Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 12

March 18, 2013

Volume 52, Issue 12

Pages 3283–3532

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Bio-Inspired Catalytic Imine Reduction by Rhodium Complexes with Tethered Hantzsch Pyridinium Groups: Evidence for Direct Hydride Transfer from Dihydropyridine to Metal-Activated Substrate (Angew. Chem. Int. Ed. 12/2013) (page 3283)

      Alex McSkimming, Dr. Mohan M. Bhadbhade and Prof. Stephen B. Colbran

      Article first published online: 28 FEB 2013 | DOI: 10.1002/anie.201301157

      Thumbnail image of graphical abstract

      Catalysis in a teacup, inspired by nature Alfred Werner (left) received the 1913 Nobel Prize for his coordination theory of transition metal compounds, and Arthur Hantzsch (right) discovered the route to (dihydro)pyridines that bear his name. In their Communication on page 3411 ff., S. B. Colbran et al. disclose that conjugation of rhodium and Hantzsch pyridine centers affords a catalyst for the transfer hydrogenation of imines in air under ambient conditions. A key step in the catalysis mimics that in metallo-(de)hydrogenase enzymes.

    2. You have free access to this content
      Inside Cover: Helical Colloidal Sphere Structures through Thermo-Reversible Co-Assembly with Molecular Microtubes (Angew. Chem. Int. Ed. 12/2013) (page 3284)

      Dr. Lingxiang Jiang, Julius W. J. de Folter, Prof. Dr. Jianbin Huang, Prof. Dr. Albert P. Philipse, Prof. Dr. Willem K. Kegel and Dr. Andrei V. Petukhov

      Article first published online: 1 MAR 2013 | DOI: 10.1002/anie.201301345

      Thumbnail image of graphical abstract

      Hierarchical self-assembly is often exploited by nature to build complex functional entities. A similar approach yielded a library of dynamic colloid-in-tube structures, such as colloidal zigzags, double- and triple-helices, by utilizing the thermo-reversible co-assembly of colloidal spheres and molecular microtubes, as reported by J. Huang, A. V. Petukhov, et al. in their Communication on page 3364 ff. The assembly and disassembly of these structures near human body temperature was explored in situ and in real time.

    3. You have free access to this content
      Inside Back Cover: Polymer Nanofiber-Embedded Microchips for Detection, Isolation, and Molecular Analysis of Single Circulating Melanoma Cells (Angew. Chem. Int. Ed. 12/2013) (page 3533)

      Dr. Shuang Hou, Dr. Libo Zhao, Qinglin Shen, Dr. Juehua Yu, Charles Ng, Xiangju Kong, Dr. Dongxia Wu, Dr. Min Song, Dr. Xiaohong Shi, Xiaochun Xu, Wei-Han OuYang, Rongxian He, Prof. Xing-Zhong Zhao, Tom Lee, Prof. F. Charles Brunicardi, Dr. Mitch André Garcia, Prof. Antoni Ribas, Prof. Roger S. Lo and Prof. Hsian-Rong Tseng

      Article first published online: 26 FEB 2013 | DOI: 10.1002/anie.201301082

      Thumbnail image of graphical abstract

      Transparent polymer-nanofiber substrates combined with a laser microdissection technique, produced a new single-cell isolation technology, as shown by M. A. Garcia, A. Ribas, R. S. Lo, H.-R. Tseng, et al. in their Communication on page 3379 ff. Using this new technique, single circulating melanoma cells (CMCs) were isolated from patients' blood for subsequent single-cell genotyping to identify a mutation in a proto-oncogene BRAF.

    4. You have free access to this content
      Back Cover: An Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation (Angew. Chem. Int. Ed. 12/2013) (page 3534)

      Xinxin Shao, Xueqiang Wang, Tao Yang, Prof. Dr. Long Lu and Prof. Dr. Qilong Shen

      Article first published online: 4 MAR 2013 | DOI: 10.1002/anie.201301409

      Thumbnail image of graphical abstract

      A powerful and valuable reagent for direct trifluoromethylthiolation is reported by L. Lu, Q. Shen, and co-workers in their Communication on page 3457 ff. This new electrophilic hypervalent iodine reagent reacts with a wide range of substrates under mild conditions. The image shows the reagent and its products within the context of the ancient Chinese symbolism of the round sky and square earth.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 12/2013 (pages 3287–3301)

      Article first published online: 13 MAR 2013 | DOI: 10.1002/anie.201390011

  3. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Corrigendum: Hypergolic Ionic Liquids with the 2,2-Dialkyltriazanium Cation (page 3301)

      Haixiang Gao, Young-Hyuk Joo, Brendan Twamley, Zhiqiang Zhou and Jean'ne M. Shreeve

      Article first published online: 13 MAR 2013 | DOI: 10.1002/anie.201300577

      This article corrects:

      Hypergolic Ionic Liquids with the 2,2-Dialkyltriazanium Cation1

      Vol. 48, Issue 15, 2792–2795, Article first published online: 5 MAR 2009

  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Reviews
    9. Highlights
    10. Minireview
    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 Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    1. Jean'ne M. Shreeve (page 3308)

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201208008

      Thumbnail image of graphical abstract

      “My motto is ‘full speed ahead.’ My favorite molecule is fluorine …” This and more about Jean'ne M. Shreeve can be found on page 3308.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    1. Water in Organic Synthesis. Science of Synthesis Workbench Edition. Edited by Shū Kobayashi. (pages 3311–3312)

      Arkadi Vigalok

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209278

      Thumbnail image of graphical abstract

      Thieme, Stuttgart, 2012. 960 pp., softcover, € 249.00.—ISBN 978-3131693518

    2. Photoinitiators for Polymer Synthesis. Scope, Reactivity, and Efficiency. By Jean-Pierre Fouassier and Jacques Lalavée. (page 3312)

      Dominik Voll and Christopher Barner-Kowollik

      Article first published online: 28 FEB 2013 | DOI: 10.1002/anie.201209688

      Thumbnail image of graphical abstract

      Wiley-VCH, Weinheim, 2012. 476 pp., hardcover, € 149.00.—ISBN 978-3527332106

  8. Highlights

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

      Multivalent Directed Assembly of Colloidal Particles (pages 3314–3316)

      Dr. Hirotaka Ejima, Joseph J. Richardson and Prof. Frank Caruso

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201209461

      Thumbnail image of graphical abstract

      Sticking together: Colloidal particles with a determined number of sticky sites arranged in precise geometries analogous to atoms were created. The kinetics of the colloidal assemblies related to specific chemical reactions (see figure) were investigated using optical microscopy. This general method should allow for a broad range of useful 3D colloidal assemblies.

    2. Asymmetric Catalysis

      Achieving Enantioselectivity with Chiral Cyclopentadienylrhodium Complexes (pages 3317–3319)

      Dr. Marko Hapke and Prof. Dr. C. Christoph Tzschucke

      Article first published online: 19 FEB 2013 | DOI: 10.1002/anie.201209889

      Thumbnail image of graphical abstract

      Chiral possibilities (Cp): In two approaches for introducing chirality into reactions of half-sandwich Rh complexes, dihydroisoquinolones have been synthesized from benzamides and olefins. In one approach C2-symmetric Cp ligands were utilized, while in the other an artificial metalloenzyme was employed as the chiral catalyst, leading to high levels of enantioselectivity.

  9. Minireview

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

      Formaldehyde in the Ambient Atmosphere: From an Indoor Pollutant to an Outdoor Pollutant? (pages 3320–3327)

      Prof. Dr. Tunga Salthammer

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201205984

      Thumbnail image of graphical abstract

      Formaldehyde is a well-known gaseous indoor pollutant. In recent years different countries and organizations have developed concepts for the evaluation of indoor air quality, and consequently, the indoor concentrations of formaldehyde have decreased. However, in the outdoor air in many metropolitan areas, formaldehyde concentrations are continuously growing and sometimes exceed guideline values for indoor air.

  10. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Reviews
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    1. C[BOND]F Activation

      Synthesis of Fluorinated Building Blocks by Transition-Metal-Mediated Hydrodefluorination Reactions (pages 3328–3348)

      Dr. Moritz F. Kuehnel, Prof. Dr. Dieter Lentz and Prof. Dr. Thomas Braun

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201205260

      Thumbnail image of graphical abstract

      Keen on fluorine: Metal-induced C[BOND]F bond activation is emerging as a promising tool to access partly fluorinated molecules (see scheme). Hydrodefluorination has been achieved in the coordination sphere of various transition-metal complexes and features a unique mechanistic diversity.

  11. Communications

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

      Using Fluorescent Post-Labeling To Probe the Subcellular Localization of DNA-Targeted Platinum Anticancer Agents (pages 3350–3354)

      Song Ding, Xin Qiao, Dr. Jimmy Suryadi, Dr. Glen S. Marrs, Prof. Gregory L. Kucera and Prof. Ulrich Bierbach

      Article first published online: 20 FEB 2013 | DOI: 10.1002/anie.201210079

      Thumbnail image of graphical abstract

      Green around the cells: A post-labeling method was developed to image a DNA-targeted platinum drug in cancer cells by confocal fluorescence microscopy. This was done using ligation chemistry between an azide-functionalized platinum-acridine anticancer drug and an alkyne-modified dye, Alexa Fluor 488 (green star, see figure). The platinum-acridine agent was shown to accumulate in the nucleoli of cancer cells (NCI-H460).

    2. Zeolites

      Formation of Hierarchically Organized Zeolites by Sequential Intergrowth (pages 3355–3359)

      Dr. Watcharop Chaikittisilp, Yuki Suzuki, Dr. Rino R. Mukti, Dr. Tatsuya Suzuki, Dr. Keisuke Sugita, Dr. Keiji Itabashi, Prof. Dr. Atsushi Shimojima and Prof. Dr. Tatsuya Okubo

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201209638

      Thumbnail image of graphical abstract

      Make intergrowth, not war! Hierarchically organized MFI zeolites with micro-, meso-, and macroporosity (see scheme) in one structure were made by sequential intergrowth by using a simple organic structure-directing agent (OSDA) without meso- or macroporogens. The use of an OSDA that imperfectly fits the zeolite framework generated very thin zeolite plates with 90° rotational intergrowth.

    3. Contracted Porphyrins

      Thiatriphyrin(2.1.1): A Core-Modified Contracted Porphyrin (pages 3360–3363)

      Dr. Daiki Kuzuhara, Yuka Sakakibara, Dr. Shigeki Mori, Prof. Dr. Tetsuo Okujima, Prof. Dr. Hidemitsu Uno and Prof. Dr. Hiroko Yamada

      Article first published online: 11 FEB 2013 | DOI: 10.1002/anie.201209678

      Thumbnail image of graphical abstract

      Elusive in its free-base form, the core-modified contracted porphyrin thiatriphyrin(2.1.1) was prepared with p-tolyl substituents by intramolecular McMurry coupling and then converted into various alkoxy-substituted analogues (see scheme; DBU=1,8-diazabicyclo[5.4.0]undec-7-ene). In the presence of trifluoroacetic acid (TFA), each of these compounds was transformed into the protonated thiatriphyrin(2.1.1), which exhibited moderate aromaticity.

    4. Self-Assembly

      Helical Colloidal Sphere Structures through Thermo-Reversible Co-Assembly with Molecular Microtubes (pages 3364–3368)

      Dr. Lingxiang Jiang, Julius W. J. de Folter, Prof. Dr. Jianbin Huang, Prof. Dr. Albert P. Philipse, Prof. Dr. Willem K. Kegel and Dr. Andrei V. Petukhov

      Article first published online: 25 FEB 2013 | DOI: 10.1002/anie.201209767

      Thumbnail image of graphical abstract

      The co-assembly of spherical colloids and surfactant–cyclodextrin microtubes yields a library of dynamic colloid-in-tube structures, including helices. In situ observations of these structures, including their thermo-reversible assembly and disassembly, demonstrate the potential of the interplay between molecular and colloidal self-assembly, thereby providing a novel route to temperature-sensitive particle alignment and release.

    5. Interface Engineering

      Revealing Interface-Assisted Charge-Transfer Mechanisms by Using Silicon Nanowires as Local Probes (pages 3369–3373)

      Jindong Wang, Zhenxing Wang, Qiaochu Li, Lin Gan, Xinjun Xu, Prof. Lidong Li and Prof. Xuefeng Guo

      Article first published online: 11 FEB 2013 | DOI: 10.1002/anie.201209816

      Thumbnail image of graphical abstract

      A semiconductor/environment interface has been formed in which suspended silicon nanowires (SiNWs) are in direct contact with photoactive TiO2 quantum dots. The photoactivity of TiO2 competes with the intrinsic photoresponses of p-type silicon nanowires. Rational control of the competitive mechanism realizes remarkable mirror-imaging photo-switching and superior rectifying effects in a single SiNW-based device.

    6. Neurochemistry

      Development of a Platinum Complex as an anti-Amyloid Agent for the Therapy of Alzheimer’s Disease (pages 3374–3378)

      Dr. Vijaya B. Kenche, Dr. Lin W. Hung, Keyla Perez, Irene Volitakes, Dr. Guiseppe Ciccotosto, Jeffrey Kwok, Nicole Critch, Nikki Sherratt, Mikhalina Cortes, Varsha Lal, Prof. Colin L. Masters, Kazuma Murakami, Prof. Roberto Cappai, Dr. Paul A. Adlard and Prof. Kevin J. Barnham

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209885

      Thumbnail image of graphical abstract

      Brainwash! A platinum complex (see scheme) was developed that could be administered orally and reduce the amyloid burden in the brains of transgenic mouse models suffering from Alzheimer's disease. Analyses of brain tissues showed that treatment with the Pt compound led to a 26 % decrease in the number of amyloid β-peptide plaques.

    7. Cancer Diagnosis

      Polymer Nanofiber-Embedded Microchips for Detection, Isolation, and Molecular Analysis of Single Circulating Melanoma Cells (pages 3379–3383)

      Dr. Shuang Hou, Dr. Libo Zhao, Qinglin Shen, Dr. Juehua Yu, Charles Ng, Xiangju Kong, Dr. Dongxia Wu, Dr. Min Song, Dr. Xiaohong Shi, Xiaochun Xu, Wei-Han OuYang, Rongxian He, Prof. Xing-Zhong Zhao, Tom Lee, Prof. F. Charles Brunicardi, Dr. Mitch André Garcia, Prof. Antoni Ribas, Prof. Roger S. Lo and Prof. Hsian-Rong Tseng

      Article first published online: 21 FEB 2013 | DOI: 10.1002/anie.201208452

      Thumbnail image of graphical abstract

      Confined to one cell: A method to detect and isolate single circulating melanoma cells (CMCs; see figure) has been produced by integrating a polymer-nanofiber-embedded nanovelcro cell-affinity assay with a laser microdissection (LMD) technique. This method is able to separate CMCs from normal white blood cells (WBCs) and sequence individual cells for a specific mutation related to cancer progression, allowing for more personalized cancer therapy.

    8. Protein Binding

      Probing Target Search Pathways during Protein–Protein Association by Rational Mutations Based on Paramagnetic Relaxation Enhancement (pages 3384–3388)

      Tae-Kyung Yu, Young-Joo Yun, Ko On Lee and Prof. Jeong-Yong Suh

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201208688

      Thumbnail image of graphical abstract

      Not just a random encounter: Protein–protein association involves short-lived encounter complexes that can be productive or non-productive according to their roles in the specific complex formation (see scheme). A study of mutant proteins forming a complex based on NMR paramagnetic relaxation enhancement demonstrates that productive encounter complexes can be directly monitored and located quantitatively.

    9. Molecular Spintronics

      Fano-Resonance-Driven Spin-Valve Effect Using Single-Molecule Magnets (pages 3389–3393)

      Kwangwoo Hong and Prof. Dr. Woo Youn Kim

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201208816

      Thumbnail image of graphical abstract

      What's your spin on it? A carbon nanotube device decorated with single-molecule magnets through π–π stacking interactions (see scheme) was shown to have spin-dependent transmission (red=spin-up, blue=spin-down) around the energy levels of the molecule owing to Fano resonance, which could be tuned by adjusting the strength of the π–π stacking. This Fano-resonance-driven spin-valve effect offers a new method to make molecular spintronics.

    10. Chiral Surfaces

      Enantioselective Separation on Naturally Chiral Metal Surfaces: d,l-Aspartic Acid on Cu(3,1,17)R&S Surfaces (pages 3394–3397)

      Yongju Yun and Prof. Andrew J. Gellman

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201209025

      Thumbnail image of graphical abstract

      Unequivocal evidence of enantioselective, equilibrium separation of a racemic mixture on a naturally chiral metal surface is presented for the first time. The enantioselectivity is much higher than that of chiral molecules on mineral surfaces. Furthermore, the quantitative nature of the 13C labeling method provides the first direct measure of an enantiospecific adsorption energy difference on a chiral metal surface.

    11. Water Splitting

      Promoting the Activity of Catalysts for the Oxidation of Water with Bridged Dinuclear Ruthenium Complexes (pages 3398–3401)

      Yi Jiang, Dr. Fei Li, Biaobiao Zhang, Dr. Xiaona Li, Xiaohong Wang, Fang Huang and Prof. Licheng Sun

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201209045

      Thumbnail image of graphical abstract

      Solar fuels: Dinuclear ruthenium catalysts prepared from two covalently bridged monomeric catalytic units show outstanding activities towards the oxidation of water with high turnover numbers up to 43 000 and turnover frequencies up to 40 s−1 (see picture). Direct comparison of the performance parameters indicates that the dimers are significantly more active as catalysts than the monomers.

    12. Adsorption Characteristics

      Metal–Organic Framework Thin Films: Crystallite Orientation Dependent Adsorption (pages 3402–3405)

      Dr. Bo Liu, M. Sc. Min Tu and Prof. Dr. Roland A. Fischer

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201207908

      Thumbnail image of graphical abstract

      Well oriented: Preferred [100] and [001] orientations of metal–organic framework crystallites, [Cu2(ndc)2(dabco)] (ndc=1,4-naphthalenedicarboxylate, dabco=1,4-diazabicyclo[2.2.2]octane), attached to surfaces were fabricated. Different pore openings owing to anisotropic properties of [Cu2(ndc)2(dabco)] result in oriented thin films exhibiting distinct adsorption kinetics for volatile organic compounds.

    13. Structure–Property Relationship

      Cs2B4SiO9: A Deep-Ultraviolet Nonlinear Optical Crystal (pages 3406–3410)

      Hongping Wu, Hongwei Yu, Prof. Shilie Pan, Zhenjun Huang, Zhihua Yang, Xin Su and Prof. Kenneth R. Poeppelmeier

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201209151

      Thumbnail image of graphical abstract

      Nonlinear optics: A new borosilicate, Cs2B4SiO9, has been synthesized (see picture). This compound represents a new kind of a boron-rich borosilicate and shows a 4.6 times stronger powder second-harmonic generation response relative to KH2PO4. In addition, Cs2B4SiO9 has a short UV cutoff edge (below 190 nm).

    14. Biomimetic Transfer Hydrogenation

      Bio-Inspired Catalytic Imine Reduction by Rhodium Complexes with Tethered Hantzsch Pyridinium Groups: Evidence for Direct Hydride Transfer from Dihydropyridine to Metal-Activated Substrate (pages 3411–3416)

      Alex McSkimming, Dr. Mohan M. Bhadbhade and Prof. Stephen B. Colbran

      Article first published online: 26 FEB 2013 | DOI: 10.1002/anie.201210086

      Thumbnail image of graphical abstract

      Inspired by Nature: A conceptually new design for a catalyst, combining a metal center abutted to an organic hydride donor, is demonstrated for the formate-driven transfer hydrogenation of imines under ambient conditions. A key step, transfer of hydride from the organohydride donor to the metal-polarized substrate, mirrors that in metallo-(de)hydrogenase enzymes.

    15. Organic Electronic Devices

      A Small-Molecule Zwitterionic Electrolyte without a π-Delocalized Unit as a Charge-Injection Layer for High-Performance PLEDs (pages 3417–3420)

      Chao Min, Changsheng Shi, Wenjun Zhang, Tonggang Jiu, Prof. Jiangshan Chen, Prof. Dongge Ma and Prof. Junfeng Fang

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201209959

      Thumbnail image of graphical abstract

      Down to the bare bones: Small-molecule zwitterionic materials were found to be more efficient as charge-injection materials in an organic electronic device than a previously described polymer (see structures). Furthermore, the superior device performance observed for 1 indicates that it is not necessary to focus only on π-delocalized systems and that solid ionic liquids may be promising alternative candidates for charge-injection materials.

    16. Natural Product Synthesis

      Syntheses of Xanthofulvin and Vinaxanthone, Natural Products Enabling Spinal Cord Regeneration (pages 3421–3424)

      Abram Axelrod, Anders M. Eliasen, Matthew R. Chin, Katherine Zlotkowski and Dr. Dionicio Siegel

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201205837

      Thumbnail image of graphical abstract

      Growth promoting: The first synthesis of the natural product xanthofulvin (SM-216289) has resolved issues regarding its structural assignment and that described for the natural product 411J. The structurally and biologically related natural product vinaxanthone was similarly prepared through a novel dimerization reaction. Treatment of C. elegans with synthetic xanthofulvin and vinaxanthone enhanced axonal branching.

    17. PELDOR Spectroscopy

      Broadband Inversion PELDOR Spectroscopy with Partially Adiabatic Shaped Pulses (pages 3425–3429)

      Philipp E. Spindler, Prof. Dr. Steffen J. Glaser, Prof. Dr. Thomas E. Skinner and Prof. Dr. Thomas F. Prisner

      Article first published online: 19 FEB 2013 | DOI: 10.1002/anie.201207777

      Thumbnail image of graphical abstract

      Distance and spins: A new broadband, frequency-selective inversion pulse has been devised for pulsed electron–electron double resonance (PELDOR) spectroscopy, a unique method used to determine distance distributions between two or more paramagnetic centers 2–10 nm apart. The PELDOR modulation depth can be increased by substituting the rectangular pump pulse by a shaped pulse.

    18. Single-Molecule Magnets

      The Inherent Single-Molecule Magnet Character of Trivalent Uranium (pages 3430–3433)

      Dr. Fabrizio Moro, Dr. David P. Mills, Dr. Stephen T. Liddle and Prof. Dr. Joris van Slageren

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201208015

      Thumbnail image of graphical abstract

      Uranium magnets: Three uranium(III) complexes with distinctly different structures and compositions are all shown to display slow relaxation of the magnetization. This study greatly expands the range of slowly relaxing uranium complexes, and demonstrates that this behavior is not limited to specific ligand types or molecular symmetries (see picture).

    19. Cross-Coupling

      Mild and Rapid Pd-Catalyzed Cross-Coupling with Hydrazine in Continuous Flow: Application to the Synthesis of Functionalized Heterocycles (pages 3434–3437)

      Dr. Andrew DeAngelis, Dr. Dong-Hui Wang and Prof. Dr. Stephen L. Buchwald

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201208544

      Thumbnail image of graphical abstract

      Minimizing risk: The synthesis of arylhydrazines through C[BOND]N cross-coupling of aryl chlorides with hydrazine is described. Through the use of continuous flow, the hazards associated with the use of hydrazine in the presence of transition metals are decreased. In addition, multistep flow sequences have also been developed for the generation of functionalized heterocycles utilizing the arylhydrazine intermediates.

    20. Telechelic Polyethylene

      Telechelic Polyethylene from Catalyzed Chain-Growth Polymerization (pages 3438–3441)

      Dr. Ian German, Wissem Kelhifi, Dr. Sébastien Norsic, Dr. Christophe Boisson and Dr. Franck D'Agosto

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201208756

      Thumbnail image of graphical abstract

      A functional chain transfer agent, bis(10-undecenyl)magnesium, was employed as cocatalyst in conjunction with [(C5Me5)2NdCl2Li(OEt2)2] to catalyze polyethylene (PE) chain growth on magnesium. Vinyl-PE-Mg-PE-vinyl units were then further functionalized. This is the first example of catalytic ethylene polymerization with single-step, in situ functionalization to telechelic polyethylenes.

    21. Natural Product Synthesis

      A Concise Total Synthesis of (R)-Puraquinonic Acid (pages 3442–3445)

      Erica A. Tiong, Daniel Rivalti, Benjamin M. Williams and Prof. James L. Gleason

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201208792

      Thumbnail image of graphical abstract

      Distant relative: The configuration of the quaternary stereocenter in puraquinonic acid (see scheme, right) is defined by groups far removed from the point of asymmetry. The use of a bicyclic thioglycolate lactam to set the quaternary stereocenter at an early stage cuts the length of the synthesis of the natural product by nearly two thirds.

    22. Medicinal Chemistry

      Design, Synthesis, and Biological Evaluation of Truncated Superstolide A (pages 3446–3449)

      Dr. Lei Chen, Kausar Begam Riaz Ahmed, Prof. Dr. Peng Huang and Prof. Dr. Zhendong Jin

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201209300

      Thumbnail image of graphical abstract

      By design: A truncated superstolide A, a simplified analogue of the potent anticancer marine macrolide superstolide A, was designed and successfully synthesized by a highly efficient and convergent approach. The biological evaluation showed that this compound maintains the potent anticancer activity of the original natural product superstolide A.

    23. Asymmetric Reactions

      Pot Economy in the Synthesis of Prostaglandin A1 and E1 Methyl Esters (pages 3450–3452)

      Prof. Dr. Yujiro Hayashi and Shigenobu Umemiya

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201209380

      Thumbnail image of graphical abstract

      Pot luck: Prostaglandins regulate a broad range of physiological processes and some of their derivatives are used as effective drugs, but previously their preparation has required many steps. The title compounds were efficiently synthesized in a small number of synthetic steps by using a recently developed organocatalyst and practical, one-pot operations involving several successive reactions.

    24. Surface Chemistry

      Adsorption of 1-(1-Naphthyl)ethylamine from Solution onto Platinum Surfaces: Implications for the Chiral Modification of Heterogeneous Catalysts (pages 3453–3456)

      Dr. Alexander D. Gordon and Prof. Francisco Zaera

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209815

      Thumbnail image of graphical abstract

      Chiral modification of catalysts: A comparative in situ reflection–absorption infrared spectroscopy study of the adsorption of 1-(1-naphthyl)ethylamine on Pt surfaces from solution indicated bonding mainly through the amine group and not the aromatic ring as commonly assumed (see picture). In light of these results, a rethinking of the existing model for chiral modification of catalysts may be needed.

    25. Synthetic Methods

      An Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation (pages 3457–3460)

      Xinxin Shao, Xueqiang Wang, Tao Yang, Prof. Dr. Long Lu and Prof. Dr. Qilong Shen

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201209817

      Thumbnail image of graphical abstract

      Sulfur and friends: A new electrophilic hypervalent iodine reagent 1 has been developed for direct trifluoromethylthiolation. A variety of nucleophiles, including β-ketoesters, aldehydes, amides, aryl or vinyl boronic acids, and alkynes, reacted with 1 under mild conditions to give the corresponding trifluoromethylthiolated compounds in good to excellent yields.

    26. Asymmetric Catalysis

      Stereoselective Synthesis of Multiple Stereocenters by Using a Double Aldol Reaction (pages 3461–3464)

      Yasushi Shimoda, Tatsunori Kubo, Prof. Dr. Masaharu Sugiura, Prof. Dr. Shunsuke Kotani and Prof. Dr. Makoto Nakajima

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201209848

      Thumbnail image of graphical abstract

      Triple play: The title reaction of an alkyl methyl ketone and two aldehydes using chiral (S)-binapo as a Lewis base catalyst allows access to 1,5-dihydroxy-3-pentanone derivatives with multiple chiral centers in good yields with high diastereo- and enantioselectivities in a single operation (see scheme).

    27. Heterogeneous Catalysis

      FePt and CoPt Nanowires as Efficient Catalysts for the Oxygen Reduction Reaction (pages 3465–3468)

      Dr. Shaojun Guo, Dongguo Li, Huiyuan Zhu, Sen Zhang, Dr. Nenad M. Markovic, Dr. Vojislav R. Stamenkovic and Prof. Shouheng Sun

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201209871

      Thumbnail image of graphical abstract

      Pt alloy nanowires (NWs) were synthesized and applied as catalysts in the title reaction. The specific activity and mass activity of 2.5 nm wide FePt NWs (see TEM picture) were higher than those of a commercial Pt catalyst. The stability of FePt NWs was tested by scanning the potential in an O2-saturated HClO4 solution. The corresponding polarization curves before and after the test (see picture) indicate that these NWs are robust catalysts.

    28. Germanium(II) Adducts

      Water and Ammonia Complexes of Germanium(II) Dications (pages 3469–3472)

      Rajoshree Bandyopadhyay, Jennifer H. Nguyen, Ala'aeddeen Swidan and Prof. Dr. Charles L. B. Macdonald

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209067

      Thumbnail image of graphical abstract

      Craftily crowned: The treatment of crown ether GeII dications with water or ammonia produces the stable complexes [([15]crown-5)Ge⋅OH2][OTf]2 (see picture; Ge orange, O red, F green, S yellow, H blue) and [([15]crown-5)Ge⋅NH3][OTf]2. The OH and NH hydrogen atoms are rendered more acidic in these compounds.

    29. Asymmetric Catalysis

      Asymmetric Synthesis of β-Amino Nitriles through a ScIII-Catalyzed Three-Component Mannich Reaction of Silyl Ketene Imines (pages 3473–3477)

      Jiannan Zhao, Prof. Dr. Xiaohua Liu, Weiwei Luo, Mingsheng Xie, Dr. Lili Lin and Prof. Dr. Xiaoming Feng

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201209093

      Thumbnail image of graphical abstract

      A range of β-amino nitriles containing contiguous tertiary and quaternary stereogenic carbon centers were synthesized by using the title reaction. The reaction was catalyzed by a chiral N,N′-dioxide scandium(III) complex under mild reaction conditions. Based on experimental investigations, a possible transition state has been proposed to explain the origin of asymmetric inductivity.

    30. Cross-Coupling

      Copper-Catalyzed Oxidative Cross-Coupling of Sulfoximines and Alkynes (pages 3478–3480)

      Long Wang, He Huang, Dr. Daniel L. Priebbenow, Fang-Fang Pan and Prof. Dr. Carsten Bolm

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209975

      Thumbnail image of graphical abstract

      A 'Cu'te couple: A synthetically useful protocol for the preparation of N-alkynylated sulfoximines (yne sulfoximines) has been developed. The method involves a mild copper-catalyzed oxidative cross-coupling of NH-sulfoximines and terminal alkynes (see scheme). The corresponding N-acyl sulfoximines were also obtained selectively after acid-catalyzed hydrolysis of the yne sulfoximines.

    31. Cage Compounds

      Phosphacycles as Building Blocks for Main Group Cages (pages 3481–3484)

      Nell S. Townsend, Sam R. Shadbolt, Prof. Michael Green and Dr. Christopher A. Russell

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201300202

      Thumbnail image of graphical abstract

      Cationic pnictogen/carbon cages are formed from reaction of 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene with the carbene mimics EX2+ (E=P, As). For E=P, 1,4-addition to the hetereoaromatic compound is observed, whereas for E=As, cage complexes are formed.

    32. Cycloaddition

      Lewis Acid Catalyzed Site-Selective Cycloadditions of 2,6-Diazasemibullvalenes with Isocyanides, Azides, and Diazo Compounds for the Synthesis of Diaza- and Triazabrexadiene Derivatives (pages 3485–3489)

      Shaoguang Zhang, Prof. Dr. Wen-Xiong Zhang and Prof. Dr. Zhenfeng Xi

      Article first published online: 19 FEB 2013 | DOI: 10.1002/anie.201210126

      Thumbnail image of graphical abstract

      Unprecedented cycloaddition pathways: Lewis acid catalyzed cycloadditions of 2,6-diazasemibullvalenes with isocyanides, azides, and diazo compounds lead to structurally interesting and otherwise unavailable cage diaza- and triazabrexadiene derivatives. Unique rearrangement/cycloaddition pathways are revealed.

    33. Asymmetric Organocatalysis

      Brønsted Acid Catalyzed Asymmetric SN2-Type O-Alkylations (pages 3490–3493)

      Ilija Čorić, Ji Hye Kim, Tjøstil Vlaar, Dr. Mahendra Patil, Prof. Dr. Walter Thiel and Prof. Dr. Benjamin List

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209983

      Thumbnail image of graphical abstract

      Bridging the gap: Brønsted acids catalyze an intramolecular SN2-type alkylation of alcohols with ethers by bridging a pentacoordinate transition state, thus simultaneously activating both the leaving group and nucleophile (see scheme). Density functional calculations provide detailed insight into the course of the reaction and the transition-state structure.

    34. Radical Reactions

      Umpolung of Hemiaminals: Titanocene-Catalyzed Dehydroxylative Radical Coupling Reactions with Activated Alkenes (pages 3494–3498)

      Assoc. Prof. Dr. Xiao Zheng, Xi-Jie Dai, Hong-Qiu Yuan, Chen-Xi Ye, Jie Ma and Prof. Pei-Qiang Huang

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201210088

      Thumbnail image of graphical abstract

      Radical measures: A radical coupling reaction, which is proposed to proceed through in situ chlorination of a hydroxy group by Me3SiCl, is used to form quaternary carbon centers with amino groups in α position. The reaction can be scaled up and is used in an efficient six-step total synthesis of (±)-9,10-diepi-stemoamide (see scheme, Cp=cyclopentadienyl, EWG=electron-withdrawing group).

    35. Binary CN Compounds

      Well Known or New? Synthesis and Structure Assignment of Binary C2N14 Compounds Reinvestigated (pages 3499–3502)

      Prof. Dr. Klaus Banert, Sebastian Richter, Dieter Schaarschmidt and Prof. Dr. Heinrich Lang

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209170

      Thumbnail image of graphical abstract

      Rapid ring closure transforms the tetraazide 1, which was thought to have been characterized at room temperature in 1961 and 2009, into the tetrazole 2. Consequently, the previously synthesized compounds actually are identical with heterocycle 2, which was also prepared by a third method in 2011. After its generation at low temperature, the open-chain compound 1 and its cyclization reaction have now been analyzed for the first time.

    36. Covalent Azides

      Formyl Azide: Properties and Solid-State Structure (pages 3503–3506)

      Dr. Xiaoqing Zeng, Dr. Eduard Bernhardt, Dr. Helmut Beckers, Prof. Dr. Klaus Banert, Dr. Manfred Hagedorn and Hailiang Liu

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209288

      Thumbnail image of graphical abstract

      The simplest acyl azide, HC(O)N3, has been prepared as the neat substance and characterized by IR and Raman spectroscopy and low-temperature X-ray crystallography (see solid-state structure; C white, H gray, N blue, O red). Photolysis of the azide in CO-doped solid noble-gas matrices furnished the first experimental proof of the elusive parent acyl isocyanate HC(O)NCO.

    37. Organocalcium Compounds

      Stabilization and Reactivity of the Lewis Acidic Solvated Phenylcalcium Cation (pages 3507–3510)

      Dr. Jens Langer, Mathias Köhler, Jörg Hildebrand, Dr. Reinald Fischer, Dr. Helmar Görls and Prof. Dr. Matthias Westerhausen

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209897

      Thumbnail image of graphical abstract

      Grignard deluxe: The 1,2-dimethoxyethane adduct of phenylcalcium iodide forms the unique solvent-separated species [(dme)3CaPh]+I with a highly Lewis acidic metal center. Degradation of DME occurs, yielding calcium methoxide cages, such as [{(dme)Ca}4(CaI)23-OMe)86-O)], and methyl vinyl ether. The picture shows the crystal structure of [(dme)3CaPh]+ (Ca brown, C gray, O red).

    38. Aggregation Inhibitors

      Mechanistic Basis of Phenothiazine-Driven Inhibition of Tau Aggregation (pages 3511–3515)

      Elias Akoury, Dr. Marcus Pickhardt, Dr. Michal Gajda, Dr. Jacek Biernat, Prof. Dr. Eckhard Mandelkow and Prof. Dr. Markus Zweckstetter

      Article first published online: 11 FEB 2013 | DOI: 10.1002/anie.201208290

      Thumbnail image of graphical abstract

      Blues brothers: Aggregation of the Tau protein is a key event in Alzheimer's disease and Tau aggregation inhibitors are important as potential drugs. Phenothiazines, such as methylene blue and its azure derivatives, have a unique mechanism, specifically modifying the Tau cysteine residues. The modification keeps Tau in a monomeric disordered conformation preventing the formation of filaments and their toxic precursors.

    39. Silicon Double Bonds

      Reversible, Complete Cleavage of Si[DOUBLE BOND]Si Double Bonds by Isocyanide Insertion (pages 3516–3520)

      Dr. Moumita Majumdar, Dr. Volker Huch, Dr. Iulia Bejan, Dr. Antje Meltzer and Prof. Dr. David Scheschkewitz

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201209281

      Thumbnail image of graphical abstract

      There and back: An isocyanide-centered silene–disilene reversibility was observed for the insertion of isocyanides into unsymmetrically substituted disilenes. This reaction leads to the formation of silenes at room temperature; the disilene is regenerated in the presence of a Lewis acid.

    40. Fullerene Chemistry

      Invertomers of Fullerenophosphates (pages 3521–3524)

      Alexander Gmehling, Wolfgang Donaubauer, Dr. Frank Hampel, Dr. Frank W. Heinemann and Prof. Dr. Andreas Hirsch

      Article first published online: 12 FEB 2013 | DOI: 10.1002/anie.201209981

      Thumbnail image of graphical abstract

      The ins and outs of fullerene chemistry: Fullerenophosphates with a C3-symmetrical e,e,e-trisaddition pattern were synthesized with high regioselectivity. In- (see structure, red O, yellow P, blue C) and out-invertomers, based on the orientation of the P[DOUBLE BOND]O group, were isolated and their structures were confirmed by X-ray-crystallography.

    41. NMR Spectroscopy of Proteins

      N–H Spin–Spin Couplings: Probing Hydrogen Bonds in Proteins (pages 3525–3528)

      Sheng-Qi Xiang, Raghavendran L. Narayanan, Dr. Stefan Becker and Prof. Markus Zweckstetter

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201209641

      Thumbnail image of graphical abstract

      Sensitive information: Hydrogen bonds stabilize protein structures and are critical for many chemical and biological phenomena. NMR studies found that the one-bond 1H–15N scalar coupling constant is increased by up to 1.6 Hz when a hydrogen bond is formed. These coupling constants therefore provide a sensitive tool for studying protein structure.

    42. Ligand-Stabilized Gold Clusters

      [Au14(PPh3)8(NO3)4]: An Example of a New Class of Au(NO3)-Ligated Superatom Complexes (pages 3529–3532)

      Dipl.-Chem. Benjamin S. Gutrath, Prof. Dr. Iris M. Oppel, Dr. Oliver Presly, Dipl.-Phys. Igor Beljakov, Dr. Velimir Meded, Prof. Wolfgang Wenzel and Prof. Dr. Ulrich Simon

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201208681

      Thumbnail image of graphical abstract

      Golden beauty: For the first time a ligand-stabilized Au14 cluster has been examined. The structure of this superatom complex bears several impressive and unique features, which will further support the understanding of certain guiding principles for molecular-precision synthesis and functionalization of ultrasmall nanoparticles.

SEARCH

SEARCH BY CITATION