiple DNA targets. Rare-earth elements, indium, and stable isotopes could be labeled with oligonucleotides serving as DNA probes. Quantitative analysis was then carried out using the designed systems (see picture) and elemental mass spectrometry.

    15. Cell Targeting

      DNA Aptamer-Mediated Cell Targeting (pages 1472–1476)

      Xiangling Xiong, Dr. Haipeng Liu, Dr. Zilong Zhao, Dr. Meghan B. Altman, Dr. Dalia Lopez-Colon, Prof. Chaoyong James Yang, Prof. Lung-Ji Chang, Prof. Chen Liu and Prof. Weihong Tan

      Article first published online: 11 DEC 2012 | DOI: 10.1002/anie.201207063

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      An apt modification: A simple and effective way to modify the cell surface with target-specific ligands, such as DNA aptamers, while minimizing the effects on the modified cells has been developed. After incubating with lipo–aptamer probes, immune cells (red, see scheme) recognize and kill cancer cells (blue) in the cell mixture.

    16. Bimetallic Nanoparticles

      Gold–Palladium Core–Shell Nanocrystals with Size and Shape Control Optimized for Catalytic Performance (pages 1477–1480)

      Anna M. Henning, Dr. John Watt, Dr. Peter J. Miedziak, Dr. Soshan Cheong, Marco Santonastaso, Dr. Minghui Song, Dr. Yoshihiko Takeda, Prof. Angus I. Kirkland, Dr. Stuart H. Taylor and Prof. Richard D. Tilley

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201207824

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      Right to the core: The design of nanocatalysts with maximized catalytic performance relies on control of the size, shape, and composition. The shell thickness of nanocrystals with core–shell structures can be controlled, thus enabling control over the nanocrystal electronic structure and catalytic properties. Monodisperse faceted icosahedral Au–Pd core–shell nanocrystals (see picture) were synthesized, and optimized for the oxidation of benzyl alcohol to benzaldehyde.

    17. Heterogeneous Catalysis

      Metal–Ligand Core–Shell Nanocomposite Catalysts for the Selective Semihydrogenation of Alkynes (pages 1481–1485)

      Dr. Takato Mitsudome, Yusuke Takahashi, Dr. Satoshi Ichikawa, Dr. Tomoo Mizugaki, Prof. Dr. Koichiro Jitsukawa and Prof. Dr. Kiyotomi Kaneda

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201207845

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      Catalysts with a sheltered upbringing: Novel core–shell nanocomposite catalysts consisting of active metal nanoparticles encapsulated by macroligands have been prepared. They have Pd nanoparticles (PdNPs) as an active core and shell ligands having sulfoxide moieties coordinated to the PdNPs. The shell protects the catalyst from coordination by alkenes and allows the lead-free selective semihydrogenation of a wide range of alkynes without any additives (see scheme).

    18. Amino Acids

      A 19F NMR Label to Substitute Polar Amino Acids in Peptides: A CF3-Substituted Analogue of Serine and Threonine (pages 1486–1489)

      Anton N. Tkachenko, Dr. Pavel K. Mykhailiuk, Dr. Sergii Afonin, Dr. Dmytro S. Radchenko, Vladimir S. Kubyshkin, Prof. Anne S. Ulrich and Prof. Igor V. Komarov

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201208069

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      Rigid & polar: The cyclobutane scaffold was used to design the first polar nonperturbing rigid CF3-substituted amino acid (left in picture) suitable for replacing the serine/threonine residues in peptides. This amino acid imitates the geometry, structure, and function of serine and threonine, but in contrast to those, it can be used in structural studies of membrane-active Ser/Thr-containing peptides by solid-state 19F NMR spectroscopy.

    19. Natural Product Synthesis

      A Telescoped Route to 2,6-Disubstituted 2,3,4,5-Tetrahydropyridines and 2,6-syn-Disubstituted Piperidines: Total Synthesis of (−)-Grandisine G (pages 1490–1493)

      Dr. James D. Cuthbertson and Prof. Richard J. K. Taylor

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201208118

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      A grand route to grandisines: A method for the conversion of 6-acyl cyclohexenones into 2,6-disubstituted 2,3,4,5-tetrahydropyridines and, after diastereoselective reduction, 2,6-syn-disubstituted piperidines has been developed. The scope of this process is outlined by the synthesis of cis-2-methoxycarbonylmethyl-6-pentylpiperidine and the first total synthesis of the Elaeocarpus-derived alkaloid (−)-grandisine G (see scheme).

    20. High-Pressure Perovskites

      Perovskite-like Mn2O3: A Path to New Manganites (pages 1494–1498)

      Dr. Sergey V. Ovsyannikov, Prof. Artem M. Abakumov, Dr. Alexander A. Tsirlin, Dr. Walter Schnelle, Dr. Ricardo Egoavil, Prof. Jo Verbeeck, Prof. Gustaaf Van Tendeloo, Dr. Konstantin V. Glazyrin, Dr. Michael Hanfland and Prof. Dr. Leonid Dubrovinsky

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201208553

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      Phases of the Mn2O3: Two new phases of Mn2O3—corundum-type ε-Mn2O3 and perovskite-type ζ-Mn2O3—were obtained by high-pressure high-temperature synthesis. Manganese atoms were found to completely occupy the A- and B-positions of perovskite simultaneously. The perovskite-type ζ-Mn2O3 has an A-site-ordered perovskite structure (see picture) containing Mn in three different oxidation states (+II, +III, and +IV).

    21. Photochemical Synthesis

      Complexity from Simplicity: Tricyclic Aziridines from the Rearrangement of Pyrroles by Batch and Flow Photochemistry (pages 1499–1502)

      Katie G. Maskill, Dr. Jonathan P. Knowles, Dr. Luke D. Elliott, Prof. Dr. Roger W. Alder and Prof. Dr. Kevin I. Booker-Milburn

      Article first published online: 10 JAN 2013 | DOI: 10.1002/anie.201208892

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      Molecular acrobatics: Irradiation of N-butenyl-substituted pyrroles that bear an electron-withdrawing group leads to complex tricyclic aziridines through an unprecedented photocycloaddition–rearrangement sequence. Gram quantities of these complex products could be produced by using a bespoke flow reactor (see picture, FEP=fluorinated ethylene propylene).

    22. Electron Density

      Pushing X-ray Electron Densities to the Limit: Thermoelectric CoSb3 (pages 1503–1506)

      Mette Stokkebro Schmøkel, Lasse Bjerg, Dr. Jacob Overgaard, Dr. Finn Krebs Larsen, Dr. Georg Kent Hellerup Madsen, Dr. Kunihisa Sugimoto, Prof. Dr. Masaki Takata and Prof. Dr. Bo Brummerstedt Iversen

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201206065

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      A big challenge: The experimental electron density of CoSb3 was determined based on short-wavelength single-crystal synchrotron data (10 K), thereby giving a view of covalently bonded Co and Sb atoms that carry only small negative and positive charges, respectively. This result contradicts the conventional view of the electrostatic properties of the structure used in thermoelectric studies.

    23. Heterocycles

      Sulfonyl-1,2,3-Triazoles: Convenient Synthones for Heterocyclic Compounds (pages 1507–1510)

      Dr. Mikhail Zibinsky and Prof. Valery V. Fokin

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201206388

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      As easy as 1,2,3: Readily available and shelf-stable 1-sulfonyl-1,2,3-triazoles react with aldehydes and aldimines in the presence of RhII catalysts to produce 4-oxazolines and 1,2,5-trisubstituted imidazoles (see scheme).

    24. Synthetic Receptors

      Narrowly Dispersed Hydrophilic Molecularly Imprinted Polymer Nanoparticles for Efficient Molecular Recognition in Real Aqueous Samples Including River Water, Milk, and Bovine Serum (pages 1511–1514)

      Yue Ma, Guoqing Pan, Ying Zhang, Xianzhi Guo and Prof. Dr. Huiqi Zhang

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201206514

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      In river water, milk, and bovine serum, molecularly imprinted polymer nanoparticles with hydrophilic polymer brushes showed excellent molecular recognition (see picture). Readily prepared by precipitation polymerization with a macromolecular chain-transfer agent, such nanoparticles are promising alternatives to antibodies for many applications owing to their superior dispersion and binding properties in biological matrices.

    25. Annulation Reactions

      Efficient Generation of ortho-Naphthoquinone Methides from 1,4-Epoxy-1,4-dihydronaphthalenes and Their Annulation with Allyl Silanes (pages 1515–1519)

      Dr. Yoshinari Sawama, Yuko Shishido, Takayoshi Yanase, Koichi Kawamoto, Ryota Goto, Dr. Yasunari Monguchi, Prof. Dr. Yasuyuki Kita and Prof. Dr. Hironao Sajiki

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201207315

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      Pharmaceutically useful dihydronaphthopyran derivatives were obtained in good yield by the regio- and stereoselective annulation of ortho-naphthoquinone methides with allyl silanes. The ortho-naphthoquinone methides were generated in situ from 1-siloxymethyl-1,4-epoxy-1,4-dihydronaphthalenes under FeCl3 catalysis (see scheme; allyl-TMS=allyltrimethylsilane, TBS=tert-butyldimethylsilyl, TMS=trimethylsilyl).

    26. Chirality

      Rhodium-Catalyzed Asymmetric Synthesis of Spirosilabifluorene Derivatives (pages 1520–1522)

      Prof. Dr. Yoichiro Kuninobu, Kanae Yamauchi, Naoya Tamura, Takayuki Seiki and Prof. Dr. Kazuhiko Takai

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201207723

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      Si goes chiral: Treatment of a bis(biphenyl)silane with a catalytic amount of a rhodium complex gave a spirosilabifluorene bearing a quaternary silicon atom. By using a rhodium catalyst with a chiral phosphine ligand (see scheme), asymmetric dehydrogenative cyclization proceeded to give chiral derivatives in good yields and enantioselectivities.

    27. Synthetic Methods

      Palladium-Catalyzed Enantioselective Allylic Alkylations through C–H Activation (pages 1523–1526)

      Prof. Barry M. Trost, David A. Thaisrivongs and Etienne J. Donckele

      Article first published online: 11 DEC 2012 | DOI: 10.1002/anie.201207870

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      A new ligand class: The title reaction was made possible by the discovery of a new class of phosphoramidite ligands. A variety of sterically and electronically diverse allylarenes undergo reaction with 2-acetyl-1-tetralones to form quaternary carbon stereocenters. This is a conceptually and mechanistically distinct strategy from traditional methods for the synthesis of enantioenriched allylic substitution products. 2,6-DMBQ=2,6-dimethylbenzoquinone.

    28. Cross-Coupling

      Synergistic Catalysis in the Sonogashira Coupling Reaction: Quantitative Kinetic Investigation of Transmetalation (pages 1527–1530)

      Chuan He, Jie Ke, Huan Xu and Prof. Aiwen Lei

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201207970

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      Rate-limiting: The transmetalation step of the Sonogashira coupling reaction has been established as the rate-limiting step. This cross-coupling has been demonstrated to be a Pd-catalyzed and Cu-catalyzed synergistic process, which exhibits a first-order kinetic dependence on both the [Pd] and [Cu] catalysts (see scheme).

    29. Clathrate Hydrates

      Low-Pressure Synthesis and Characterization of Hydrogen-Filled Ice Ic (pages 1531–1534)

      Dr. Rajnish Kumar, Dr. Dennis D. Klug, Dr. Christopher I. Ratcliffe, Dr. Christopher A. Tulk and Dr. John A. Ripmeester

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201208367

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      A hydrogen storage material: When vapor-deposited amorphous ice is exposed to a low pressure (about 12 MPa) of hydrogen at 140 K a hydrogen-filled cubic ice results (see picture). Calculations suggest that this material has the potential for hydrogen storage with a capacity of 10 wt % hydrogen at full loading.

    30. Visible-Light Photocatalysis

      Tandem Cyclizations of 1,6-Enynes with Arylsulfonyl Chlorides by Using Visible-Light Photoredox Catalysis (pages 1535–1538)

      Guo-Bo Deng, Zhi-Qiang Wang, Jia-Dong Xia, Peng-Cheng Qian, Ren-Jie Song, Ming Hu, Lu-Bin Gong and Prof. Dr. Jin-Heng Li

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201208380

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      Ray of light: 10a,11-Dihydro-10H-benzo[b]fluorenes were synthesized by a visible-light-catalyzed tandem cyclization of 1,6-enynes with arylsulfonyl chlorides. This method extends the scope of enyne cyclizations and represents a new synthetic application of arylsulfonyl chlorides.

    31. Domino Reactions

      Highly Diastereoselective Multicomponent Cascade Reactions: Efficient Synthesis of Functionalized 1-Indanols (pages 1539–1542)

      Jun Jiang, Xiaoyu Guan, Shunying Liu, Baiyan Ren, Xiaochu Ma, Xin Guo, Fengping Lv, Xiang Wu and Prof. Wenhao Hu

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201208391

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      Trapped: A Michael-aldol-type cascade reaction including the trapping of an oxonium ylide through a delayed proton shift leads to the formation of multiple stereocenters in a mild one-pot synthesis. Enantiomerically pure indanol derivatives with four stereocenters and a stereogenic quaternary carbon center were easily obtained through this method in moderate to good yields.

    32. Total Synthesis

      Syntheses and Structural Confirmations of Members of a Heterocycle-Containing Family of Labdane Diterpenoids (pages 1543–1547)

      Daniel J. Mack and Prof. Jon T. Njardarson

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201208412

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      Building with berries! Several labdane natural products have been synthesized for the first time by the combination of a copper-catalyzed vinyl oxirane ring expansion reaction with an abundant, inexpensive, chiral natural source (juniper berries; see scheme). These expedient (1–5 step) syntheses have resulted in the structural confirmations of five natural products and one reassignment. Reagent-controlled oxidation and 1,3-diene isomerization results are also presented.

    33. Trifluoromethylthiolation

      An Air-Stable Copper Reagent for Nucleophilic Trifluoromethylthiolation of Aryl Halides (pages 1548–1552)

      Prof. Dr. Zhiqiang Weng, Weiming He, Chaohuang Chen, Richmond Lee, Davin Tan, Prof. Dr. Zhiping Lai, Dedao Kong, Prof. Dr. Yaofeng Yuan and Prof. Dr. Kuo-Wei Huang

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201208432

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      A series of copper(I) trifluoromethyl thiolate complexes have been synthesized from the reaction of CuF2 with Me3SiCF3 and S8 (see scheme; Cu red, F green, N blue, S yellow). These air-stable complexes serve as reagents for the efficient conversion of a wide range of aryl halides into the corresponding aryl trifluoromethyl thioethers in excellent yields.

    34. Structure Elucidation

      You have full text access to this OnlineOpen article
      Absolute Configuration of Beer′s Bitter Compounds (pages 1553–1555)

      Dr. Jan Urban, Dipl.-Chem. Clinton J. Dahlberg, Dr. Brian J. Carroll and Prof. Werner Kaminsky

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201208450

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      During the beer brewing process, bitter tasting cis and trans iso-α-acids are generated from the precursor α-acids found in hops. The absolute configurations of the α-acid (−)-humulone and several of its derivatives have now been elucidated by X-ray crystallography, thus resolving decades of confusion over the humulone isomerization mechanism.

    35. Directed Asymmetric Hydrogenation

      Carboxy-Directed Asymmetric Hydrogenation of 1,1-Diarylethenes and 1,1-Dialkylethenes (pages 1556–1559)

      Dr. Song Song, Prof. Shou-Fei Zhu, Yan-Bo Yu and Prof. Qi-Lin Zhou

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201208606

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      Carboxy marks the spot: A carboxy-directed asymmetric hydrogenation of 1,1-diarylethenes and 1,1-dialkylethenes with chiral iridium/spiro phosphine–oxazoline catalysts has been developed. A wide range of chiral diarylethanes and chiral γ-methyl fatty acids were synthesized with excellent enantioselectivity (see scheme).

    36. Acids

      Synthesis, Characterization, and Applications of Zwitterions Containing a Carbanion Moiety (pages 1560–1563)

      Dr. Hikaru Yanai, Tasuku Yoshino, Masaya Fujita, Haruhiko Fukaya, Dr. Akira Kotani, Prof. Dr. Fumiyo Kusu and Prof. Dr. Takeo Taguchi

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201208809

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      A trifle of triflyl: N-substituted anilines react with 1,1,3,3-tetrakis(triflyl)propane to give a 2,2-bis(triflyl)ethyl group at the para position of the ring. The product is a zwitterion with a carbanion and an ammonium moiety, and can be used as an acid catalyst for organic reactions (see scheme).

    37. Asymmetric Synthesis

      Iterative Asymmetric Hydroformylation/Wittig Olefination Sequence (pages 1564–1567)

      Gene W. Wong and Prof. Clark R. Landis

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201208819

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      Over and over again: Various alkenes underwent the title reaction in the presence of rhodium/bis(diazaphospholane) complexes to give γ-chiral α,β-unsaturated carbonyl products (46–96 % yield) with high enantioselectivity (90–99 % ee). Iterative sequences of the reaction lead to stereoselective C[BOND]C bond formations between achiral reactants to produce products having multiple stereocenters (see scheme, acac=acetylacetonate).

    38. Gas-Phase Chemistry

      IR Spectrum and Structure of a Protonated Disilane: Probing the Si[BOND]H[BOND]Si Proton Bridge (pages 1568–1571)

      Dipl.-Phys. Marco Savoca, Dr. Judith Langer and Prof. Dr. Otto Dopfer

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201208958

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      Structure elucidation: The IR spectrum of the protonated disilane Si2H7+ has been derived by resonant IR photodissociation spectroscopy of weakly bound Si2H7+⋅Ne clusters (see picture). Analysis of the spectra provides the first characterization of this fundamental polysilane cation and direct evidence for the nonlinear Si[BOND]H[BOND]Si proton bridge with a three-center two-electron bond.

    39. Selective Cell Adhesion

      Functionalizing αvβ3- or α5β1-Selective Integrin Antagonists for Surface Coating: A Method To Discriminate Integrin Subtypes In Vitro (pages 1572–1575)

      Florian Rechenmacher, Stefanie Neubauer, Dr. Julien Polleux, Dr. Carlos Mas-Moruno, Dr. Mariarosaria De Simone, Dr. Elisabetta Ada Cavalcanti-Adam, Prof. Joachim P. Spatz, Prof. Reinhard Fässler and Prof. Dr. Horst Kessler

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201206370

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      Stuck with the right choice: αvβ3- or α5β1-selective integrin ligands were functionalized for surface coating without losing activity and selectivity. The coating of nanostructured gold surfaces with these compounds stimulated subtype-selective cell adhesion of genetically modified αvβ3- or α5β1-expressing fibroblasts in vitro.

    40. Hydrocyanation

      Enantioselective Nickel-Catalyzed Hydrocyanation of Vinylarenes Using Chiral Phosphine–Phosphite Ligands and TMS-CN as a Source of HCN (pages 1576–1580)

      Dipl.-Chem. Anna Falk, B. Sc. Anna-Lena Göderz and Prof. Dr. Hans-Günther Schmalz

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201208082

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      Anti-headache chemistry: In the presence of a tailored modular P,P ligand the nickel-catalyzed addition of HCN, generated in situ from TMS-CN, to styrene derivatives proceeds with an unprecedented level of stereocontrol (up to 97 % ee) to give 2-aryl-acetonitriles, for example, the depicted precursor of Ibuprofen.

    41. Cobalt Catalysis

      Insights into the Cobalt(II)-Catalyzed Decomposition of Peroxide (pages 1581–1585)

      Eyal Spier, Dr. Ulrich Neuenschwander and Prof. Dr. Ive Hermans

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201207920

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      Two cycles: Based on a computational study, CoIIIOOR is put forward as the pivotal intermediate in the title reaction. Depending on the coordination environment of CoII, two very different catalytic cycles are accessible (see scheme). Irreversible catalyst deactivation takes place via the formation of an inactive dimer. Immobilization of cobalt on alumina results in a stable heterogeneous catalyst that is not subject to deactivation, since dimerization is prohibited.

    42. Catalyst Recycling

      Temperature-Controlled Catalyst Recycling in Homogeneous Transition-Metal Catalysis: Minimization of Catalyst Leaching (pages 1586–1589)

      M. Sc. Yvonne Brunsch and Prof. Dr. Arno Behr

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201208667

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      Reduce–reuse–recycle! One of the challenges in applied homogeneous catalysis is the efficient recycling of the valuable metal catalyst. The catalyst recycling concept of temperature-controlled multicomponent solvent systems was successfully applied to the hydroformylation of long-chain alkenes. The factors that signficantly influence catalyst leaching and how it can be minimized effectively were systematically investigated for the first time.

    43. Natural Products

      Homologous NRPS-like Gene Clusters Mediate Redundant Small-Molecule Biosynthesis in Aspergillus flavus (pages 1590–1594)

      Ry R. Forseth, Dr. Saori Amaike, Daniel Schwenk, Katharyn J. Affeldt, Prof. Dr. Dirk Hoffmeister, Prof. Dr. Frank C. Schroeder and Prof. Dr. Nancy P. Keller

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201207456

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      Biosynthetic crosstalk: Most gene clusters in fungi are orphans with no known associated metabolites. NMR-based comparative metabolomics was used to identify the products of two highly homologous orphan clusters in Aspergillus flavus. The two clusters encode partially redundant biosynthetic pathways that produce overlapping sets of novel fungal alkaloids, feature NRPS-like genes with unusual functions, and regulate fungal development.

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