Angewandte Chemie International Edition

Cover image for Vol. 46 Issue 48

December 10, 2007

Volume 46, Issue 48

Pages 9119–9451

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
    1. Cover Picture: Controlled Nanoscale Mechanical Phenomena Discovered with Ultrafast Electron Microscopy (Angew. Chem. Int. Ed. 48/2007) (page 9119)

      David J. Flannigan, Vladimir A. Lobastov and Ahmed H. Zewail

      Version of Record online: 5 DEC 2007 | DOI: 10.1002/anie.200790245

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      Ultrafast electron microscopy …… has been used to view the reversible expansion and contraction of a single crystal of [Cu(TCNQ)] (see film strip; TCNQ=7,7,8,8-tetracyanoquinodimethane), induced with near-infrared laser pulses, as well as the photoinduced reduction of copper ions to form discrete metal clusters (see picture, top right), as described by A. H. Zewail et al. in their Communication on Page 9206 ff. The crystal expands along the π-stacking axis of the TCNQ molecules upon exposure to light, but rapidly returns to its original state in the absence of laser light.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
    1. Inside Cover: Total Synthesis and Configurational Assignment of Pasteurestin A and B (Angew. Chem. Int. Ed. 48/2007) (page 9120)

      Marion Kögl, Lothar Brecker, Ralf Warrass and Johann Mulzer

      Version of Record online: 5 DEC 2007 | DOI: 10.1002/anie.200790246

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      Application in veterinary medicine was proposed for the sesquiterpenoids pasteurestins A and B because of their strong and selective activity against Pasteurella haemolytica. A Vollhardt [2+2+2] cycloaddition was the key step in their total synthesis, which is described by J. Mulzer et al. on page 9320 ff., and subsequently their absolute and relative configurations could be established and their biological activities more precisely specified. Another feature of the synthesis of pasteurestin B is a tin(II) enolate mediated Reformatsky-type condensation.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
  4. Corrigenda

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
    1. You have free access to this content
      [12]Annulene Gemini Surfactants: Structure and Self-Assembly (page 9135)

      Lei Shi, Dan Lundberg, Djamaladdin G. Musaev and Fredric M. Menger

      Version of Record online: 5 DEC 2007 | DOI: 10.1002/anie.200790248

      This article corrects:

      [12]Annulene Gemini Surfactants: Structure and Self-Assembly1

      Vol. 46, Issue 31, 5889–5891, Version of Record online: 6 JUL 2007

    2. You have free access to this content
      Metal-Free Catalytic Hydrogenation (page 9136)

      Preston A. Chase, Gregory C. Welch, Titel Jurca and Douglas W. Stephan

      Version of Record online: 5 DEC 2007 | DOI: 10.1002/anie.200790249

      This article corrects:

      Metal-Free Catalytic Hydrogenation1

      Vol. 46, Issue 42, 8050–8053, Version of Record online: 15 AUG 2007

  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
  6. Book Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
  7. Highlight

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
    1. Enantioselective Insertion of Metal Carbenes into N[BOND]H Bonds: A Potentially Versatile Route to Chiral Amine Derivatives (pages 9148–9150)

      Christopher J. Moody

      Version of Record online: 24 OCT 2007 | DOI: 10.1002/anie.200703016

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      Back to copper: The Rh-catalyzed reactions of diazocarbonyl compounds with amines, leading to N[BOND]H insertion products, have found wide application. However, an enantioselective variant has remained elusive. A return to copper catalysis, first reported for carbene N[BOND]H insertions over 50 years ago, in the presence of chiral ligands and a large noncoordinating counterion, has resulted in enantioselective N[BOND]H insertion into anilines.

  8. Correspondence

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
    1. 1,7-Diaza[12]annulene Derivatives? 100-Year-Old Pyridinium Salts! (pages 9152–9153)

      Manfred Christl

      Version of Record online: 28 NOV 2007 | DOI: 10.1002/anie.200704704

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      The 103-year-old reaction of N-(2,4-dinitrophenyl)pyridinium chloride with primary amines was rediscovered by two research groups recently. Since neither authors nor referees knew the pertinent literature, the products were assigned the structure of the diaza[12]annulenes 1, although they are nothing but N-substituted pyridinium salts.

  9. Essay

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
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    1. Interconnections and Independence: Heinrich Wieland (1877–1957) and His Era (pages 9154–9179)

      Elisabeth Vaupel

      Version of Record online: 5 DEC 2007 | DOI: 10.1002/anie.200702255

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      The dramatic societal upheavals and radical value shifts that occurred during the first half of the 20th century influenced every aspect of life, including the scientific and research systems. A biography of Heinrich Wieland, awarded the Nobel Prize for Chemistry in 1927, one embedded in a chronicle of the times, shows clearly how this one individual adapted to multiple drastic changes in his environment.

  10. Review

    1. Top of page
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    4. Graphical Abstract
    5. Corrigenda
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    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
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    1. Trifluoromethylboranes and -Borates: New Synthetic Strategies and Applications (pages 9180–9196)

      Maik Finze, Eduard Bernhardt and Helge Willner

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200700826

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      Sought for weak coordination: The first synthesis of the [B(CF3)4] ion by fluorination of the [B(CN)4] ion marks the beginning of a new development in the field of B-CF3 chemistry. In concentrated sulfuric acid one of the CF3 groups is transformed into a CO ligand. The borane carbonyl (CF3)3BC[TRIPLE BOND]O is a reactive species and excellent starting material for the synthesis of various (CF3)3B compounds, for example, the pnicogeneethynyl complexes [(CF3)3BC[TRIPLE BOND]Pnic] (Pnic=N, P, As).

  11. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
    1. Reactivity of an Aromatic σ,σ,σ-Triradical: The 2,4,6-Tridehydropyridinium Cation (pages 9198–9201)

      Bartłomiej J. Jankiewicz, Anthony Adeuya, Michael J. Yurkovich, Nelson R. Vinueza, Samuel J. Gardner III, Meng Zhou, John J. Nash and Hilkka I. Kenttämaa

      Version of Record online: 24 SEP 2007 | DOI: 10.1002/anie.200701732

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      Tri-, bi-, and monoradicals: The reactivity of a σ,σ,σ-triradical, 2,4,6-tridehydropyridinium cation, was compared with that of related mono- and biradicals in a Fourier transform ion cyclotron resonance mass spectrometer. The triradical has a doublet ground state and contains three interacting radical sites. The reactivity of the triradical more closely resembles that of related monoradicals than related biradicals.

    2. How to Make Five Contiguous Stereocenters in One Reaction: Asymmetric Organocatalytic Synthesis of Pentasubstituted Cyclohexanes (pages 9202–9205)

      Efraím Reyes, Hao Jiang, Andrea Milelli, Petteri Elsner, Rita G. Hazell and Karl Anker Jørgensen

      Version of Record online: 5 NOV 2007 | DOI: 10.1002/anie.200704454

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      Give me five! An organocatalyzed two-component domino reaction has been developed in which two new C[BOND]C bonds and five stereocenters are created in a one-pot fashion (see scheme; DABCO=1,4-diazabicyclo[2.2.2]octane, TMS=trimethylsilyl). The striking features of this transformation are the high preference for one diastereomer (out of 32 possible isomers) and enantioselectivities of up to 94 %.

    3. Controlled Nanoscale Mechanical Phenomena Discovered with Ultrafast Electron Microscopy (pages 9206–9210)

      David J. Flannigan, Vladimir A. Lobastov and Ahmed H. Zewail

      Version of Record online: 6 NOV 2007 | DOI: 10.1002/anie.200704147

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      On again, off again: The reversible expansion and contraction of single crystals of [Cu(TCNQ)] induced by near-infrared laser pulses was studied with ultrafast electron microscopy (TCNQ=7,7,8,8-tetracyanoquinodimethane). The crystal expands along the π-stacking axis of the TCNQ molecules, but not perpendicular to this axis, when exposed to light. The crystal returned to its original structure when the laser light was blocked.

    4. Total Synthesis and Stereochemical Reassignment of (+)-Neopeltolide (pages 9211–9214)

      Willmen Youngsaye, Jason T. Lowe, Frauke Pohlki, Paul Ralifo and James S. Panek

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200704122

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      Take a closer look! The first enantioselective total synthesis, stereochemical reassignment, and absolute configuration of the metabolite neopeltolide is described (see picture). Synthetic highlights of this route include a modified Evans–Tishchenko reduction to introduce the C11 stereocenter, [4+2] annulation to construct the pyran system, and a Still–Gennari olefination to install the oxazole side chain.

    5. Rhodanine-Based Tau Aggregation Inhibitors in Cell Models of Tauopathy (pages 9215–9219)

      Bruno Bulic, Marcus Pickhardt, Inna Khlistunova, Jacek Biernat, Eva-Maria Mandelkow, Eckhard Mandelkow and Herbert Waldmann

      Version of Record online: 5 NOV 2007 | DOI: 10.1002/anie.200704051

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      Breaking up the crowd: The pathological aggregation of tau protein correlates closely with the progression of Alzheimer's disease. Rhodanine-based inhibitors of tau aggregation (e.g. 1) have been identified, and it has been shown that tau aggregation in a cell model is reversible and can be inhibited by small molecules at nanomolar concentrations (see SEM images).

    6. i-Motif Formation with Locked Nucleic Acid (LNA) (pages 9220–9222)

      Niti Kumar, Jakob T. Nielsen, Souvik Maiti and Michael Petersen

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200701667

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      Dotting the i: The i-motif is a four-stranded DNA structure that consists of intercalated hemiprotonated C:C+ base pairs. Although they contain 2′-ribo oxygen atoms, LNA-modified TC5 oligonucleotides are also able to form stable tetrameric i-motif structures at low pH values (see view into one of the two narrow grooves of such a structure), as shown by a combination of CD, UV, and NMR spectroscopy.

    7. Thiamine Biosynthesis in Escherichia coli: Identification of the Intermediate and By-Product Derived from Tyrosine (pages 9223–9226)

      Marco Kriek, Filipa Martins, Martin R. Challand, Anna Croft and Peter L. Roach

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200702554

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      In anaerobic organisms such as E. coli the tyrosine lyase ThiH is essential for the biosynthesis of the thiazole moiety of the vitamin thiamine. ThiH is a member of the “radical AdoMet” family. The products formed by cleavage of tyrosine in vitro have been identified and suggest a radical-mediated cleavage resulting in p-cresol and dehydroglycine which is hydrolyzed to glyoxylate.

    8. Covalent Interlinking of an Aldehyde and an Amine on a Au(111) Surface in Ultrahigh Vacuum (pages 9227–9230)

      Sigrid Weigelt, Carsten Busse, Christian Bombis, Martin M. Knudsen, Kurt V. Gothelf, Thomas Strunskus, Christof Wöll, Mats Dahlbom, Bjørk Hammer, Erik Lægsgaard, Flemming Besenbacher and Trolle R. Linderoth

      Version of Record online: 29 OCT 2007 | DOI: 10.1002/anie.200702859

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      Getting a reaction: A condensation reaction occurs between a dialdehyde and an amine coadsorbed on a Au(111) surface in an ultrahigh vacuum. The self-assembled structures formed by the diimine reaction product on the surface have been investigated by scanning tunneling microscopy (see image). A solvent-free reaction path is proposed from DFT calculations.

    9. Enantioselective Radical Reactions: Stereoselective Aldol Synthesis from Cyclic Ketones (pages 9231–9234)

      Mukund P. Sibi and Sukanya Nad

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200702976

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      Radicalized aldols: Enones with a fixed s-cis geometry can undergo enantioselective radical reactions. The synthesis of aldol products derived from cyclic ketones in excellent yields and enantioselectivity demonstrates that s-cis-enones are excellent substrates for radical reactions. A tentative model to explain the stereochemical outcome of the reaction consists of nucleophilic radical addition to the si face (see picture).

    10. Interfacial Assembly of Nanoparticles in Discrete Block-Copolymer Aggregates (pages 9235–9238)

      Brenda L. Sanchez-Gaytan, Weihong Cui, YooJin Kim, Miguel A. Mendez-Polanco, Timothy V. Duncan, Michael Fryd, Bradford B. Wayland and So-Jung Park

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200703032

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      In the nanosphere: The cooperative self-assembly of CdSe/ZnS nanoparticles and an amphiphilic block copolymer leads to unique spherical assemblies. In these assemblies, the nanoparticles (green circles) are located at the interface between an outer polymer shell and an inner polymer core (see picture).

    11. A Genetically Encoded Bidentate, Metal-Binding Amino Acid (pages 9239–9242)

      Jianming Xie, Wenshe Liu and Peter G. Schultz

      Version of Record online: 24 SEP 2007 | DOI: 10.1002/anie.200703397

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      A two-ring binder: To facilitate the design of metalloproteins, the bidentate, metal-binding amino acid bipyridylalanine (BpyAla) was genetically encoded in E. coli in response to the amber nonsense codon with high fidelity and yield. The incorporation of BpyAla requires a BpyAla-specific aminoacyl-tRNA synthetase, which was evolved in a stepwise fashion. The structural basis of selective recognition of BpyAla by this synthetase was also determined.

    12. Direct Synthesis of Anisotropic Polymer Nanoparticles (pages 9243–9247)

      Tao He, Dave J. Adams, Michael F. Butler, Chert Tse Yeoh, Andrew I. Cooper and Steven P. Rannard

      Version of Record online: 15 NOV 2007 | DOI: 10.1002/anie.200703348

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      No (self-)assembly required: Both spherical and anisotropic “dumbbell” polymer nanoparticles with targeted shapes in the <100-nm size range were prepared by direct synthesis not relying on self-assembly. Atom-transfer polymerization techniques at high concentrations produce both spherical and dumbbell-like nanoparticles directly from simple vinyl monomers on a multigram scale.

    13. Free-Radical-Based, Specific Desulfurization of Cysteine: A Powerful Advance in the Synthesis of Polypeptides and Glycopolypeptides (pages 9248–9252)

      Qian Wan and Samuel J. Danishefsky

      Version of Record online: 28 NOV 2007 | DOI: 10.1002/anie.200704195

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      Being specific: The specific conversion of Cys (seleno-Cys) into Ala by a free-radical-mediated reduction can be achieved in an aqueous medium under mild conditions (see scheme, PG=protecting group). The conversion can be achieved in the presence of all 20 natural amino acids as well as a range of functional groups. This native chemical ligation followed by the Cys into Ala conversion will enable the synthesis of complex peptides and glycopeptides.

    14. Origin and Dynamics of Oxygen Storage/Release in a Pt/Ordered CeO2–ZrO2 Catalyst Studied by Time-Resolved XAFS Analysis (pages 9253–9256)

      Takashi Yamamoto, Akane Suzuki, Yasutaka Nagai, Toshitaka Tanabe, Fei Dong, Yasuhiro Inada, Masaharu Nomura, Mizuki Tada and Yasuhiro Iwasawa

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200703085

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      Electronic and structural dynamics of an industrially relevant Pt/CeO2–ZrO2 catalyst with an ordered arrangement of Ce and Zr ions during oxygen storage/release processes at 573–773 K were studied in real time by time-resolved energy-dispersive XAFS at the Zr K edge and Ce L3 edge (see experimental setup). On the basis of these results, the roles of Ce and Zr ions in the function of the mixed-oxide catalyst were elucidated.

    15. Alkylation of Aryl N-(2-Pyridylsulfonyl)aldimines with Organozinc Halides: Conciliation of Reactivity and Chemoselectivity (pages 9257–9260)

      Jorge Esquivias, Ramón Gómez Arrayás and Juan Carlos Carretero

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200703239

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      The best of both worlds: With a coordinating 2-pyridylsulfonyl group as the N-activating group, aromatic aldimines show unprecedented high reactivity towards the direct addition of alkyl zinc bromide reagents in the presence of catalytic amounts of Cu(OTf)2. The reaction combines high reactivity with wide functional-group compatibility to provide ready access to functionalized benzylamines and derivatives (see example). Tf=trifluoromethanesulfonyl.

    16. Oligopyrrole Synthesis by 1,3-Dipolar Cycloaddition of Azomethine Ylides with Bissulfonyl Ethylenes (pages 9261–9264)

      Ana López-Pérez, Rocío Robles-Machín, Javier Adrio and Juan Carlos Carretero

      Version of Record online: 23 OCT 2007 | DOI: 10.1002/anie.200703258

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      One by one or two by two: In a general approach to the iterative construction of oligopyrroles, the cycloaddition of azomethine ylides derived from pyrrolyl α-iminoesters with 1,2-bis(phenylsulfonyl)ethylene is followed by the elimination of the sulfonyl groups in situ under basic conditions. This strategy is amenable to the introduction of one or two pyrrole units in each iterative cycle.

    17. Total Syntheses of Amphidinolide H and G (pages 9265–9270)

      Alois Fürstner, Laure C. Bouchez, Jacques-Alexis Funel, Vilnis Liepins, François-Hugues Porée, Ryan Gilmour, Florent Beaufils, Daniel Laurich and Minoru Tamiya

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200704024

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      Eureka! The first conquest of the exceptionally potent cytotoxic agent amphidinolide H, which exhibits activity in the picomolar range against human epidermoid cancer cells, was long overdue. The successful route critically hinges upon the scrupulous optimization of the fragment-coupling events (see picture; RCM=ring-closing metathesis) and on the careful adjustment of the peripheral protecting-group pattern.

    18. Combining Resonant Piezoelectric Micromembranes with Molecularly Imprinted Polymers (pages 9271–9274)

      Cédric Ayela, Fanny Vandevelde, Denis Lagrange, Karsten Haupt and Liviu Nicu

      Version of Record online: 29 OCT 2007 | DOI: 10.1002/anie.200703881

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      Layered chips: The experimental proof of concept of the combination of resonant microelectromechanical systems with molecularly imprinted polymers (MIPs) has been shown for the first time. The use of micromembrane gravimetric sensors carrying piezoelectric thin films, the surfaces of which are coated with MIPs by using a cantilever-based deposition tool (see image), is reported. The multiplexed format of the chips shows the potential of the system for the specific, label-free, reliable detection of target molecules.

    19. Concise Total Synthesis of Cruentaren A (pages 9275–9278)

      Alois Fürstner, Martin Bindl and Ludovic Jean

      Version of Record online: 31 OCT 2007 | DOI: 10.1002/anie.200703839

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      Converging on the target: The highly cytotoxic F-ATPase inhibitor cruentaren A constitutes an interesting lead in the quest for innovative chemotherapeutic agents for the treatment of various diseases, including cancer. Its synthesis was achieved in an overall yield of 3 % by an expeditious convergent route involving a ring-closing alkyne metathesis reaction (RCAM) for the formation of the macrocyclic ring (see picture).

    20. A Water-Based Synthesis of Octahedral, Decahedral, and Icosahedral Pd Nanocrystals (pages 9279–9282)

      Byungkwon Lim, Yujie Xiong and Younan Xia

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200703755

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      Shapes from water: Pd nanocrystals with controllable shapes are synthesized by reducing a Pd salt with citric acid in aqueous solution. Citric acid favors the formation of octahedra, icosahedra, or decahedra (see picture) owing to its strong binding to the {111} facets of Pd. Shape control of these nanocrystals is readily accomplished by adjusting the amounts of Na2PdCl4 precursor and citric acid added to the reaction mixture.

    21. Longer Guests Drive the Reversible Assembly of Hyperextended Capsules (pages 9283–9286)

      Dariush Ajami and Julius Rebek Jr.

      Version of Record online: 6 NOV 2007 | DOI: 10.1002/anie.200702245

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      Hyperextension: A hydrogen-bonded, dimeric capsule can be expanded with four, eight, or twelve glycoluril spacers (see picture) that increase the cavity's volume by up to 530 Å3 and its length by up to 21 Å. The extended assemblies are chiral and encapsulate a variety of normal alkanes. The expanded capsules suggest that increasingly complex capsules may emerge from other spacers with hydrogen-bonding capabilities and curved surfaces.

    22. A Stable Room-Temperature Molecular Assembly of Zwitterionic Organic Dipoles Guided by a Si(111)-7×7 Template Effect (pages 9287–9290)

      Younes Makoudi, Madjid Arab, Frank Palmino, Eric Duverger, Christophe Ramseyer, Fabien Picaud and Frédéric Chérioux

      Version of Record online: 6 NOV 2007 | DOI: 10.1002/anie.200702794

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      Chiral assemblies of achiral molecules: High-resolution STM images of zwitterionic organic dipoles deposited on Si(111)-7×7 show a chiral molecular assembly on this surface (see picture). Density functional calculations demonstrate that a sulfonato group can act as an electrostatic shield that protects the π skeleton of organic molecules from the dangling bonds of semiconductor surfaces, which is a major advance in the deposition of π-conjugated molecules.

    23. Diastereodivergent Synthesis of Enantiomerically Pure Homoallylic Amine Derivatives Containing Quaternary Carbon Stereocenters (pages 9291–9294)

      Goren Kolodney, Genia Sklute, Sylvie Perrone, Paul Knochel and Ilan Marek

      Version of Record online: 24 SEP 2007 | DOI: 10.1002/anie.200702981

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      Freedom of choice: Both enantiomers of free homoallylic amines with two stereogenic centers (including a quaternary center) can be prepared at will from vinyl copper intermediates derived from either a vinyl iodide or an alkyne (see examples; the sulfinyl group is cleaved readily under mild acidic conditions). In this one-pot strategy, zinc homologation of the vinyl copper species is followed by treatment with a sulfinylimine derivative.

    24. All-Carbon Intramolecular Conjugate Displacement Reactions: An Effective Route to Carbocycles (pages 9295–9297)

      Bodhuri Prabhudas and Derrick L. J. Clive

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200703022

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      Working together: Synergy between Michael addition and SN2′ displacement allows stabilized carbanions or the nucleophilic carbon atoms of enamines to undergo intramolecular addition to an α,β-unsaturated ester unit bearing an allylic leaving group to generate unsaturated carbocycles (see scheme). The starting esters are available by a selenium-based alternative to the classical Baylis–Hillman reaction, and complex structures can be assembled.

    25. Enzymatic Release and Macrolactonization of Cryptophycins from a Safety-Catch Solid Support (pages 9298–9300)

      Wolfgang Seufert, Zachary Q. Beck and David H. Sherman

      Version of Record online: 2 NOV 2007 | DOI: 10.1002/anie.200703665

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      Thioesters need not apply: Cryptophycin thioesterase (Crp TE) cleaves and macrolactonizes linear cryptophycin substrates bound to activated safety-catch PEGA resin. This novel enzymatic solid-phase approach was used to further investigate the tolerance of Crp TE for structural variations of substrates.

    26. Alkene-Directed Regioselective Nickel-Catalyzed Cross-Coupling of Cyclic Anhydrides with Diorganozinc Reagents (pages 9301–9304)

      Rebecca L. Rogers, Jennifer L. Moore and Tomislav Rovis

      Version of Record online: 5 NOV 2007 | DOI: 10.1002/anie.200703124

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      The -enes have it! A resident alkene directs a nickel-catalyzed cross-coupling of cyclic anhydrides with diorganozinc reagents. Relative directing effects parallel the stability of nickel–alkene complexes, with less-hindered terminal olefins dominating over internal olefins.

    27. Interaction of Malachite Green with Guanine-Rich Single-Stranded DNA: Preferential Binding to a G-Quadruplex (pages 9305–9307)

      Achikanath C. Bhasikuttan, Jyotirmayee Mohanty and Haridas Pal

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200703251

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      Bound to be better: The formation of a strong complex between the chromophoric dye malachite green (MG, in green) and the G-quadruplex structure (represented in black) of the guanine-rich single-strand oligomer sequence d(G2T)13G results in a 100-fold enhancement of the fluorescence yield of MG. The existence of an intra- or interstrand G-quadruplex structure depends on the oligomer concentration and the ionic strength of the solution.

    28. DNA-Based Catalytic Enantioselective Michael Reactions in Water (pages 9308–9311)

      David Coquière, Ben L. Feringa and Gerard Roelfes

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200703459

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      High, but not dry: A highly enantioselective Michael reaction in water has been developed by using a simple DNA-based catalyst. Enantioselectivities of up to 99 % ee could be obtained by using nitromethane and dimethyl malonate as the nucleophiles and α,β-unsaturated 2-acylimidazoles as the Michael acceptors. The reactions can be performed on a preparative scale and the catalyst can be recycled.

    29. The 1,2,3-Triazole Ring as a Peptido- and Olefinomimetic Element: Discovery of Click Vanilloids and Cannabinoids (pages 9312–9315)

      Giovanni Appendino, Sara Bacchiega, Alberto Minassi, Maria Grazia Cascio, Luciano De Petrocellis and Vincenzo Di Marzo

      Version of Record online: 29 OCT 2007 | DOI: 10.1002/anie.200703590

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      Fooling nature: The replacement of amide and alkene groups in a biological setting with the 1,2,3-triazole group led to the discovery of compounds with a unique vanilloid/cannabinoid mixed profile. For example, the natural amides (see picture, above) and their triazole mimics (below) exhibit similar agonistic (X=H) or antagonistic (X=I) activity towards the TRPV1 receptor; however, only the triazole derivatives also show cannabinomimetic activity.

    30. Bond Formation with Maintenance of Twofold Charge: Generation of C2O32+ in the Reaction of CO22+ with CO2 (pages 9316–9319)

      Jana Roithová, Claire L. Ricketts, Detlef Schröder and Stephen D. Price

      Version of Record online: 31 OCT 2007 | DOI: 10.1002/anie.200704286

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      100 years after the prediction of the existence of C2O3 by Berthelot, doubly charged C2O32+ has been identified as a product in the reaction of CO22+ with CO2 (see scheme). The occurrence of this reaction for such a small dication indicates that bond-forming processes might play a much larger role in reactions of dications than has been anticipated to date.

    31. Total Synthesis and Configurational Assignment of Pasteurestin A and B (pages 9320–9322)

      Marion Kögl, Lothar Brecker, Ralf Warrass and Johann Mulzer

      Version of Record online: 2 OCT 2007 | DOI: 10.1002/anie.200703457

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      Fresh pasture for the [2+2+2] cycloaddition: The two sesquiterpenoids pasteurestin A and B, which exhibit strong and selective antibacterial activity against Pasteurella haemolytica, have been prepared in a synthesis relying on a [2+2+2] Vollhardt enediyne cycloaddition. The previously unknown absolute and relative configurations were established, and the biological profile was specified more precisely.

    32. Unusual Coordination Behavior of Pn-Ligand Complexes with Tl+ (pages 9323–9326)

      Stefan Welsch, Laurence J. Gregoriades, Marek Sierka, Manfred Zabel, Alexander V. Virovets and Manfred Scheer

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200704015

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      Pentaphosphaferrocene coordinates as a π ligand to the large monocation Tl+. In addition, one of the phosphorus atoms of each cyclo-P5 moiety coordinates to a neighboring Tl+ ion to give a one-dimensional polymer. Even at low temperatures, fast rotation of the P5 rings is observed in solution and in the solid state.

    33. Strong Evidence for a Transient Phosphinidenoid Complex (pages 9327–9330)

      Aysel Özbolat, Gerd von Frantzius, Janaina Marinas Pérez, Martin Nieger and Rainer Streubel

      Version of Record online: 5 NOV 2007 | DOI: 10.1002/anie.200701962

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      Caught in the trap: Two different routes to the thermally unstable phosphinidenoid complex I are described, and chemical evidence for this novel intermediate is provided through selective reactions. For example, methyl iodide, dimethylcyanamide, or butyraldehyde furnished complexes II, III, and IV (see scheme) under very mild conditions.

    34. Enantioselective Preparation of 1,1-Diarylethanes: Aldehydes as Removable Steering Groups for Asymmetric Synthesis (pages 9331–9334)

      Thomas C. Fessard, Stephen P. Andrews, Hajime Motoyoshi and Erick M. Carreira

      Version of Record online: 6 NOV 2007 | DOI: 10.1002/anie.200702995

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      Cut it out! Convenient procedures have been delineated for the synthesis of optically active, functionalized 1,1-diarylethanes by decarbonylation of β,β-diarylpropionaldehydes. The process can be conducted as a one-pot 1,4-addition/decarbonylation sequence. Aldehydes are used as removable steering groups in this new strategy for the preparation of optically active building blocks.

    35. Chiral Recognition with Silicon-Stereogenic Silanes: Remarkable Selectivity Factors in the Kinetic Resolution of Donor-Functionalized Alcohols (pages 9335–9338)

      Hendrik F. T. Klare and Martin Oestreich

      Version of Record online: 7 NOV 2007 | DOI: 10.1002/anie.200703847

      Thumbnail image of graphical abstract

      Slick silicon: A low-molecular-weight silane (C13H20Si, 204.38 g mol−1) with silicon-centered chirality is capable of discriminating enantiomeric rhodium–substrate complexes in dehydrogenative Si[BOND]O coupling reactions with outstanding selectivity factors (see scheme, s=selectivity factor).

    36. Enantioselective Strecker Reaction Catalyzed by an Organocatalyst Lacking a Hydrogen-Bond-Donor Function (pages 9339–9341)

      Mihaela Negru, Dieter Schollmeyer and Horst Kunz

      Version of Record online: 29 OCT 2007 | DOI: 10.1002/anie.200703179

      Thumbnail image of graphical abstract

      Self-activation: N-Glycosyl imines A of planar chiral [2.2]paracyclophane carbaldehydes act as efficient enantioselective organocatalysts for the Strecker synthesis of α-amino nitriles, although they do not contain a hydrogen-bond donor or a Brønsted acid function. They activate themselves by deprotononation of hydrogen cyanide and catalyze the formation of both aliphatic and aromatic amino nitriles with high enantioselctivity.

  12. Index

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
  13. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Reviews
    8. Highlight
    9. Correspondence
    10. Essay
    11. Review
    12. Communications
    13. Index
    14. Preview
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