Angewandte Chemie International Edition

Cover image for Vol. 47 Issue 1

December 17, 2007

Volume 47, Issue 1

Pages 1–217

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Cover Picture: Increasing the Complexity of Periodic Protein Nanostructures by the Rolling-Circle-Amplified Synthesis of Aptamers (Angew. Chem. Int. Ed. 1/2008) (page 1)

      Zoya Cheglakov, Yossi Weizmann, Adam B. Braunschweig, Ofer I. Wilner and Itamar Willner

      Version of Record online: 13 DEC 2007 | DOI: 10.1002/anie.200790254

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      A self-inking roller can be used to print an extended strip with periodic repeating units. In the same way, by the biochemical technique of rolling-circle amplification (RCA), a circular oligonucleotide sequence serves as a template for the synthesis of a complementary single-stranded DNA chain. If the DNA chain contains aptamers for a protein such as thrombin or lysozyme, subsequent complexation results in periodic protein–DNA composites. I. Willner et al. describe such compounds and even assemblies of DNA, protein, and gold nanoparticles on pp. 126 ff.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Inside Cover: Catalytic Asymmetric Boration of Acyclic α,β-Unsaturated Esters and Nitriles (Angew. Chem. Int. Ed. 1/2008) (page 2)

      Ji-Eon Lee and Jaesook Yun

      Version of Record online: 13 DEC 2007 | DOI: 10.1002/anie.200790256

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      Asymmetric conjugate addition of bis(pinacolato)diboron to α,β-unsaturated carbonyl compounds would provide easy access to enantioenriched functionalized organoboron compounds, which are useful intermediates in organic synthesis. In their Communication on page 145 ff., J.-E. Lee and J. Yun describe the enantioselective β-boration of α,β-unsaturated esters and nitriles using a copper catalyst and planar chiral diphosphine ligands.

  3. Editorial

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
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      2007/5000/500/10/2008/120/75/48[RIGHTWARDS ARROW]52/CEJ/CAJ/CMC/CSC—Without Words? (pages 5–9)

      Peter Gölitz and Felicitas Schöck

      Version of Record online: 13 DEC 2007 | DOI: 10.1002/anie.200705239

  4. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
  6. Book Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
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    1. Sensory-Directed Flavor Analysis. Edited by Ray Marsili. (pages 31–32)

      Katharina Breme, Xavier Fernandez and Uwe J. Meierhenrich

      Version of Record online: 13 DEC 2007 | DOI: 10.1002/anie.200685540

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Total Synthesis of Azadirachtin—Finally Completed After 22 Years (pages 34–37)

      Johann Jauch

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/anie.200703814

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      Patience pays off: 22 years ago Ley and co-workers started their project on the synthesis of azadirachtin (1)—a project which they recently completed successfully with the first total synthesis of this complex natural product. This milestone of natural product synthesis is acknowledged in this Highlight. Tig=tigloyl=(E)-2-methyl-2-butenoyl

    2. Heterolytic H2 Activation by Nonmetals (pages 38–41)

      Alyson L. Kenward and Warren E. Piers

      Version of Record online: 19 OCT 2007 | DOI: 10.1002/anie.200702816

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      Nice cleavage: Two new strategies for the transition-metal-free activation of σ bonds are presented, namely, Bertrand's activation of dihydrogen by carbenes (see picture, left) and Stephan's “frustrated” Lewis acid/base pairs (right; R=Me3C6H2).

  8. Essay

    1. Top of page
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    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Organocatalysis Lost: Modern Chemistry, Ancient Chemistry, and an Unseen Biosynthetic Apparatus (pages 42–47)

      Carlos F. Barbas III

      Version of Record online: 17 OCT 2007 | DOI: 10.1002/anie.200702210

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      One enigma leads in three directions: The Hajos–Wiechert reaction presented an enigma that went unsolved for three decades. With the unravelling of this enigma, organocatalysis plays a major role in the development of efficient catalytic asymmetric methodologies. The mechanisms of organocatalysis also shed light on the origin of homochirality essential for life and provide clues to yet-to-be-discovered biosynthetic mechanisms at work in living organisms today.

  9. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Towards the Optimal Screening Collection: A Synthesis Strategy (pages 48–56)

      Thomas E. Nielsen and Stuart L. Schreiber

      Version of Record online: 13 DEC 2007 | DOI: 10.1002/anie.200703073

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      Variety is the spice of life: A new strategy for the synthesis of small molecules that involves three phases is discussed: the building of chiral components, their intermolecular coupling, and intramolecular cyclization of strategically placed functional groups. This build/couple/pair strategy efficiently yields stereochemically and skeletally diverse small molecules and is a promising path in the discovery of effective probes and drugs.

  10. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Polymer–Fullerene Composite Solar Cells (pages 58–77)

      Barry C. Thompson and Jean M. J. Fréchet

      Version of Record online: 28 NOV 2007 | DOI: 10.1002/anie.200702506

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      Energy from the sun: Polymer–fullerene (P3HT–PCBM) solar cells have attracted a great deal of attention recently as a result of reports of devices with efficiencies approaching 5 %. The current state-of-the-art in the field is critically examined with a focus on the lessons learned on the electronic and morphological interactions of the polymer and the fullerene, and the areas where improvements still need to be made for the optimization of such devices.

  11. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Book Reviews
    8. Highlights
    9. Essay
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Rediscovering Pasteur's Quasiracemates (pages 78–81)

      Kraig A. Wheeler, Rebecca C. Grove, Raymond E. Davis and W. Scott Kassel

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200704007

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      A fresh Pasteur: Reconstruction of Pasteur's 1853 account of peculiar three-component crystals has confirmed the identities of the two crystalline phases as ammonium (+)-bitartrate (central crystal) and a quasiracemate of ammonium (+)-bitartrate/(−)-bimalate (adjoining crystal laths). The quasiracemate contains approximately inversion-related molecular assemblies in which each bitartrate and bimalate component forms a homomeric catemeric motif.

    2. Reactions of a Copper(II) Superoxo Complex Lead to C[BOND]H and O[BOND]H Substrate Oxygenation: Modeling Copper-Monooxygenase C[BOND]H Hydroxylation (pages 82–85)

      Debabrata Maiti, Dong-Heon Lee, Katya Gaoutchenova, Christian Würtele, Max C. Holthausen, Amy A. Narducci Sarjeant, Jörg Sundermeyer, Siegfried Schindler and Kenneth D. Karlin

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200704389

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      Donor makes the difference: The mononuclear η1-superoxo copper(II) complex 1 undergoes dioxygen activation with the addition of hydrogen-atom donors. Net O2-derived O-atom insertion into the N-methyl group of the ligand leads to formation of a copper(II)-alkoxide product 2. The cupric superoxo species 1 itself is not capable of the observed hydroxylation reaction.

    3. Topochemical Synthesis of Monometallic (Co2+–Co3+) Layered Double Hydroxide and Its Exfoliation into Positively Charged Co(OH)2 Nanosheets (pages 86–89)

      Renzhi Ma, Kazunori Takada, Katsutoshi Fukuda, Nobuo Iyi, Yoshio Bando and Takayoshi Sasaki

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/anie.200703941

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      From platelets to sheets: A topochemical phase conversion employing bromine in acetonitrile transforms β-Co(OH)2 into monometallic Co2+–Co3+ layered double hydroxide (LDH) with a Co2+/Co3+ ratio of 2:1 (see the elemental maps of Co, Br, and O in a Br-intercalated Co2+–Co3+ LDH platelet). Further treatment allows exfoliation of Co2+–Co3+ LDH into positively charged Co(OH)2 nanosheets. Scale bars: 2 μm.

    4. Diazirine-Based DNA Photo-Cross-Linking Probes for the Study of Protein–DNA Interactions (pages 90–93)

      Uddhav Kumar Shigdel, Junliang Zhang and Chuan He

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/anie.200703625

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      Small modification, large effect: Diazirine can be installed quickly and simply in the major or minor groove of DNA for efficient photo-cross-linking to proteins (see picture). This method should be suitable for mapping out protein–DNA interactions, in particular those that may be sensitive to steric hindrance.

    5. Methanol Behavior in Direct Methanol Fuel Cells (pages 94–96)

      Younkee Paik, Seong-Soo Kim and Oc Hee Han

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/anie.200703190

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      Methanol crossover and reaction intermediates are studied in a direct methanol fuel cell (DMFC) by means of 2D and 13C MAS NMR spectroscopy. A membrane electrode assembly (MEA) composed of three polymer electrolyte membrane (PEM) layers is used in the DMFC, and the middle PEM film is extracted to perform the NMR measurements (see image).

    6. Cooperative Ion–Ion Interactions in the Formation of Interpenetrated Molecules (pages 97–101)

      Dennis J. Hoffart, Jorge Tiburcio, Ana de la Torre, Lisa K. Knight and Stephen J. Loeb

      Version of Record online: 15 NOV 2007 | DOI: 10.1002/anie.200703019

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      Anionic wheels for cationic axles: Significant electrostatic ion–ion interactions dramatically increase the stability of interpenetrated molecules. In highly polar solvents, formation of [2]pseudorotaxanes is observed, in which crown ether wheels (see picture, red) having anionic sulfonate groups counter the pyridinium cations of the axle (blue).

    7. A Submicrogram-Scale Protocol for Biomolecule-Based PET Imaging by Rapid 6π-Azaelectrocyclization: Visualization of Sialic Acid Dependent Circulatory Residence of Glycoproteins (pages 102–105)

      Katsunori Tanaka, Tatsuro Masuyama, Koki Hasegawa, Tsuyoshi Tahara, Hiroshi Mizuma, Yasuhiro Wada, Yasuyoshi Watanabe and Koichi Fukase

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200702989

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      On target: Lysine residues in picomole samples of a peptide, proteins, and a monoclonal antibody were rapidly and selectively labeled by a dota-based probe (1, see scheme). Positron emission tomography imaging of [68Ga]dota-labeled orosomucoid and asialoorosomucoid for the first time visualized a difference in the clearance process of glycoproteins in the presence or absence of the sialic acid residue.

    8. Amplification of Molecular Information through Self-Assembly: Nanofibers Formed from Amino Acids and Cyanine Dyes by Extended Molecular Pairing (pages 106–108)

      Tomohiro Shiraki, Masa-aki Morikawa and Nobuo Kimizuka

      Version of Record online: 13 NOV 2007 | DOI: 10.1002/anie.200702793

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      A pretty pair: Self-assembly has been used to amplify and translate the structural information of amino acids into spectroscopic and morphological information (see scheme). It combines in situ premodification of various amino acids and their specific association with a cyanine dye. Conversion of the amino acids into their isoindole derivatives enhances the intermolecular interactions of the amino acid/dye pair to spontaneously form nanostructures.

    9. Sc(OTf)3-Mediated Silylation of Hydroxy Functional Groups on a Solid Surface: A Catalytic Grafting Method Operating at Room Temperature (pages 109–112)

      Ye-Rim Yeon, Young Jun Park, Ji-Sung Lee, Jung-Woo Park, Sin-Gun Kang and Chul-Ho Jun

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/anie.200703112

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      Surface paradise: Facile catalytic post-grafting of the surface of glass or indium tin oxide (ITO, see picture) with a variety of functional groups has been achieved. Methallylsilanes serve as the grafting reagent and the surfaces show remarkable chemical stability.

    10. A Rare (3,4)-Connected Chalcogenide Superlattice and Its Photoelectric Effect (pages 113–116)

      Qichun Zhang, Yang Liu, Xianhui Bu, Tao Wu and Pingyun Feng

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/anie.200703442

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      Light switch: A photoelectric chalcogenide with a (3,4)-connected open-framework structure based on large Cd–S–SAr clusters with boracite-type topology has been synthesized. Its structure (depicted: Cd green, S yellow; Ar omitted) and optical properties have been characterized. The superlattice reproducibly generates a transient photocurrent on excitation by visible light (see picture). SAr=3-methylbenzenethiolate.

    11. Water and Hydrogen Halides Serve the Same Structural Role in a Series of 2+2 Hydrogen-Bonded Dimers Based on 2,6-Bis(2-anilinoethynyl)pyridine Sulfonamide Receptors (pages 117–120)

      Orion B. Berryman, Charles A. Johnson II, Lev N. Zakharov, Michael M. Haley and Darren W. Johnson

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/anie.200703971

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      Mix and match: A new series of receptors reveals an unusual propensity to form 2+2 hydrogen-bonded dimers with water or hydrogen halides. Remarkably, water and hydrogen chloride impart nearly identical structural features to the dimers. In fact, in one case (see picture, Cl green, O red, N blue, S yellow), one water molecule and one chloride ion work in concert to form a hydrogen-bonded dimer stitched together with seven hydrogen bonds.

    12. An Unexpected Organocatalytic Asymmetric Tandem Michael/Morita–Baylis–Hillman Reaction (pages 121–125)

      Silvia Cabrera, José Alemán, Patrick Bolze, Søren Bertelsen and Karl Anker Jørgensen

      Version of Record online: 15 NOV 2007 | DOI: 10.1002/anie.200704076

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      Simply complex: An organocatalytic tandem Michael/Morita–Baylis–Hillman reaction has been developed in which secondary amine catalysts allow for a very selective, scalable synthesis of highly substituted optically active cyclohexanones (see scheme, TMS=trimethylsilyl). Mechanistic studies indicate an active role of the secondary amine catalyst in the Morita–Baylis–Hillman reaction.

    13. Increasing the Complexity of Periodic Protein Nanostructures by the Rolling-Circle-Amplified Synthesis of Aptamers (pages 126–130)

      Zoya Cheglakov, Yossi Weizmann, Adam B. Braunschweig, Ofer I. Wilner and Itamar Willner

      Version of Record online: 23 NOV 2007 | DOI: 10.1002/anie.200703688

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      The biomachinery of rolling-circle amplification relying on protein–aptamer interactions on DNA scaffolds was used to create one-dimensional DNA–protein/DNA–protein–nanoparticle hierarchical assemblies. These conjugates can serve as further templates for the immobilization of gold nanoparticles.

    14. Highly Efficient Stereocontrolled Total Synthesis of (+)-Upial (pages 131–133)

      Kazunori Takahashi, Masayuki Watanabe and Toshio Honda

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/anie.200704423

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      Dual benefit:(+)-Upial, isolated from the sponge Dysidea fragilis (Kaneohe Bay, Hawaii), as a nonisoprenoid sesquiterpene aldehyde lactone, was efficiently synthesized. The key step involved an intramolecular carbonyl–ene reaction, in which the stereocontrolled construction of a bicyclo[3.3.1]nonane ring with five asymmetric carbon centers and the facile introduction of the exo-methylene unit were achieved in a single step (see scheme).

    15. Amphiphilic Helical Peptides Containing Two Acridine Moieties Display Picomolar Affinity toward HIV-1 RRE and TAR (pages 134–137)

      Yeongran Lee, Soonsil Hyun, Hyun Jin Kim and Jaehoon Yu

      Version of Record online: 6 NOV 2007 | DOI: 10.1002/anie.200703090

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      Hold on tight: Amphiphilic α-helical peptides that contain acridine moieties were synthesized, and their binding affinities toward hairpin RNA targets were evaluated. The dramatic increase in binding affinities (40-fold for RRE, 170-fold for TAR) demonstrates that conjugation of intercalators that operate by different binding modes (ionic or hydrogen bonding) leads to one of the most tightly binding pharmacophores against RNA targets.

    16. Oxidant-Free Alcohol Dehydrogenation Using a Reusable Hydrotalcite-Supported Silver Nanoparticle Catalyst (pages 138–141)

      Takato Mitsudome, Yusuke Mikami, Hisashi Funai, Tomoo Mizugaki, Koichiro Jitsukawa and Kiyotomi Kaneda

      Version of Record online: 23 NOV 2007 | DOI: 10.1002/anie.200703161

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      Additive free: Hydrotalcite-supported silver nanoparticles act as a highly efficient heterogeneous catalyst for the dehydrogenation of diverse alcohols (see picture) in the absence of any acceptors such as molecular oxygen, hydrogen peroxide, or unsaturated organic compounds. The solid Ag catalyst was readily reusable without any loss of activity and selectivity.

    17. Eutectic Gallium–Indium (EGaIn): A Moldable Liquid Metal for Electrical Characterization of Self-Assembled Monolayers (pages 142–144)

      Ryan C. Chiechi, Emily A. Weiss, Michael D. Dickey and George M. Whitesides

      Version of Record online: 23 NOV 2007 | DOI: 10.1002/anie.200703642

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      A great GaIn: Micrometer-sized conformal electrodes formed from the title compound are shown to be ideal for measuring the electrical properties of self-assembled monolayers. The image shows the bifurcation of the EGaIn between a metal needle and an Ag surface (not shown) at the point indicated by the two white arrows. The portion above the arrows will form the EGaIn electrode.

    18. Catalytic Asymmetric Boration of Acyclic α,β-Unsaturated Esters and Nitriles (pages 145–147)

      Ji-Eon Lee and Jaesook Yun

      Version of Record online: 8 OCT 2007 | DOI: 10.1002/anie.200703699

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      Asymmetric β-boration of acyclic α,β-unsaturated carbonyl compounds provides ready access to enantioenriched functionalized organoboron compounds. A range of acyclic unsaturated esters and nitriles reacted with high enantioselectivity and good yields at room temperature using a copper catalyst and planar chiral diphosphine ligands (L).

    19. Superhyperfine Interaction in [MnF6]3− (pages 148–150)

      Quirin Scheifele, Torben Birk, Jesper Bendix, Philip L. W. Tregenna-Piggott and Høgni Weihe

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/anie.200703771

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      Resolved at last: A conventional spectrometer afforded the first EPR spectrum of a manganese(III) complex, namely [MnF6]3−, featuring clearly resoved superhyperfine interactions. It is shown how the nature of the Jahn–Teller distortion and the concomitant electronic structure (see picture) can be deduced from a single EPR spectrum and how the electronic structure of the central ion is reflected in the superhyperfine interaction with the surrounding ligands.

    20. Multiply Charged (Di-)Radicals (pages 151–154)

      Fabiane M. Nachtigall, Yuri E. Corilo, Cláudia C. Cassol, Günter Ebeling, Nelson H. Morgon, Jairton Dupont and Marcos N. Eberlin

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/anie.200703858

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      A window of opportunity: New types of gaseous multiply charged (di-)radicals based on ionic liquids have been prepared by ESI MS/MS techniques by using imidazolium ion sites to act as “handles”. Dissociation of gaseous (CH2)n-bridged triimidazolium ions leads to groups of multiply charged (di-)radicals contained within a narrow window of one m/z unit (see spectrum).

    21. The Existence of Two Short-Bond Isomers for Bicyclo[1.1.0]butane Derivatives Based on Boron and Phosphorus (pages 155–159)

      Vincent Gandon, Jean-Baptiste Bourg, Fook S. Tham, Wolfgang W. Schoeller and Guy Bertrand

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/anie.200704008

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      Really (di)radical: Calculations show that parent 2,4-diborata-1,3-diphosphoniocyclobutane-1,3-diyl I has a negligible singlet–triplet energy gap (1.2 kcal mol−1) and would be a perfect diradical that could undergo both disrotatory and conrotatory ring closures to give bicyclo[1.1.0]butane derivatives I′ and I′′. The synthesis of a type I′ derivative is presented.

    22. Reversible Phototuning of Ferromagnetism at Au–S Interfaces at Room Temperature (pages 160–163)

      Masayuki Suda, Naoto Kameyama, Motohiro Suzuki, Naomi Kawamura and Yasuaki Einaga

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/anie.200704027

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      Out of nowhere: Significant photoinduced changes in ferromagnetism have been observed at the interfaces between gold nanoparticles (Au NPs) and azobenzene-derivatized thiols. These photomagnetic effects could be attributed to photoinduced changes in d-charge losses resulting from the photoisomerization of the azo ligands (see picture), which are accompanied by the inversion of surface dipoles to the opposite sign.

    23. Desymmetrization-like Catalytic Enantioselective Fluorination of Malonates and Its Application to Pharmaceutically Attractive Molecules (pages 164–168)

      Dhande Sudhakar Reddy, Norio Shibata, Jun Nagai, Shuichi Nakamura, Takeshi Toru and Shuji Kanemasa

      Version of Record online: 13 NOV 2007 | DOI: 10.1002/anie.200704093

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      At the leading edge: Chiral fluoromalonates can be prepared with very high stereocontrol by enantioselective fluorination of racemic malonates and using a Zn(OAc)2/DBFOX[BOND]Ph catalyst (see scheme), thus providing an efficient alternative route to conventional microbial desymmetrization for the preparation of fluorinated chiral building blocks. Several pharmaceutically attractive compounds were prepared by using this method.

    24. A Reactive Niobium Phosphinidene P8 Cluster Obtained by Reductive Coupling of White Phosphorus (pages 169–172)

      Brandi M. Cossairt and Christopher C. Cummins

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/anie.200704354

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      Eight's company: Disproportionation of [NbI(OC[2Ad]Mes)3(thf)] in the presence of P4 results in reductive coupling of two molecules of P4. The resulting complex, which features a niobium phosphinidene moiety, can subsequently be hydrolyzed (see picture; P orange, Nb blue, O red; 2Ad=2-adamantylidene; Mes=2,4,6-Me3C6H2).

    25. Au–Fe3O4 Dumbbell Nanoparticles as Dual-Functional Probes (pages 173–176)

      Chenjie Xu, Jin Xie, Don Ho, Chao Wang, Nathan Kohler, Edward G. Walsh, Jeffrey R. Morgan, Y. Eugene Chin and Shouheng Sun

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/anie.200704392

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      Heavy lifting: Dumbbell-shaped Au–Fe3O4 nanoparticles are made biocompatible and suitable for attachment to A431 cells. The particles are magnetically and optically active and are useful for simultaneous magnetic and optical detection (see picture). The Au–Fe3O4 nanoparticles are promising as a new type of multifunctional probe for diagnostic and therapeutic applications.

    26. Palladium-Catalyzed γ-Arylation of β,γ-Unsaturated Ketones: Application to a One-Pot Synthesis of Tricyclic Indolines (pages 177–180)

      Alan M. Hyde and Stephen L. Buchwald

      Version of Record online: 21 NOV 2007 | DOI: 10.1002/anie.200704529

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      Indolines in short order: A catalyst system which allows for efficient γ-arylation of β,γ-unsaturated ketones is described (see scheme; dippf=1,1′-bis(diisopropylphosphanyl)ferrocene, dba= trans,trans-dibenzylideneacetone). This method can be applied to a one-pot, two-step synthesis of polycyclic indolines from simple starting materials.

    27. Selective Detection of 5-Methylcytosine Sites in DNA (pages 181–184)

      Sébastian Bareyt and Thomas Carell

      Version of Record online: 26 NOV 2007 | DOI: 10.1002/anie.200702159

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      A distinguished result: 5-Methylcytosine can be distinguished from all other nucleobases in DNA by selective conversion of the C5[BOND]C6 double bond into a bromohydrine followed by piperidine-induced strand cleavage at the reaction site (see picture). This procedure allows the methylation status of the p16 promotor to be determined under in vitro conditions.

    28. Asymmetric Synthesis and Biological Properties of Uncialamycin and 26-epi-Uncialamycin (pages 185–189)

      K. C. Nicolaou, Jason S. Chen, Hongjun Zhang and Ana Montero

      Version of Record online: 3 DEC 2007 | DOI: 10.1002/anie.200704577

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      The highly potent DNA-cleaving molecule uncialamycin (1) was prepared in an asymmetric total synthesis featuring an enantioselective Noyori reduction. Compound 1 and its C26 epimer exhibit impressive broad-spectrum antibacterial properties and highly potent antitumor activities against a variety of cell lines.

    29. Mg6F2(OMe)10(MeOH)14—An Alkoxide Fluoride of an Alkaline Earth Metal (pages 190–192)

      Anton Dimitrov, Stefan Wuttke, Sergey Troyanov and Erhard Kemnitz

      Version of Record online: 13 NOV 2007 | DOI: 10.1002/anie.200703516

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      Partial fluorolysis of magnesium alkoxide with HF leads to an unexpected crystalline magnesium alkoxide fluoride intermediate. The hexanuclear, cationic dicubane unit is bridged by unusual μ4-F atoms and hydrogen-bonded to two methoxide anions, resulting in a triple-ionic structure (see picture, F green, Mg blue, O red, C gray, H black).

    30. A Core-Modified Rubyrin with meso-Aryl Substituents and Phenanthrene-Fused Pyrrole Rings: A Highly Conjugated Near-Infrared Dye and Hg2+ Probe (pages 193–197)

      Di Wu, Ana B. Descalzo, Fritz Weik, Franziska Emmerling, Zhen Shen, Xiao-Zeng You and Knut Rurack

      Version of Record online: 13 NOV 2007 | DOI: 10.1002/anie.200702854

      Thumbnail image of graphical abstract

      Sending signals: The first core-modified, expanded porphyrin with polyaromatic units fused to the pyrrole rings absorbs far into the near-infrared and shows fluorescence that stretches into the second optical window of telecommunication. Doping a polyurethane membrane with the dye yields Hg2+-responsive optical test strips.

    31. Ligand-Dependent Mechanistic Dichotomy in Iron-Catalyzed Allylic Substitutions: σ-Allyl versus π-Allyl Mechanism (pages 198–201)

      Bernd Plietker, André Dieskau, Katrin Möws and Anja Jatsch

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/anie.200703874

      Thumbnail image of graphical abstract

      Iron at the crossroads: A remarkable mechanistic dichotomy in iron-catalyzed allylic substition increases not only the scope of regioselective allylic alkylation but could also herald the development of asymmetric allylic substitution (see Scheme, MTBE=methyl tert-butyl ether). Depending on the ligand used, either a σ- or a π-allyl mechanism is observed.

    32. Relative Rates of Bromine–Magnesium Exchange Reactions in Substituted Bromobenzene Derivatives (pages 202–204)

      Lei Shi, Yuanyuan Chu, Paul Knochel and Herbert Mayr

      Version of Record online: 23 NOV 2007 | DOI: 10.1002/anie.200704100

      Thumbnail image of graphical abstract

      Against expectation: How can the site of Br–Mg exchange in multiply brominated compounds be predicted? Competition experiments with different substituents X and Y (see scheme; X, Y=H, F, Cl, Br, CF3, CO2tBu, CN) reveal a counterintuitive order of substituent effects. The aim of the study is to enable the selectivity of halogen–magnesium exchange reactions of polyfunctional compounds to be predicted.

    33. On the Origin of the Haouamine Alkaloids (pages 205–208)

      Noah Z. Burns and Phil S. Baran

      Version of Record online: 23 NOV 2007 | DOI: 10.1002/anie.200704576

      Thumbnail image of graphical abstract

      Not what it seemed: Careful reinvestigation of the classic Chichibabin pyridine synthesis has provided evidence against a spontaneous tetramerization pathway in the biosynthesis of the haouamine alkaloids. A simple enantioselective synthesis of haouamine A has illuminated its absolute configuration and points towards a phenylalanine-based biosynthesis.

    34. PtCl4-Catalyzed Domino Synthesis of Fused Bicyclic Acetals (pages 209–212)

      Alejandro Diéguez-Vázquez, C. Christoph Tzschucke, Wing Yee Lam and Steven V. Ley

      Version of Record online: 5 DEC 2007 | DOI: 10.1002/anie.200704595

      Thumbnail image of graphical abstract

      At sixes and sevens: The synthesis of [4.2.1]- and [3.2.1]-fused bicyclic acetals by an intramolecular double alkoxylation of alkyne diols is reported. The course of the reaction depends on the substitution of the triple bond. Terminal alkynes give the [3.2.1]bicyclic product by a 6-exo pathway, whereas aryl alkynes undergo almost exclusively a 7-endo cyclization to give the [4.2.1]bicycles (see scheme, Ts=toluene-4-sulfonyl).

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      Preview: Angew. Chem. Int. Ed. 2/2008 (page 217)

      Version of Record online: 13 DEC 2007 | DOI: 10.1002/anie.200790255

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