Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 46

November 12, 2012

Volume 51, Issue 46

Pages 11391–11637

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: At Last: Erythropoietin as a Single Glycoform (Angew. Chem. Int. Ed. 46/2012) (page 11391)

      Dr. Ping Wang, Dr. Suwei Dong, Dr. John A. Brailsford, Dr. Karthik Iyer, Dr. Steven D. Townsend, Dr. Qiang Zhang, Dr. Ronald C. Hendrickson, Dr. JaeHung Shieh, Dr. Malcolm A. S. Moore and Prof. Samuel J. Danishefsky

      Article first published online: 22 OCT 2012 | DOI: 10.1002/anie.201208087

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      A glycoprotein with multiple glycosylations can be prepared by chemical synthesis as a single glycoform. In their Communication on page 11576 ff., S. J. Danishefsky et al. describe the first total synthesis of fully glycosylated erythropoietin. Glycosylation has significantly increased the stability of the protein. The fully glycosylated native protein has demonstrated substantial erythropoietic activity.

    2. You have free access to this content
      Inside Cover: The First Generation of β-Galactosidase-Responsive Prodrugs Designed for the Selective Treatment of Solid Tumors in Prodrug Monotherapy (Angew. Chem. Int. Ed. 46/2012) (page 11392)

      Thibaut Legigan, Dr. Jonathan Clarhaut, Dr. Isabelle Tranoy-Opalinski, Dr. Arnaud Monvoisin, Dr. Brigitte Renoux, Dr. Mikaël Thomas, Dr. Alain Le Pape, Dr. Stéphanie Lerondel and Dr. Sébastien Papot

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201207805

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      A galactoside prodrug has been designed that can be selectively activated by lysosomal β-galactosidase located inside cancer cells expressing a specific tumor-associated receptor. In their Communication on page 11606 ff. S. Papot and co-workers show that this efficient enzymatic process triggers a potent cytotoxic effect, releasing the potent antimitotic agent MMAE and allowing the destruction of both receptor-positive and surrounding receptor-negative tumor cells.

    3. You have free access to this content
      Inside Back Cover: Microwave-Assisted Synthesis of Porous Ag2S–Ag Hybrid Nanotubes with High Visible-Light Photocatalytic Activity (Angew. Chem. Int. Ed. 46/2012) (page 11639)

      Wenlong Yang, Dr. Lei Zhang, Prof. Yong Hu, Yijun Zhong, Hao Bin Wu and Prof. Xiong Wen (David) Lou

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201207795

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      Semiconductor–metal heterostructure nanotubes have been rationally synthesized through rapid microwave-assisted sulfidation of Ag2CO3 nanorods, as described by X. W. Lou et al. in their Communication on page 11501 ff. The relative amounts of Ag2S and Ag in the resulting hybrid structure can be easily tuned. The optimized Ag2S–Ag hybrid structure manifests superior photocatalytic activity for both degredation of methyl orange and reduction of aqueous CrVI under visible-light irradiation.

    4. You have free access to this content
      Back Cover: Sulfur and Nitrogen Dual-Doped Mesoporous Graphene Electrocatalyst for Oxygen Reduction with Synergistically Enhanced Performance (Angew. Chem. Int. Ed. 46/2012) (page 11640)

      Ji Liang, Yan Jiao, Mietek Jaroniec and Prof. Shi Zhang Qiao

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201208086

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      Developing highly active and cheap catalysts for the oxygen reduction reaction (ORR) is crucial to the commercialization of fuel cells and lithium–air batteries. In their Communication on page 11496 ff., S. Z. Qiao et al. describe an inexpensive mesoporous graphene catalyst dual-doped with sulfur and nitrogen that has high ORR activity. The superior performance can be attributed to synergistic effects between the dopants, resulting in increased spin and charge densities.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 46/2012 (pages 11395–11408)

      Article first published online: 21 NOV 2012 | DOI: 10.1002/anie.201290078

    2. Graphical Abstract: Angew. Chem. Int. Ed. 46/2012 (pages 11395–11408)

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201290075

  3. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Oliver Reiser (page 11416)

      Article first published online: 11 JUL 2012 | DOI: 10.1002/anie.201203999

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      “My not-so-secret passion is electronic gadgets. The greatest scientific advance in the next decade will be catalytic C[BOND]O activation. …” This and more about Oliver Reiser can be found on page 11416.

  5. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Comprehensive Chiroptical Spectroscopy. Two volume set. Edited by Nina Berova, Prasad L. Polavarapu, Koji Nakanishi, and Robert W. Woody. (pages 11418–11419)

      Pedro Cintas

      Article first published online: 28 SEP 2012 | DOI: 10.1002/anie.201206736

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      John Wiley & Sons, Hoboken, 2012. 1840 pp., hardcover, € 339.00.—ISBN 978-0470641354

  7. Highlights

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

      Designing Red-Light-Activated Multifunctional Agents for the Photodynamic Therapy (pages 11420–11422)

      Samantha L. H. Higgins and Karen J. Brewer

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201204933

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      Cell death by visible light: Photodynamic therapy (PDT) is a relatively underemployed method for treatment of diseases including cancer. Recent improvements in synthetic and analysis methods of metal complexes provide for red-light-activated drugs with potential application in PDT (see picture).

    2. Relay Catalysis

      Relay Catalysis Enables Hydrogen Gas to Participate in Asymmetric Organocatalytic Hydrogenation (pages 11423–11425)

      Dr. Feng Shi and Prof. Liu-Zhu Gong

      Article first published online: 8 OCT 2012 | DOI: 10.1002/anie.201204234

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      Teamwork: Through relay catalysis by a RuII complex and a chiral phosphoric acid ((S)-BPA in the scheme) recently developed by Zhou's group, hydrogen gas can act as the terminal reductant in the catalytic asymmetric hydrogenation of heterocycles. This is a completely new concept in the area of asymmetric hydrogenation.

  8. Minireview

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. >18F Radiochemistry

      18F Labeling of Arenes (pages 11426–11437)

      Dr. Matthew Tredwell and Prof. Véronique Gouverneur

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201204687

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      On the radio: The 18F labeling of arenes is formally carried out by nucleophilic fluorination with [18F]fluoride (SNAr) and electrophilic fluorination with [18F]F2, [18F]OF, or [18F]NF reagents. Imposing a reactivity switch (umpolung) on either the 18F source or the arene substrate allows for the long-awaited labeling of electron-neutral and electron-rich arenes with [18F]fluorides (see examples; RCY=radiochemical yield, SA=specific activity).

  9. Review

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Posttranslational Modifications

      Chemical Biology of Glycosylphosphatidylinositol Anchors (pages 11438–11456)

      Dr. Yu-Hsuan Tsai, Prof. Dr. Xinyu Liu and Prof. Dr. Peter H. Seeberger

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201203912

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      Protein anchors: Glycosylphosphatidylinositol (GPI) glycolipids anchor proteins on the extracellular membrane. This mode of protein posttranslational modification is common and important in eukaryotes. Insight into the structure and function of GPIs is discussed, with an emphasis on the recent progress in using structurally defined synthetic GPIs as tools to dissect their biological functions.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. [FeFe] Hydrogenase Mechanism

      Identification and Characterization of the “Super-Reduced” State of the H-Cluster in [FeFe] Hydrogenase: A New Building Block for the Catalytic Cycle? (pages 11458–11462)

      Agnieszka Adamska, Dr. Alexey Silakov, Dr. Camilla Lambertz, Dr. Olaf Rüdiger, Prof. Thomas Happe, Dr. Edward Reijerse and Prof. Wolfgang Lubitz

      Article first published online: 26 OCT 2012 | DOI: 10.1002/anie.201204800

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      Super-reduced and super-active: A new redox state in the active site of algal [FeFe] hydrogenases has been identified and characterized by EPR and FTIR spectroscopy. Electrochemical and in vitro essays show that this species is highly active in hydrogen production and suggest that it is a key intermediate in the catalytic cycle of all [FeFe] hydrogenases.

    2. Drug Design

      Small-Molecule Inhibitors of the Interaction between the E3 Ligase VHL and HIF1α (pages 11463–11467)

      Dennis L. Buckley, Dr. Jeffrey L. Gustafson, Dr. Inge Van Molle, Dr. Anke G. Roth, Dr. Hyun Seop Tae, Dr. Peter C. Gareiss, Prof. William L. Jorgensen, Dr. Alessio Ciulli and Prof. Craig M. Crews

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206231

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      By design: Novel small-molecule inhibitors of the interaction between the von Hippel–Lindau ligase (VHL) and its molecular target HIF1α, a transcription factor involved in oxygen sensing, have been developed and studied. The most potent inhibitor binds with an IC50 value of 0.9 μM and is thus the first sub-micromolar inhibitor of the VHL–HIF1α interaction.

    3. Vancomycin Biosynthesis

      Substituent Effects on the Phenol Coupling Reaction Catalyzed by the Vancomycin Biosynthetic P450 Enzyme OxyB (pages 11468–11472)

      Patrick C. Schmartz, Dr. Katharina Wölfel, Dr. Katja Zerbe, Emad Gad, Prof. El Sayed El Tamany, Prof. Hassen K. Ibrahim, Prof. Khaled Abou-Hadeed and Prof. John A. Robinson

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201204458

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      Oxidative phenol coupling reactions are required to establish the cross-linked heptapeptide backbone of vancomycin. The first cross-linking reaction, catalyzed by the P450 enzyme OxyB, is dramatically slower when a chlorine substituent is present in the hexapeptide-S-PCP substrate and is abolished when chlorine is introduced into a potential heptapeptide-S-PCP substrate.

    4. Bimetallic Catalysis

      Ni/Pd@MIL-101: Synergistic Catalysis with Cavity-Conform Ni/Pd Nanoparticles (pages 11473–11477)

      Justus Hermannsdörfer, Martin Friedrich, Dr. Nobuyoshi Miyajima, Prof. Dr. Rodrigo Q. Albuquerque, Prof. Dr. Stephan Kümmel and Prof. Dr. Rhett Kempe

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201205078

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      A perfect fit: Cavity-conform bimetallic Ni/Pd nanoparticles of different composition were generated in the metal–organic framework MIL-101. Experimental evidence and molecular dynamic simulations indicate the existence of mixed bimetallic particles. Pronounced synergistic effects have been observed in liquid-phase catalysis.

    5. Pincer Ligands

      Pushing the σ-Donor Strength in Iridium Pincer Complexes: Bis(silylene) and Bis(germylene) Ligands Are Stronger Donors than Bis(phosphorus(III)) Ligands (pages 11478–11482)

      Dr. Andreas Brück, M. Sc. Daniel Gallego, Dipl.-Chem. Wenyuan Wang, Elisabeth Irran, Prof. Dr. Matthias Driess and Prof. Dr. John F. Hartwig

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201205570

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      Breaking the donor limits: The remarkable coordination chemistry of ECHE (E=Si, Ge) ligands with Group 9 metals (Ir, Rh) and their application in catalytic C[BOND]H borylation of arenes was investigated. The spectroscopic and structural features of the first [ECE] iridium complexes show the stronger σ-donating properties of the divalent Si and Ge pincer ligands compared to analogous PIII-based ligands.

    6. Ionic Liquids

      Pseudo-Encapsulation—Nanodomains for Enhanced Reactivity in Ionic Liquids (pages 11483–11486)

      Cameron C. Weber, Assoc. Prof. Dr. Anthony F. Masters and Prof. Dr. Thomas Maschmeyer

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206113

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      Domain constrained: Polar and nonpolar domains within 1-alkyl-3-methylimidazolium ionic liquids can affect reaction outcomes by pseudo-encapsulation of reactants and this has been explored for a nucleophilic substitution reaction using a cationic substrate and a range of nucleophiles. The significant rate enhancements observed correlate with the concentration of the polar reactants within the ionic liquid's polar domain. ([CnMIM]=1-alkyl-3-methylimidazolium).

    7. Homogeneous Catalysis

      Copper-Catalyzed Silacarboxylation of Internal Alkynes by Employing Carbon Dioxide and Silylboranes (pages 11487–11490)

      Prof. Dr. Tetsuaki Fujihara, Yosuke Tani, Kazuhiko Semba, Prof. Dr. Jun Terao and Prof. Dr. Yasushi Tsuji

      Article first published online: 8 OCT 2012 | DOI: 10.1002/anie.201207148

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      Silalactones: The copper-catalyzed reaction of internal alkynes with (dimethylphenylsilyl)pinacolborane (Me2PhSi-B(pin)) as the silicon source and CO2 at atmospheric pressure afforded silalactones selectively in good to high yields. The silalactones can be used as substrates for the Hiyama cross-coupling reaction as demonstrated for one substrate.

    8. Sesquiterpenes

      Scalable, Enantioselective Synthesis of Germacrenes and Related Sesquiterpenes Inspired by Terpene Cyclase Phase Logic (pages 11491–11495)

      Klement Foo, Ippei Usui, Daniel C. G. Götz, Erik W. Werner, Dane Holte and Phil S. Baran

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206904

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      Terpene cyclase phase: Inspired by this logic, a scalable and enantioselective divergent synthesis of germacrane-type sesquiterpenes is developed. Salient features of this work include: 1) the direct ring closure of a farnesol derivative to the 10-membered carbocycle 1, and 2) subsequent synthetic operations on 1 to gain access to different bicyclic frameworks such as guaianes, cadinanes, selinanes, and elemenes.

    9. Heterogeneous Catalysis

      Sulfur and Nitrogen Dual-Doped Mesoporous Graphene Electrocatalyst for Oxygen Reduction with Synergistically Enhanced Performance (pages 11496–11500)

      Ji Liang, Yan Jiao, Mietek Jaroniec and Prof. Shi Zhang Qiao

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201206720

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      Doping duo: Mesoporous graphene doped with both N and S atoms (N-S-G) was prepared in one step and studied as an electrochemical catalyst for the oxygen reduction reaction (ORR). The catalyst shows excellent ORR performance comparable to that of commercial Pt/C. The outstanding activity of N-S-G results from both the large number and the synergistic effect of the dopant heteroatoms.

    10. Nanotubes

      Microwave-Assisted Synthesis of Porous Ag2S–Ag Hybrid Nanotubes with High Visible-Light Photocatalytic Activity (pages 11501–11504)

      Wenlong Yang, Dr. Lei Zhang, Prof. Yong Hu, Yijun Zhong, Hao Bin Wu and Prof. Xiong Wen (David) Lou

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206715

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      Brought to light: Ag2S–Ag hybrid nanotubes were synthesized by rapid microwave-assisted sulfidation of Ag2CO3 nanorods. The relative amounts of Ag2S and Ag in the hybrid structure can be controlled easily by varying the concentration of the sulfur precursor. The optimized Ag2S–Ag hybrid structure has superior photocatalytic activity (yellow) for both degradation of methyl orange (see graph) and reduction of aqueous CrVI under visible-light irradiation.

    11. Asymmetric Catalysis

      Reconciling the Stereochemical Course of Nucleopalladation with the Development of Enantioselective Wacker-Type Cyclizations (pages 11505–11509)

      Adam B. Weinstein and Prof. Shannon S. Stahl

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201206702

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      A stereochemical substrate probe was used to assess the factors that affect the stereochemical course of nucleopalladation in the context of an enantioselective Wacker-type reaction. The enantioselectivity correlates directly with the nucleopalladation pathway, and both the neutral-donor and anionic ligands on palladium are capable of controlling selectivity for cis- or trans-nucleopalladation (see scheme; TFA=trifluoroacetate).

    12. Synthetic Methods

      Asymmetric Cross-Coupling of Aryl Triflates to the Benzylic Position of Benzylamines (pages 11510–11513)

      Genette I. McGrew, Dr. Corneliu Stanciu, Jiadi Zhang, Dr. Patrick J. Carroll, Dr. Spencer D. Dreher and Prof. Patrick J. Walsh

      Article first published online: 4 OCT 2012 | DOI: 10.1002/anie.201201874

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      Ligand in a haystack: The first catalytic asymmetric cross-coupling of benzyllithiums α to tertiary amines using [Cr(CO)3] activation of benzylic Cmath image[BOND]H bonds is described. The stabilized organolithium undergoes Pd-catalyzed coupling with aryl triflates (ArOTf) by a novel dynamic kinetic resolution to yield enantioenriched diarylmethylamines. The chiral ligand for this reaction was identified using high-throughput experimentation with 192 ligands.

    13. Biosynthetic Mechanism

      Mimicking Dimethylallyltryptophan Synthase: Experimental Evidence for a Biosynthetic Cope Rearrangement Process (pages 11514–11516)

      M. Sc. Darius D. Schwarzer, Dipl.-Ing. Philipp J. Gritsch and Dr. Tanja Gaich

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201203586

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      Easy to cope with: Experimental evidence was found to support an enzymatic [3,3]-sigmatropic rearrangement catalyzed by dimethylallyltryptophan (DMAT) synthase (see scheme). A bio-inspired system showed the feasibility of Cope rearrangement to the C-4 position of the indole nucleus. The tricyclic benzo[cd]indole core of welwitindolinones and dragmacidin E was synthesized using this transformation.

    14. Heterogeneous Catalysis

      Hydration of Epoxides on [CoIII(salen)] Encapsulated in Silica-Based Nanoreactors (pages 11517–11521)

      Dr. Bo Li, Shiyang Bai, Dr. Xuefeng Wang, Mingmei Zhong, Prof. Dr. Qihua Yang and Prof. Dr. Can Li

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201203774

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      A confined workspace has its benefits in the case of a non-acid solid catalyst prepared by encapsulating [CoIII(salen)] in the nanocages of mesoporous silica. The catalytic activity and selectivity of [CoIII(salen)] were increased significantly owing to the enhanced cooperative activation effect in the nanoreactors. Thus, ethylene oxide (EO) underwent hydration at a low 2:1 H2O/EO molar ratio to give ethylene glycol in up to 96 % yield.

    15. Assisted Tandem Catalysis

      Tandem Palladium(0) and Palladium(II)-Catalyzed Allylic Alkylation Through Complementary Redox Cycles (pages 11522–11526)

      Prof. Barry M. Trost, David A. Thaisrivongs and Max M. Hansmann

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201204251

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      Here it goes again: A tandem catalytic process effects sequential Pd0-catalyzed allylic alkylations through leaving group ionization and PdII-catalyzed allylic alkylations by C[BOND]H activation. By employing an oxidative trigger to convert the catalytic species from Pd0 into PdII, both transformations can be conducted in a single reaction vessel using the same precatalyst. This allows for the selective introduction of otherwise indistinguishable allyl groups.

    16. Sandwich Complexes

      Threshold Ionization of Cobaltocene: The Metallocene Molecule Revealing Zero Kinetic Energy States (pages 11527–11530)

      Prof. Dr. Sergey Y. Ketkov and Priv.-Doz. Dr. Heinrich L. Selzle

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201205164

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      Playing it cool: The mass-analyzed threshold ionization (MATI) spectrum of jet-cooled cobaltocene shows a surprisingly rich vibronic structure which provides high-resolution adiabatic (Iad.) and vertical (Ivert.) ionization energies of the neutral molecule, as well as vibrational frequencies of the gas-phase cation. The spectrum is indicative of both Jahn–Teller (JT) and pseudo-Jahn–Teller (PJT) activity in the 19-electron [Cp2Co] sandwich complex.

    17. Synthetic Methods

      A Simple Synthesis of Sugar Nucleoside Diphosphates by Chemical Coupling in Water (pages 11531–11534)

      Hidenori Tanaka, Yayoi Yoshimura, Malene R. Jørgensen, Jose A. Cuesta-Seijo and Ole Hindsgaul

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201205433

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      Sugar nucleotides made easy: The new reagent “ImIm”, which is formed in situ in water, is shown to activate nucleoside 5′-phosphates to their imidazolides, these can subsequently couple with sugar-1-phosphates; the whole procedure takes place in water. This truly simple method yields a crude product mixture that can be used directly as a source of donors for glycosyltransferase-mediated oligsaccharide synthesis. In the scheme, B stands for the nucleobases U, A, or G.

    18. Stable Isopeptide Bond

      N-Methylation of Isopeptide Bond as a Strategy to Resist Deubiquitinases (pages 11535–11539)

      Mahmood Haj-Yahya, Najat Eltarteer, Shimrit Ohayon, Efrat Shema, Eran Kotler, Prof. Moshe Oren and Prof. Ashraf Brik

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201205771

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      Stable like a rock: An efficient method to generate N-methylated isopeptide bonds has been developed. The strategy was used to generate highly stable ubiquitinated peptides and proteins that are resistant to deubiquitinases (DUBs; see scheme). Thus, the behavior of several stable ubiquitin conjugates with different DUBs was studied in vitro and within a cellular environment.

    19. Homogeneous Catalysis

      Highly Efficient Stereoselective Catalytic C(sp3)[BOND]H Insertions with Donor Rhodium Carbenoids Generated from Cyclopropenes (pages 11540–11544)

      Alexis Archambeau, Dr. Frédéric Miege, Dr. Christophe Meyer and Prof. Dr. Janine Cossy

      Article first published online: 8 OCT 2012 | DOI: 10.1002/anie.201205913

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      Rings of five and six: Donor alkenyl rhodium carbenoids generated from 3,3-dimethylcyclopropenylcarbinols exhibit high reactivity in intramolecular C[BOND]H insertions. The reactions proceed under remarkably mild conditions, tolerate the presence of the free hydroxy group, and afford an efficient and stereoselective access to a variety of functionalized carbocycles and oxygen heterocycles.

    20. Synthetic Methods

      Copper-Catalyzed Difluoromethylation of β,γ-Unsaturated Carboxylic Acids: An Efficient Allylic Difluoromethylation (pages 11545–11547)

      Dr. Zhengbiao He, Mingyou Hu, Tao Luo, Lingchun Li and Prof. Dr. Jinbo Hu

      Article first published online: 15 OCT 2012 | DOI: 10.1002/anie.201206556

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      Not one but two! A new strategy for the regiospecific construction of compounds with allylic CF2H groups has been developed. The decarboxylative (phenylsulfonyl)difluoromethylation of β,γ-unsaturated carboxylic acids is catalyzed by a Lewis acid (CuCl2⋅2 H2O), and the resulting product easily undergoes desulfonylation.

    21. Cycloaddition

      Construction of Monocyclic Eight-Membered Rings: Intermolecular Rhodium(I)-Catalyzed [6+2] Cycloaddition of 4-Allenals with Alkynes (pages 11548–11551)

      Dr. Yoshihiro Oonishi, Akihito Hosotani and Prof. Dr. Yoshihiro Sato

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206508

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      Rounding up: A RhI-catalyzed intermolecular cycloaddition of 4-allenals with alkynes has been developed that provides various monocyclic eight-membered rings in good to high yields in a stereoselective manner (see scheme). In addition, the chirality of the starting allene is transferred in this reaction, thereby giving optically active monocyclic eight-membered ring compounds.

    22. Asymmetric Catalysis

      Intermolecular [2+2] Reaction of N-Allenylsulfonamides with Vinylarenes: Enantioselective Gold(I)-Catalyzed Synthesis of Cyclobutane Derivatives (pages 11552–11555)

      Dr. Samuel Suárez-Pantiga, Cristina Hernández-Díaz, Dr. Eduardo Rubio and Prof. Dr. José M. González

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206461

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      Golden touch: N-allenylsulfonamides react with styrene derivatives to furnish chiral cyclobutanes in both high yield and enantioselectivity at −70 °C. Phosphoramidite ligands such as 1, facilitate this asymmetric gold(I)-catalyzed [2+2] cycloaddition. Tf=trifluoromethanesulfonyl.

    23. Homogeneous Catalysis

      Efficient and Convenient Palladium-Catalyzed Amination of Allylic Alcohols with N-Heterocycles (pages 11556–11560)

      Dr. Debasis Banerjee, Dr. Rajenahally V. Jagadeesh, Dr. Kathrin Junge, Dr. Henrik Junge and Prof. Dr. Matthias Beller

      Article first published online: 28 SEP 2012 | DOI: 10.1002/anie.201206319

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      Atom economic: A commercially available palladium catalyst system is applied for an environmentally benign allylation of electron-deficient N-heterocycles using allylic alcohols (see scheme). The system is also applied for the N-allylation of biologically important uridine and thymidine derivatives.

    24. Synthetic Methods

      Activation of a C(sp3)[BOND]H Bond by a Transient σ-Alkylpalladium(II) Complex: Synthesis of Spirooxindoles Through a Palladium-Catalyzed Domino Carbopalladation/C(sp3)[BOND]C(sp3) Bond-Forming Process (pages 11561–11565)

      Tiffany Piou, Dr. Luc Neuville and Prof. Dr. Jieping Zhu

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201206267

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      Heck shortens the distance: A method for the palladium-catalyzed activation of a C(sp3)[BOND]H bond by a σ-alkyl PdII complex generated in situ from a remote arylhalide function has been developed. This approach allows a novel domino carbopalladation/C(sp3)[BOND]C(sp3) bond-forming process to provide rapid access to biologically relevant spirooxindoles.

    25. Peptide Synthesis

      Convergent Solid-Phase Synthesis of N-Glycopeptides Facilitated by Pseudoprolines at Consensus-Sequence Ser/Thr Residues (pages 11566–11570)

      Vera Ullmann, Marisa Rädisch, Irene Boos, Jutta Freund, Dr. Claudia Pöhner, Dr. Stefan Schwarzinger and Prof. Carlo Unverzagt

      Article first published online: 3 SEP 2012 | DOI: 10.1002/anie.201204272

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      Remote control: The formation of aspartimides is greatly decreased during peptide elongation and during convergent sugar couplings of Asp-X-Ser/Thr peptides that contain a pseudoproline (red; see scheme). The robust approach efficiently joins complex peptides and N-glycans on the solid phase thus facilitating the availability of glycopeptides and glycoproteins.

    26. Glycoprotein Synthesis

      An Advance in the Chemical Synthesis of Homogeneous N-Linked Glycopolypeptides by Convergent Aspartylation (pages 11571–11575)

      Dr. Ping Wang, Dr. Baptiste Aussedat, Yusufbhai Vohra and Prof. Samuel J. Danishefsky

      Article first published online: 25 SEP 2012 | DOI: 10.1002/anie.201205038

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      Like a Pro: A one-flask aspartylation/deprotection method, wherein long peptide fragments, bearing proximal pseudoproline functionality, are merged with complex glycan domains has been developed. Following aspartylation, acid-mediated global deprotection reveals the elaborated glycopeptide. The temporary pseudoproline functionality serves to suppress formation of aspartimide side products during solid-phase peptide synthesis and aspartylation.

    27. Total Synthesis

      At Last: Erythropoietin as a Single Glycoform (pages 11576–11584)

      Dr. Ping Wang, Dr. Suwei Dong, Dr. John A. Brailsford, Dr. Karthik Iyer, Dr. Steven D. Townsend, Dr. Qiang Zhang, Dr. Ronald C. Hendrickson, Dr. JaeHung Shieh, Dr. Malcolm A. S. Moore and Prof. Samuel J. Danishefsky

      Article first published online: 25 SEP 2012 | DOI: 10.1002/anie.201206090

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      Wild thing: The first total synthesis of wild-type erythropoietin glycoprotein (see picture) has been accomplished. The erythropoietic activity of the synthetic folded protein has been demonstrated.

    28. Sensors

      Surface Plasmon Resonance Chemical Sensing on Cell Phones (pages 11585–11588)

      Pakorn Preechaburana, Marcos Collado Gonzalez, Dr. Anke Suska and Dr. Daniel Filippini

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201206804

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      Chemosensing based on angle-resolved surface plasmon resonance is demonstrated on intact cell phones using a disposable optical coupler and software to configure illumination and acquisition. This coupler operates on different cell phones and is applied for classical affinity assays with commercial chips and custom-made tests with embedded calibration. Measured performance (2.14x10−6 refractive index units) is comparable with compact SPR systems.

    29. Catalytic Oxidation

      Water Oxidation by Single-Site Ruthenium Complexes: Using Ligands as Redox and Proton Transfer Mediators (pages 11589–11593)

      Markus D. Kärkäs, Torbjörn Åkermark, Dr. Eric V. Johnston, Shams R. Karim, Tanja M. Laine, Bao-Lin Lee, Dr. Tobias Åkermark, Prof. Timofei Privalov and Prof. Björn Åkermark

      Article first published online: 28 SEP 2012 | DOI: 10.1002/anie.201205018

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      Light me up: Through the use of an imidazole motif it is possible to introduce a combined redox and proton-transfer mediator into single-site ruthenium water-oxidation catalysts. With the complex (see picture), high turnover numbers and high initial turnover frequencies were attained with the mild oxidant [Ru(bpy)3]3+ (bpy=2,2′-bipyridine).

    30. Lithium-Rich Compounds

      Copper Silicides with the Highest Lithium Content: Li7CuSi2 Containing the 16-Electron Group [CuSi2]7− and Li7.3CuSi3 with Heterographene Nets equation image[CuSi]3.3− (pages 11594–11596)

      Adam Slabon, Dr. Serhiy Budnyk, Dr. Eduardo Cuervo-Reyes, Dr. Michael Wörle, Dipl.-Ing. Christian Mensing and Prof. Dr. Reinhard Nesper

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201203504

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      Incredibly rich in lithium: The ternary silicides Li7CuSi2 with the linear [Si-Cu-Si]7− Zintl anion (see picture) and Li7.3CuSi3 are compounds with the highest lithium content in the ternary system. The crystal and electronic structures of both compounds are discussed.

    31. Solid–Liquid Interface

      First In Situ Observation of the LiCoO2 Electrode/Electrolyte Interface by Total-Reflection X-ray Absorption Spectroscopy (pages 11597–11601)

      Dr. Daiko Takamatsu, Prof. Dr. Yukinori Koyama, Dr. Yuki Orikasa, Shinichiro Mori, Takayuki Nakatsutsumi, Tatsumi Hirano, Prof. Dr. Hajime Tanida, Prof. Dr. Hajime Arai, Prof. Dr. Yoshiharu Uchimoto and Prof. Dr. Zempachi Ogumi

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201203910

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      Surface analysis: In situ total-reflection fluorescence X-ray absorption spectroscopy showed that reduction of cobalt at the surface of a LiCoO2 electrode occurs by contact with a liquid electrolyte. An irreversible behavior was observed at the surface of LiCoO2 during a first charge/discharge process whereas the bulk material showed a reversible behavior. This Co reduction is an initial electrode deterioration.

    32. Electrochemical Lithography

      Electrochemical X-ray Photolithography (pages 11602–11605)

      Dr. Andrei A. Eliseev, Nina A. Sapoletova, Dr. Irina Snigireva, Dr. Anatoly Snigirev and Dr. Kirill S. Napolskii

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201204801

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      Best of both worlds: Electrochemical X-ray photolithography combines the advantages of X-ray photolithography with the versatility of electrochemical processing. A proof-of-concept was carried out by electrochemical deposition of nickel under coherent X-ray illumination guided through a lithographic mask with a 4 micrometer pitch, resulting in formation of a nickel grating (see picture).

    33. Tumor Targeting

      The First Generation of β-Galactosidase-Responsive Prodrugs Designed for the Selective Treatment of Solid Tumors in Prodrug Monotherapy (pages 11606–11610)

      Thibaut Legigan, Dr. Jonathan Clarhaut, Dr. Isabelle Tranoy-Opalinski, Dr. Arnaud Monvoisin, Dr. Brigitte Renoux, Dr. Mikaël Thomas, Dr. Alain Le Pape, Dr. Stéphanie Lerondel and Dr. Sébastien Papot

      Article first published online: 20 SEP 2012 | DOI: 10.1002/anie.201204935

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      Massive attack: Galactoside prodrugs have been designed that can be selectively activated by lysosomal β-galactosidase located inside cancer cells expressing a specific tumor-associated receptor. This efficient enzymatic process triggers a potent cytotoxic effect, releasing the potent antimitotic agent MMAE and allowing the destruction of both receptor-positive and surrounding receptor-negative tumor cells.

    34. Natural Products

      Genomics-Driven Discovery of Burkholderic Acid, a Noncanonical, Cryptic Polyketide from Human Pathogenic Burkholderia Species (pages 11611–11615)

      Jakob Franke, Dr. Keishi Ishida and Prof. Dr. Christian Hertweck

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201205566

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      Biosynthetic secrets unveiled: Targeted promoter exchange in a cryptic biosynthesis gene cluster conserved among certain pathogenic Burkholderia species yielded a highly unstable, structurally unprecedented polyketide, burkholderic acid (1). Labeling experiments, gene knock-outs, and bioinformatics analyses grant first insights into a fascinating polyketide pathway. BurA is an unusual nonribosomal peptide synthetase/polyketide synthase featuring internal thioesterase domains.

    35. Polymersomes

      Light-Switchable Vesicles from Liquid-Crystalline Homopolymer–Surfactant Complexes (pages 11616–11619)

      Lei Li, Dr. Martin Rosenthal, Heng Zhang, Dr. Jaime J. Hernandez, Dr. Markus Drechsler, Dr. Kim Hô Phan, Stephan Rütten, Dr. Xiaomin Zhu, Dr. Dimitri A. Ivanov and Prof. Dr. Martin Möller

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201205660

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      Polymeric onions: A concept of vesicle fabrication based on nonstoichiometric complexation of a polybase with an amphiphilic ligand bearing a sulfonic acid group is developed (see picture). In contrast to conventional polymersomes, the polymer backbones are oriented mainly parallel to the vesicle walls. The vesicles can collapse under UV irradiation because of a UV-triggered transcis isomerization of the azo-group-containing ligand.

    36. Asymmetric Catalysis

      A Chiral Cagelike Copper(I) Catalyst for the Highly Enantioselective Synthesis of 1,1-Cyclopropane Diesters (pages 11620–11623)

      Chao Deng, Dr. Li-Jia Wang, Jun Zhu and Prof. Dr. Yong Tang

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206376

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      Triangulation method: The catalytic enantioselective cyclopropanation of multisubstituted olefins with phenyliodonium ylide malonate has been achieved in the presence of a chiral bisoxazoline copper(I) complex (see scheme). A wide range of substrates undergo the reaction to provide optically active 1,1-cyclopropane diesters in high yield with up to >99 % ee. A rationale for the enantioselective induction has been proposed.

    37. Synthetic Methods

      A Photocatalyst/Enzyme Couple That Uses Solar Energy in the Asymmetric Reduction of Acetophenones (pages 11624–11628)

      Dr. Sumit Choudhury, Dr. Jin-Ook Baeg, Dr. No-Joong Park and Dr. Rajesh K. Yadav

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206019

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      Artificial Photosynthesis System: A novel photocatalyst/enzyme-coupled artificial photosynthesis system harvests solar energy as seen in green plants through the combination of photocatalysis and biocatalysis and induces asymmetry in an achiral substrate (see picture; ADPR=adenosine diphosphate ribose, NADP=nicotinamide adenine dinucleotide phosphate).

    38. Electronic Structure

      π-Stacked Oligo(phenylene vinylene)s Based on Pseudo-Geminal Substituted [2.2]Paracyclophanes: Impact of Interchain Geometry and Interactions on the Electronic Properties (pages 11629–11632)

      Dr. Sukrit Mukhopadhyay, Dr. Subodh P. Jagtap, Dr. Veaceslav Coropceanu, Prof. Jean-Luc Brédas and Prof. David M. Collard

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201205738

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      A clever combination: A series of phenylene vinylene oligomers, in which the conjugated segments are held in a well-defined stacked arrangement along their entire length, was studied experimentally and theoretically (see picture). The impact of the extended interchain interactions on the photophysics of the π-stacked systems is reported.

    39. Vesicles

      “Breathing” Vesicles with Jellyfish-like On–Off Switchable Fluorescence Behavior (pages 11633–11637)

      Dr. Ruijiao Dong, Prof. Bangshang Zhu, Prof. Yongfeng Zhou, Deyue Yan and Xinyuan Zhu

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201206362

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      Controlled, deep breathing: Polymeric vesicles that exhibit reversible pH-induced “breathing” behavior accompanied by switchable fluorescence (see picture) were prepared through the aqueous self-assembly of an amphiphilic block copolymer. Mechanistic studies showed that this jellyfish-like breathing and light-emitting behavior originates from protonation- or deprotonation-induced changes in the conformation of the azobenzene chromophores.

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