Angewandte Chemie International Edition

Cover image for Vol. 49 Issue 39

September 17, 2010

Volume 49, Issue 39

Pages 6909–7137

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: Aldehyde Umpolung by N-Heterocyclic Carbenes: NMR Characterization of the Breslow Intermediate in its Keto Form, and a Spiro-Dioxolane as the Resting State of the Catalytic System (Angew. Chem. Int. Ed. 39/2010) (page 6909)

      Prof. Dr. Albrecht Berkessel, Silvia Elfert, Dr. Kerstin Etzenbach-Effers and Dr. J. Henrique Teles

      Article first published online: 26 AUG 2010 | DOI: 10.1002/anie.201001705

      Thumbnail image of graphical abstract

      N-heterocyclic carbenes are prominent organocatalysts for transformations based on aldehyde Umpolung, such as the benzoin condensation. The cover picture shows a triazolylidene carbene and two hitherto unknown adducts formed from this catalyst and the aldehyde substrate. Both the ketone and the dioxolane shown were identified by NMR spectroscopy by A. Berkessel and co-workers in their Communication on page 7120 ff. (Graphics by Silvia Elfert and Adrian von der Höh.)

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: Monolithic and Flexible Polyimide Film Microreactors for Organic Microchemical Applications Fabricated by Laser Ablation (Angew. Chem. Int. Ed. 39/2010) (page 6910)

      Kyoung-Ik Min, Tae-Ho Lee, Dr. Chan Pil Park, Prof. Zhi-Yong Wu, Prof. Hubert H. Girault, Prof. Ilhyong Ryu, Dr. Takahide Fukuyama, Yu Mukai and Prof. Dong-Pyo Kim

      Article first published online: 2 JUL 2010 | DOI: 10.1002/anie.201003239

      Thumbnail image of graphical abstract

      A monolithic and flexible polyimide film microreactor with passive mixing patterns is fabricated by laser ablation. In their Communication on page 7063 ff. D. P. Kim and co-workers show the excellent stability of these film microreactors by using them to perform various organic synthesis reactions under harsh conditions. The simple fabrication and the facile adhesive sealing step facilitate mass production of this flexible film microfluidic device.

  3. Graphical Abstract

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. You have free access to this content
      Corrigendum: Bis(1,3-trimethylsilylallyl)beryllium (page 6924)

      Stephen C. Chmely, Timothy P. Hanusa and William W. Brennessel

      Article first published online: 14 SEP 2010 | DOI: 10.1002/anie.201090126

      This article corrects:

      Bis(1,3-trimethylsilylallyl)beryllium1

      Vol. 49, Issue 34, 5870–5874, Article first published online: 23 JUN 2010

  5. News

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Leroy (Lee) Cronin (pages 6930–6932)

      Article first published online: 6 SEP 2010 | DOI: 10.1002/anie.201004474

      Thumbnail image of graphical abstract

      “My ultimate goal is to assemble/discover artificial (inorganic) biology. When I was eighteen I wanted to be a fast jet pilot …” This and more about Leroy (Lee) Cronin can be found on page 6930.

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Trityloxy Radical

      The Rearrangement of the Trityloxy Radical: Sherlock Holmes’ Most Recent Case (pages 6934–6935)

      Dr. Götz Bucher

      Article first published online: 20 JUL 2010 | DOI: 10.1002/anie.201002914

      Thumbnail image of graphical abstract

      Reopening the case: One hundred years after Wieland's original publication, the rearrangement of the trityloxy radical was studied by K. Ingold et al., who investigated the title reaction with the logical reasoning and intellectual prowess of true detectives.

    2. Ammosamides

      Treasures from the Sea: Discovery and Total Synthesis of Ammosamides (pages 6936–6938)

      Dipl.-Chem. Didier Zurwerra, MSc. Chem. Christoph W. Wullschleger and Prof. Dr. Karl-Heinz Altmann

      Article first published online: 2 AUG 2010 | DOI: 10.1002/anie.201002788

      Thumbnail image of graphical abstract

      Out of the blue: Ammosamides A (1) and B (2) were isolated from a marine streptomycete collected at a depth of more than 1600 m. By employing a blue-fluorescent diaminocoumarin conjugate of 2 (see structure), myosin was identified as a cellular target of these antiproliferative natural products. The total synthesis of 1 and 2 has now been completed, thus allowing further elaboration of the chemical biology of these fascinating compounds.

  8. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. N-Heterocyclic Carbenes

      The Measure of All Rings—N-Heterocyclic Carbenes (pages 6940–6952)

      Dipl.-Chem. Thomas Dröge and Prof. Dr. Frank Glorius

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201001865

      Thumbnail image of graphical abstract

      Beyond measure? N-Heterocyclic carbenes (NHCs) have become ubiquitous ligands for organometallic chemistry as well as organocatalysts. The key concepts used for the quantification of the characteristic properties of NHCs are described. The ability to quantify, modify, maximize, or minimize these properties should eventually enable the design, selection, and utilization of tailor-made NHC ligands for a desired catalytic application.

  9. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Designed to Deliver

      Polymeric Multilayer Capsules in Drug Delivery (pages 6954–6973)

      Liesbeth J. De Cock, Dr. Stefaan De Koker, Dr. Bruno G. De Geest, Prof. Dr. Johan Grooten, Prof. Dr. Chris Vervaet, Prof. Dr. Jean Paul Remon, Prof. Dr. Gleb B. Sukhorukov and Dr. Maria N. Antipina

      Article first published online: 19 JUL 2010 | DOI: 10.1002/anie.200906266

      Thumbnail image of graphical abstract

      Layer-by-layer coating of a sacrificial template followed by dissolution of the template can be used to generate polymeric multilayer capsules. By varying the capsule components and their physicochemical properties, multifunctional microcarriers (red circles) can be designed with high potential for drug delivery.

  10. Communications

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

      The Hierarchical Self-Assembly of Charge Nanocarriers: A Highly Cooperative Process Promoted by Visible Light (pages 6974–6978)

      Dr. Emilie Moulin, Fréderic Niess, Prof. Dr. Mounir Maaloum, Prof. Dr. Eric Buhler, Dr. Irina Nyrkova and Prof. Dr. Nicolas Giuseppone

      Article first published online: 19 JUL 2010 | DOI: 10.1002/anie.201001833

      Thumbnail image of graphical abstract

      Let there be more light: Triarylamine-based building blocks respond to visible-light exposure by the formation of cationic radicals that hierarchically self-assemble into molecular wires, which in turn combine within larger fibers (see picture). The stimuli-responsive supramolecular scaffold, which is created by charge transfer and reversibly broken up by heating, prevents the quenching of holes within the wires.

    2. Heterogeneous Catalysis

      A Polymer-Supported Chiral Dirhodium(II) Complex: Highly Durable and Recyclable Catalyst for Asymmetric Intramolecular C[BOND]H Insertion Reactions (pages 6979–6983)

      Dr. Koji Takeda, Tadashi Oohara, Dr. Masahiro Anada, Dr. Hisanori Nambu and Prof. Dr. Shunichi Hashimoto

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201003730

      Thumbnail image of graphical abstract

      A highly effective immobilization of [Rh2(S-PTTL)4] (PTTL=N-phthaloyl-tert-leucinate) has been achieved by copolymerization of monomer 1 with styrene and a flexible cross-linker. The immobilized catalyst promoted the title reaction at −78 °C with high enantioselectivity, and could be used for up to 100 cycles with a low level of leaching (0.28 ppm).

    3. Polyoxometalate Frameworks

      Modular Inorganic Polyoxometalate Frameworks Showing Emergent Properties: Redox Alloys (pages 6984–6988)

      Johannes Thiel, Dr. Chris Ritchie, Dr. Haralampos N. Miras, Dr. Carsten Streb, Scott G. Mitchell, Thomas Boyd, M. Nieves Corella Ochoa, Mali H. Rosnes, Jim McIver, Dr. De-Liang Long and Prof. Leroy Cronin

      Article first published online: 14 JUL 2010 | DOI: 10.1002/anie.201002672

      Thumbnail image of graphical abstract

      Alloy, alloy: A pure cobalt-based Keggin network linked by W-O-Co interactions is “alloyed” with a pure manganese-based Keggin network, linked by W-O-Mn interactions. These isostructural alloys are solid solutions of the Co and Mn nets. The alloys are prepared by the stoichiometric mixing of the components of each discrete network, leading to a series of single-crystalline mixed transition-metal frameworks with novel redox properties.

    4. Time-Resolved Spectroscopy

      Remarkable Site Difference of Vibrational Energy Relaxation in Benzene Dimer: Picosecond Time-Resolved IR–UV Pump–Probe Spectroscopy (pages 6989–6992)

      Ryoji Kusaka and Prof. Takayuki Ebata

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002230

      Thumbnail image of graphical abstract

      VERy relaxing: Vibrational energy relaxation (VER) of benzene dimer isotopologues in the CH stretching vibrational level has been investigated by picosecond time-resolved IR–UV pump–probe spectroscopy (see picture, h=C6H6, d=C6D6). A remarkable difference is found in the relaxation lifetime: the lifetime of the stem site (110 ps) is 4.5 times shorter than that of the top site (500 ps).

    5. Dimpled Gold Nanoplates

      Morphosynthesis of Nanostructured Gold Crystals by Utilizing Interstices in Periodically Arranged Silica Nanoparticles as a Flexible Reaction Field (pages 6993–6997)

      Yoshiyuki Kuroda and Prof. Dr. Kazuyuki Kuroda 

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201002430

      Thumbnail image of graphical abstract

      Rigid but flexible: Gold nanoplates with highly ordered surface dimples (see picture) are deposited in the interstices of periodically arranged silica nanoparticles. The silica nanoparticles not only act as rigid templates to form dimples or mesopores, but also provide a flexible reaction field that allows anisotropic crystal growth of gold in a simultaneously formed two-dimensional nanospace.

    6. Decorated Pt Nanoparticles

      Pd Adatom Decorated (100) Preferentially Oriented Pt Nanoparticles for Formic Acid Electrooxidation (pages 6998–7001)

      Dr. Francisco J. Vidal-Iglesias, Dr. José Solla-Gullón, Prof. Enrique Herrero, Prof. Antonio Aldaz and Prof. Juan M. Feliu

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002501

      Thumbnail image of graphical abstract

      Decorating platinum nanoparticles having preferential (100) orientation with palladium adatoms in the submonolayer range enhances their catalytic performance in the electrooxidation of formic acid (see picture). Moreover, as the palladium adatoms are deposited in a similar way to that used in analogous single-crystal studies, proper relationships between single-crystal and nanoparticle catalysis or electrocatalysis can be established.

    7. Dendrimers

      Deconstruction as a Strategy for the Design of Libraries of Self-Assembling Dendrons (pages 7002–7005)

      Dr. Brad M. Rosen, Dr. Mihai Peterca, Chenghong Huang, Prof. Xiangbing Zeng, Prof. Goran Ungar and Prof. Virgil Percec

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002514

      Thumbnail image of graphical abstract

      Bringing down the dendron: The deconstruction of self-assembling dendrons represents a new strategy for the rational design of libraries of self-assembling dendrons with unprecedented primary structure (see picture). In this strategy, molecular targets are designed by systematically removing branches from a parent dendron. This approach provides a diversity of molecular topologies unencountered in the generational synthesis of dendrons.

    8. Chiral Quantum Dots

      Circularly Polarized Luminescent CdS Quantum Dots Prepared in a Protein Nanocage (pages 7006–7009)

      Dr. Masanobu Naito, Dr. Kenji Iwahori, Dr. Atsushi Miura, Midori Yamane and Prof. Dr. Ichiro Yamashita

      Article first published online: 25 AUG 2010 | DOI: 10.1002/anie.201002552

      Thumbnail image of graphical abstract

      CdS quantum dots prepared in ferritin, an α-helix-rich rhombic dodecahedral protein, showed left-handed cicularly polarized luminescence (CPL) from both direct transition and surface-trapping sites with relatively large anisotropy factors. Utilizing laser photoetching, the PL/CPL bands from surface-trapping sites blue-shifted with decreased QD size, but the direct transition band disappeared.

    9. Atroposelectivity

      Biocatalytic Desymmetrization of an Atropisomer with both an Enantioselective Oxidase and Ketoreductases (pages 7010–7013)

      Bo Yuan, Abigail Page, Christopher P. Worrall, Dr. Franck Escalettes, Dr. Simon C. Willies, Dr. Joseph J. W. McDouall, Prof. Nicholas J. Turner and Prof. Jonathan Clayden

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002580

      Thumbnail image of graphical abstract

      All roads lead to … atropisomeric diaryl ethers containing a benzylic hydroxy group and an aldehyde unit. The isomers were synthesized in enantiomerically enriched form by desymmetrizing atroposelective enzymatic oxidation (with a galactose oxidase (GOase) variant) or reduction (with a ketoreductase (KRED); see scheme).

    10. Peptide Structures

      Structural Characterization of a Microperoxidase Inside a Metal-Directed Protein Cage (pages 7014–7018)

      Thomas W. Ni and Prof. Dr. F. Akif Tezcan

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201001487

      Thumbnail image of graphical abstract

      Caged to submission: The zinc-ion-directed assembly of tetrahedral protein cages (Zn30:CFMC-112) in a rhombohedral crystal lattice is presented. The histidine side chains and exposed hydrophobic groups lining up the cavities of these cages enabled a flexible c-type heme peptide fragment (a microperoxidase) to be immobilized within and its crystal structure to be determined at 1.9 Å resolution.

    11. Biogenic Nanoparticles

      In Vivo Synthesis of Diverse Metal Nanoparticles by Recombinant Escherichia coli (pages 7019–7024)

      Dr. Tae Jung Park, Prof. Sang Yup Lee, Nam Su Heo and Prof. Tae Seok Seo

      Article first published online: 14 SEP 2010 | DOI: 10.1002/anie.201001524

      Thumbnail image of graphical abstract

      A metal-nanoparticle factory: Various metal nanoparticles with tailored optical, electronic, chemical, and magnetic properties were synthesized in vivo in a size-tunable manner in recombinant E. coli (see picture) through interaction with the metal-binding protein metallothionein and the metal-binding peptide phytochelatin, which was synthesized by phytochelatin synthase.

    12. Fluorescence Sensing

      Polyfluorophores on a DNA Backbone: Sensors of Small Molecules in the Vapor Phase (pages 7025–7029)

      Dr. Florent Samain, Dr. Samantak Ghosh, Yin Nah Teo and Prof. Dr. Eric T. Kool

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201002701

      Thumbnail image of graphical abstract

      With a response for any occasion: Oligodeoxyfluorosides (ODFs) conjugated to poly(ethylene glycol)–polystyrene beads were used as fluorescent sensors of multiple organic vapors (see picture). The ODFs—DNA-like oligomers in which fluorophores, spacers, and quencher groups replace DNA bases—had sufficient electronic diversity to show a wide range of responses to chemically varied volatile organic compounds.

    13. Molecular Dynamics

      Backbone Dynamics of Cyclotide MCoTI-I Free and Complexed with Trypsin (pages 7030–7034)

      Shadakshara S. Puttamadappa, Dr. Krishnappa Jagadish, Dr. Alexander Shekhtman and Dr. Julio A. Camarero

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002906

      Thumbnail image of graphical abstract

      Showing some backbone: Most of the backbone NH groups of cyclotide MCoTI-I are constrained in the free state, which results in a well-folded compact structure, as indicated by {15N,1H} NMR spectroscopy (see picture). According to the backbone order parameter S2, the backbone mobility in trypsin-bound MCoTI-I is significantly increased.

      Corrected by:

      Corrigendum: Corrigendum: Backbone Dynamics of Cyclotide MCoTI-I Free and Complexed with Trypsin

      Vol. 50, Issue 31, 6948–6949, Article first published online: 21 JUL 2011

    14. Gas Separation

      Cinchona Alkaloid–Metal Complexes: Noncovalent Porous Materials with Unique Gas Separation Properties (pages 7035–7039)

      Prof. Dr. Janusz Lewiński, Tomasz Kaczorowski, Daniel Prochowicz, Dr. Teodozja Lipińska, Dr. Iwona Justyniak, Dr. Zbigniew Kaszkur and Prof. Dr. Janusz Lipkowski

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002925

      Thumbnail image of graphical abstract

      Pores for thought: Dinuclear aluminum–cinchone complexes are used to construct chiral architectures through noncovalent-interaction-driven self-assembly (see picture). The flexible desolvated material with ultramicropores is a selective adsorbent with unique properties, such as temperature-triggered adsorption of N2 and high affinities for H2, CO2, and CH4.

    15. Non-Innocent Ligands

      Exploiting Non-Innocent Ligands to Prepare Masked Palladium(0) Complexes (pages 7040–7044)

      Dan A. Smith, Dr. Andrei S. Batsanov, Dr. Karine Costuas, Dr. Ruth Edge, Dr. David C. Apperley, Prof. David Collison, Dr. Jean-François Halet, Prof. Judith A. K. Howard and Dr. Philip W. Dyer

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201003946

      Thumbnail image of graphical abstract

      Is it or isn't it: Reaction of [PdMe2(tmeda)] with pyridyl-N-di(tert-butyl)phosphinoimine spontaneously affords an unusual bimetallic palladium(I) ligand-based biradical complex, which behaves as a “masked” form of Pd0 in its reactions with neutral ligands and chlorobenzene.

    16. Nanotechnology

      Uniform Hollow Carbon Shells: Nanostructured Graphitic Supports for Improved Oxygen-Reduction Catalysis (pages 7045–7048)

      Zachary L. Schaefer, Matthew L. Gross, Prof. Michael A. Hickner and Prof. Raymond E. Schaak

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201003213

      Thumbnail image of graphical abstract

      C-shell catalysts: Uniform hollow nanoshells of graphitic carbon have been synthesized by phase separation of Ni3C nanoparticles (NPs) followed by chemical leaching of the nickel core gave graphite-shell particles (see picture). Pt NPs anchored onto the shell show high apparent activity for the oxygen reduction reaction.

    17. Peptide Ligation

      Traceless Ligation of Cysteine Peptides Using Selective Deselenization (pages 7049–7053)

      Dr. Norman Metanis, Prof. Ehud Keinan and Prof. Philip E. Dawson

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201001900

      Thumbnail image of graphical abstract

      Selective deselenization: Native chemical ligation at selenocysteine is followed by selective deselenization of the selenocysteine to alanine, in the presence of cysteine residues without protecting groups (see scheme). This selectivity is achieved by using the water-soluble tris(2-carboxyethyl)phosphine (TCEP) in the absence of a radical initiator.

    18. Heterobimetallic Oxygenation

      Monooxygenase-Like Reactivity of an Unprecedented Heterobimetallic {FeO2Ni} Moiety (pages 7054–7058)

      Dr. Shenglai Yao, Dr. Christian Herwig, Dr. Yun Xiong, Dr. Anna Company, Dr. Eckhard Bill, Prof. Dr. Christian Limberg and Prof. Dr. Matthias Driess

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201001914

      Thumbnail image of graphical abstract

      Pool together: Oxidative addition of the superoxo ligand inherent to the nickel(II) superoxide 1 onto iron(I) precursor complexes 2 a/2 b leads unexpectedly and exclusively to the first NiFe alkoxo hydroxides 3 a (R=Me) and 3 b (R=tBu). The latter result from an unexpected, selective oxygenation of a C[BOND]H bond of one of the isopropyl groups at the β-diketiminato ligand coordinated to nickel.

    19. Zethrenes

      Synthesis, Structure, and Photophysical Properties of Dibenzo[de,mn]naphthacenes (pages 7059–7062)

      Tsun-Cheng Wu, Chia-Hua Chen, Daijiro Hibi, Dr. Akihiro Shimizu, Prof. Yoshito Tobe and Prof. Yao-Ting Wu

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201001929

      Thumbnail image of graphical abstract

      Zethrenes were synthesized by Pd-catalyzed cyclodimerization of 1-ethynyl-8-iodonaphthalenes. The structure of these cycloadducts was confirmed by X-ray crystal analysis. The bond lengths and bond alternation in the crystal structures reveal that the central two six-membered rings of the title compounds lack aromaticity.

    20. Microreactors

      Monolithic and Flexible Polyimide Film Microreactors for Organic Microchemical Applications Fabricated by Laser Ablation (pages 7063–7067)

      Kyoung-Ik Min, Tae-Ho Lee, Dr. Chan Pil Park, Prof. Zhi-Yong Wu, Prof. Hubert H. Girault, Prof. Ilhyong Ryu, Dr. Takahide Fukuyama, Yu Mukai and Prof. Dong-Pyo Kim

      Article first published online: 23 JUN 2010 | DOI: 10.1002/anie.201002004

      Thumbnail image of graphical abstract

      Keeping limber: A monolithic and flexible polyimide film microreactor is introduced for organic reactions and syntheses. Unlike glass microreactors, it is easy to fabricate, yet it is inert to solvents and acids under harsh conditions, unlike other polymer microreactors.

    21. Oxidation

      Enantiodifferentiating endo-Selective Oxylactonization of ortho-Alk-1-enylbenzoate with a Lactate-Derived Aryl-λ3-Iodane (pages 7068–7071)

      Prof. Dr. Morifumi Fujita, Yasushi Yoshida, Kazuyuki Miyata, Dr. Akihiro Wakisaka and Prof. Dr. Takashi Sugimura

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201003503

      Thumbnail image of graphical abstract

      It's the hype: The asymmetric synthesis of 3-alkyl-4-oxyisochroman-1-one is achieved by oxylactonization of ortho-alk-1-enylbenzoate with a series of optically active hypervalent iodine(III) reagents prepared from lactate or valine as a chiral source (see scheme). The oxylactonization is highly regio-, diastereo-, and enantioselective.

    22. Organocatalysis

      Enantioselective Phase-Transfer Catalysis: Synthesis of Pyrazolines (pages 7072–7075)

      Olivier Mahé, Dr. Isabelle Dez, Dr. Vincent Levacher and Dr. Jean-François Brière

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002485

      Thumbnail image of graphical abstract

      All paired up: Under catalytic phase-transfer conditions the formation of a chiral ion pair between quininium cation 1 and hydrazine anion 2 led to an enantioselective aza-Michael cyclocondensation domino reaction to furnish pyrazolines. A convenient one-pot protocol allowed exchange of the functional group (R1) on the nitrogen atom.

    23. Microreactors

      An Integrated Microreactor System for Self-Optimization of a Heck Reaction: From Micro- to Mesoscale Flow Systems (pages 7076–7080)

      Jonathan P. McMullen, Dr. Matthew T. Stone, Prof. Stephen L. Buchwald and Prof. Klavs F. Jensen

      Article first published online: 19 AUG 2010 | DOI: 10.1002/anie.201002590

      Thumbnail image of graphical abstract

      Set it and forget it: The combination of feedback control and continuous-flow operations in microreactors (see picture) enables online and fully automated reaction optimization. A Heck reaction demonstrates the potential for rapid multivariable reaction optimization while requiring a minimal amount of material. Optimal conditions are quickly scaled-up by a factor of 50.

    24. Nanostructures

      Nanopeapods by Galvanic Displacement Reaction (pages 7081–7085)

      Dr. Carlos M. Hangarter, Young-In Lee, Sandra C. Hernandez, Yong-ho Choa and Prof. Nosang V. Myung

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201001559

      Thumbnail image of graphical abstract

      Like peas in a pod: Galvanic displacement of electrodeposited multisegmented nanowires was used to synthesize nanopeapod structures at room temperature (see scheme). Depending on the redox potential of the displacement process, a variety of nanopeapod materials could be prepared, e.g., semiconductor/metal, p-type/n-type, metal/metal, ferromagnetic/nonmagnetic materials.

    25. Silicon Compounds

      Synthesis, Isolation, and Characterization of 1,1-DiGrignard and 1,1-Dizincio Silanes (pages 7086–7088)

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

      Article first published online: 24 AUG 2010 | DOI: 10.1002/anie.201002876

      Thumbnail image of graphical abstract

      Two metals are better than one: A cyclic 1,1-dimagnesiosilane, a 1,1-di(chloromagnesio)silane, and a 1,1-di(chlorozincio)silane have been synthesized using transmetalation reactions (see scheme; THF=tetrahydrofuran) and characterized by X-ray crystallography. Cyclic 1,1-dimagnesiosilane was studied in redox reactions that led to a lithium-substituted silyl radical and a vicinal 1,2-dilithiosilane.

    26. Stereoselctive Synthesis

      Complete Regio- and Stereoselective Construction of Highly Substituted Silyl Enol Ethers by Three-Component Coupling (pages 7089–7091)

      Dr. Akira Tsubouchi, Shouko Enatsu, Ryo Kanno and Prof. Dr. Takeshi Takeda

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201003152

      Thumbnail image of graphical abstract

      Three components for total control: Trisubstituted silyl enol ethers were prepared by three-component coupling of α-silyl α,β-unsaturated ketones, organocopper reagents, and organic halides with complete regio- and stereoselectivity (see scheme). The reaction proceeded through a 1,3 migration of the silyl group via cyclic silicate intermediates, which controlled the configuration of the silyl enol ethers.

    27. Synthetic Methods

      Efficient Silver-Catalyzed Regio- and Stereospecific Aziridination of Dienes (pages 7092–7095)

      Josep Llaveria, Álvaro Beltrán, Dr. M. Mar Díaz-Requejo, Dr. M. Isabel Matheu, Prof. Sergio Castillón and Prof. Pedro J. Pérez

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201003167

      Thumbnail image of graphical abstract

      Nitrene transfer: Unsymmetric dienes bearing a terminal hydroxy group can be regio- and stereospecifically converted into vinylaziridines upon nitrene transfer from PhINTs using a silver-based catalyst. Stoichiometric mixtures of dienes and PhINTs were employed at low catalyst loadings (0.5 %; see scheme). The method has been applied to the synthesis of (±)-sphingosine and gave good yields in a three-step procedure. Ts=4-toluenesulfonyl.

    28. Asymmetric Catalysis

      Enantioselective Addition of Boronates to Chromene Acetals Catalyzed by a Chiral Brønsted Acid/Lewis Acid System (pages 7096–7100)

      Philip N. Moquist, Dr. Tomohiro Kodama and Prof. Dr. Scott E. Schaus

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201003469

      Thumbnail image of graphical abstract

      Chiral α,β-dihydroxy carboxylic acids catalyze the enantioselective addition of alkenyl and aryl boronates to chromene acetals. The optimal carboxylic acid is the easily available tartaric acid amide shown in the scheme. Spectroscopic and kinetic mechanistic studies demonstrate that an exchange process generates a reactive dioxoborolane intermediate leading to enantioselective addition to the pyrylium ion formed from the chromene acetal.

    29. Microreactors

      Synthesis of 5-Substituted 1H-Tetrazoles from Nitriles and Hydrazoic Acid by Using a Safe and Scalable High-Temperature Microreactor Approach (pages 7101–7105)

      Bernhard Gutmann, Dr. Jean-Paul Roduit, Dr. Dominique Roberge and Prof. Dr. C. Oliver Kappe

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201003733

      Thumbnail image of graphical abstract

      Harnessing hydrazoic acid in a microreactor! Tetrazoles have been synthesized in a very efficient manner by using a high-temperature/high-pressure process intensification regime. Despite the toxic and explosive nature of hydrazoic acid, the synthesis was conducted safely in continuous flow format with residence times as short as 2.5 minutes at 260 °C (see picture).

    30. Carbon(0) Compounds

      Carbodiylides C(ECp*)2 (E=B–Tl): Another Class of Theoretically Predicted Divalent Carbon(0) Compounds (pages 7106–7110)

      Dipl.-Chem. Susanne Klein and Prof. Dr. Gernot Frenking

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201002773

      Thumbnail image of graphical abstract

      Carbone machine: Quantum-chemical calculations predict that the experimentally still unknown carbodiylides C(ECp*)2 (E=B–Tl; Cp*=C5Me5) are a class of divalent carbon(0) compounds (“carbones”) that should be synthetically accessible.

    31. Peptide Mimetics

      Addressing Protein–Protein Interactions with Small Molecules: A Pro-Pro Dipeptide Mimic with a PPII Helix Conformation as a Module for the Synthesis of PRD-Binding Ligands (pages 7111–7115)

      Dr. Jan Zaminer, Dr. Christoph Brockmann, Dipl.-Chem. Peter Huy, Dipl.-Biophys. Robert Opitz, Dipl.-Chem. Cédric Reuter, Dr. Michael Beyermann, Priv.-Doz. Dr. Christian Freund, Dipl.-Biochem. Matthias Müller, Prof. Dr. Hartmut Oschkinat, Dr. Ronald Kühne and Prof. Dr. Hans-Günther Schmalz

      Article first published online: 27 AUG 2010 | DOI: 10.1002/anie.201001739

      Thumbnail image of graphical abstract

      X marks the spot: The synthetic tricyclic amino acid X (see structure; C gray, H cyan, N blue, O red, double bond yellow) can be incorporated, without loss of binding ability, as a Pro-Pro substitute into two peptides that bind to the proline-rich motif-recognizing domains Fyn-SH3. The dipeptide analogue X, which is locked in a polyproline type II helix conformation, is created by stereoselective introduction of a vinylidene bridge into a diproline unit.

    32. Ionic Liquids

      Low-Viscosity Paramagnetic Ionic Liquids with Doubly Charged [Co(NCS)4]2− Ions (pages 7116–7119)

      Dipl.-Chem. Tim Peppel, Prof. Dr. Martin Köckerling, Dr. Monika Geppert-Rybczyńska, Dipl.-Chem. Ricardas V. Ralys, Dr. Jochen K. Lehmann, Prof. Dr. Sergey P. Verevkin and Prof. Dr. Andreas Heintz

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201000709

      Thumbnail image of graphical abstract

      Magic ink: Ionic liquids that consist of paramagnetic [Co(NCS)4]2− anions and imidazolium-based cations have glass-transition temperatures below −60 °C. The ink-like liquids also have unexpected low viscosities, ion conductivities, and low heats of vaporization, along with high hydrolytic stability and insensitivity to air.

    33. Organocatalysis

      Aldehyde Umpolung by N-Heterocyclic Carbenes: NMR Characterization of the Breslow Intermediate in its Keto Form, and a Spiro-Dioxolane as the Resting State of the Catalytic System (pages 7120–7124)

      Prof. Dr. Albrecht Berkessel, Silvia Elfert, Dr. Kerstin Etzenbach-Effers and Dr. J. Henrique Teles

      Article first published online: 19 AUG 2010 | DOI: 10.1002/anie.200907275

      Thumbnail image of graphical abstract

      Surprises from a classic: The Breslow intermediate of triazolylidene-catalyzed benzoin condensations was characterized for the first time by NMR spectroscopy in its keto form (K, energetic minimum). The hitherto unknown spiro-dioxolane S, generated from the carbene catalyst and two equivalents of aldehyde, is the resting state of the catalytic system.

    34. Luminescence Chemosensors

      Modular Chemosensors from Self-Assembled Vesicle Membranes with Amphiphilic Binding Sites and Reporter Dyes (pages 7125–7128)

      Benjamin Gruber, Dr. Stefan Stadlbauer, Dr. Andreas Späth, Stefan Weiss, Prof. Maria Kalinina and Prof. Dr. Burkhard König

      Article first published online: 16 AUG 2010 | DOI: 10.1002/anie.201001101

      Thumbnail image of graphical abstract

      Tiny analysts: Co-embedding of amphiphilic binding sites and environment-sensitive dyes in vesicular membranes allows rapid and easy preparation of self-assembled modular chemosensors. The fluorescent particles thus obtained respond to the presence of analytes by changes in their emission intensity.

    35. Sonochemistry

      Selective Ultrasonic Cavitation on Patterned Hydrophobic Surfaces (pages 7129–7133)

      Dr. Valentina Belova, Dr. Dmitry A. Gorin, Dr. Dmitry G. Shchukin and Prof. Helmuth Möhwald

      Article first published online: 19 AUG 2010 | DOI: 10.1002/anie.201002069

      Thumbnail image of graphical abstract

      Sonochemistry at surfaces can be controlled by suitable surface patterning. Bubble nucleation occurs predominantly on hydrophobic surfaces (see picture, left), which thus can be selectively treated by ultrasound. The right-hand picture shows a structurally modified aluminum plate after ultrasound treatment. The inner circular region is hydrophobic, and the outer region is hydrophobic.

  11. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Preview: Angew. Chem. Int. Ed. 40/2010 (page 7137)

      Article first published online: 14 SEP 2010 | DOI: 10.1002/anie.201090128

SEARCH

SEARCH BY CITATION