Angewandte Chemie International Edition

Cover image for Vol. 46 Issue 13

March 19, 2007

Volume 46, Issue 13

Pages 2123–2331

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Cover Picture: Lock-and-Key Principle on a Microscopic Scale: The Case of the Propylene Oxide⋅⋅⋅Ethanol Complex (Angew. Chem. Int. Ed. 13/2007) (page 2123)

      Nicole Borho and Yunjie Xu

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200790045

      The lock-and-key principle is illustrated on a microscopic scale by the binding between propylene oxide (PO) and ethanol. PO acts as a rigid ‘lock’ and EtOH offers keys in the form of the gauche−, gauche+, and trans conformers. In their Communication on page 2276 ff., N. Borho and Y. Xu use rotational spectroscopy and ab initio calculations to analyze the six possible hydrogen-bonded conformers (three of which are shown in the cover picture) of the 1:1 PO⋅⋅⋅EtOH molecular complex.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Inside Cover: Rings of Nanorods (Angew. Chem. Int. Ed. 13/2007) (page 2124)

      Bishnu P. Khanal and Eugene R. Zubarev

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200790046

      Rodlike nanocrystals typically pack in a parallel fashion as dictated by their anisometric shape and stiffness. In their Communication on page 2195 ff., E. R. Zubarev and B. P. Khanal report the spontaneous self-organization of polymer-coated metallic nanorods into circular arrays (see picture). These superstructures—“rings of nanorods”—are templated by water microdroplets that condense on the surface of nonpolar organic solvents and can be produced in near-quantitative yield in a matter of seconds.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. You have free access to this content
      Hydrogen-Bonded Helical Organic Nanotubes (page 2138)

      G. Dan Pantoş, Paolo Pengo and Jeremy K. M. Sanders

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200790048

      This article corrects:

      Hydrogen-Bonded Helical Organic Nanotubes1

      Vol. 46, Issue 1-2, 194–197, Article first published online: 7 NOV 2006

  5. Obituary

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Alan G. MacDiarmid (1927–2007) (pages 2140–2141)

      Alan J. Heeger

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200700747

  6. Book Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Nanomaterials Handbook. Edited by Yury Gogotsi. (page 2143)

      Alf Mews

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200685445

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Rhenium-Catalyzed C[BOND]H and C[BOND]C Bond Activation (pages 2144–2146)

      Yoshikazu Horino

      Article first published online: 27 FEB 2007 | DOI: 10.1002/anie.200605228

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      Making rings: The Re-catalyzed insertion of phenylacetylene into cyclic 1,3-keto esters to give medium-sized-ring compounds is discussed in context. The rhenium catalyst promises to be more general since it is required in low amounts and reacts under mild conditions with nonstrained substrates.

    2. Reversible Sugar Transfer by Glycosyltransferases as a Tool for Natural Product (Bio)synthesis (pages 2147–2150)

      Helge B. Bode and Rolf Müller

      Article first published online: 15 FEB 2007 | DOI: 10.1002/anie.200604671

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      A bit of give and take: The recently described reversibility of sugar transfer by glycosyltransferases allows the exchange of sugar or aglycon moieties resulting in the formation of novel glycosylated compounds in a one-pot reaction (see picture; NDP=nucleoside diphosphate, GT=glycosyltransferase).

  8. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Control of Magnetic Properties through External Stimuli (pages 2152–2187)

      Osamu Sato, Jun Tao and Yuan-Zhu Zhang

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200602205

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      Under control: The behavior of certain magnetic materials can be controlled by external stimuli such as temperature, light, and pressure. Typical examples of such switchable materials are valence-tautomeric compounds, molecular photomagnets, and spin-crossover complexes, which could find application in memory devices or optical switches.

  9. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. Obituary
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. A Classical Silver Carbonyl Complex [{MeB[3-(Mes)pz]3}Ag(CO)] and the Related Silver Ethylene Adduct [{MeB[3-(Mes)pz]3}Ag(C2H4)] (pages 2188–2191)

      H. V. Rasika Dias and Mauro Fianchini

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200604084

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      Sting in the tale: A thermally stable silver(I) ethylene complex and the first classical silver(I) carbonyl adduct (see structure) have been isolated using the nonfluorinated, relatively electron-rich scorpionate ligand [MeB{3-(Mes)pz}3] (Mes=2,4,6-trimethylphenyl, pz=pyrazolate).

    2. Arene-Sandwiched Silver(I) Pyrazolates (pages 2192–2194)

      H. V. Rasika Dias and Chammi S. Palehepitiya Gamage

      Article first published online: 8 FEB 2007 | DOI: 10.1002/anie.200604585

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      A silver filling: The π-acidic, trinuclear silver(I) pyrazolate [{[3,5-(CF3)2pz]Ag}3] readily reacts with simple electron-rich aromatic hydrocarbon compounds to form sandwich complexes. The type of complex formed depends on the solvent and the arene, and includes supramolecular stacks. Additionally, some of these complexes appear to have interesting luminescence properties.

    3. Rings of Nanorods (pages 2195–2198)

      Bishnu P. Khanal and Eugene R. Zubarev

      Article first published online: 27 FEB 2007 | DOI: 10.1002/anie.200604889

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      Ring-a-ring o'rods: Hybrid gold/polymer core–shell nanorods spontaneously organize into ringlike arrays when a drop of their solution is dried on a substrate. The process is highly reproducible and generates thousands of well-defined rings of nanorods in a matter of seconds (see TEM image). Studies revealed that water droplets, which condense on the surface of nonpolar solvents, template the formation of the rings.

    4. Total Synthesis of Paecilomycine A (pages 2199–2202)

      Sun-Joon Min and Samuel J. Danishefsky

      Article first published online: 15 FEB 2007 | DOI: 10.1002/anie.200605058

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      Piecing together paecilomycine: The first total synthesis of paecilomycine A, a terpenoid that enhances nerve growth factor levels in certain human cells, has been achieved. Two highly stereoselective key steps in this concise route include an intermolecular Diels–Alder reaction and an intramolecular Pauson–Khand reaction (see scheme).

    5. Kinetic Recognition of AT-Rich DNA by Ruthenium Complexes (pages 2203–2206)

      Pär Nordell, Fredrik Westerlund, L. Marcus Wilhelmsson, Bengt Nordén and Per Lincoln

      Article first published online: 20 FEB 2007 | DOI: 10.1002/anie.200604294

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      Finding AT tracts: High selectivity for long AT sequences can be attained through kinetically controlled DNA threading intercalation by binuclear ruthenium(II) complexes (see picture). The rate of intercalation is strongly correlated to the number of consecutive AT base pairs and is up to 2500-times higher with poly(dAdT)2 than with mixed-sequence DNA.

    6. Raftlike Polyvalent Inhibitors of the Anthrax Toxin: Modulating Inhibitory Potency by Formation of Lipid Microdomains (pages 2207–2209)

      Prakash R. Rai, Arundhati Saraph, Randolph Ashton, Vincent Poon, Jeremy Mogridge and Ravi S. Kane

      Article first published online: 20 FEB 2007 | DOI: 10.1002/anie.200604317

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      The good fat: Anthrax toxin inhibitors that contain lipid microdomains have been synthesized. The clustering of inhibitory peptides in membrane microdomains results in a significant increase in inhibitory potency. Peptide clustering and microdomain formation can be actively modulated in response to an external stimulus.

    7. The Structure of the Hyponitrite Species in a Heme Fe[BOND]Cu Binuclear Center (pages 2210–2214)

      Constantinos Varotsis, Takehiro Ohta, Teizo Kitagawa, Tewfik Soulimane and Eftychia Pinakoulaki

      Article first published online: 13 FEB 2007 | DOI: 10.1002/anie.200602963

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      NO laughing matter: The enzymatic production of laughing gas (N2O) from two molecules of NO requires the formation of the N[BOND]N bond and the subsequent cleavage of the N[BOND]OH bond. Resonance Raman spectroscopic studies have now provided evidence for the formation of the key intermediate, the hyponitrite species (see the optimized molecular structure), in the heme a3 Fe[BOND]CuB binuclear center of ba3-oxidoreductase from Thermus thermophilus.

    8. Self-Assembled Monolayers of a Multifunctional Organic Radical (pages 2215–2219)

      Núria Crivillers, Marta Mas-Torrent, Sandrine Perruchas, Nans Roques, José Vidal-Gancedo, Jaume Veciana, Concepció Rovira, Lourdes Basabe-Desmonts, Bart Jan Ravoo, Mercedes Crego-Calama and David N. Reinhoudt

      Article first published online: 20 FEB 2007 | DOI: 10.1002/anie.200603599

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      A radical switch: Covalent and noncovalent interactions have been used to functionalize silicon oxide surfaces with polychlorotriphenylmethyl radicals, which are electroactive and can be reversibly reduced or oxidized to nonmagnetic and nonfluorescent species. Thus, the self-assembled monolayers behave as chemical switches that combine electronic absorption, fluorescence emission (see picture), and magnetic outputs.

    9. Well-Designed Supramolecular Clusters Comprising Triphenylmethylamine and Various Sulfonic Acids (pages 2220–2223)

      Norimitsu Tohnai, Yuji Mizobe, Michiko Doi, Shin-ichiro Sukata, Tomoaki Hinoue, Tetsuharu Yuge, Ichiro Hisaki, Yozo Matsukawa and Mikiji Miyata

      Article first published online: 13 FEB 2007 | DOI: 10.1002/anie.200603841

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      Potential nanoparticle precursors: Triphenylmethylamine (TritylNH2) and various sulfonic acids (RSO3H; R=phenyl in the space-filling representation) assemble into [4+4] ion-pair clusters in the solid state and in solution. The shapes and sizes of these clusters are controlled by the sulfonic acid substituents. Fabrication of the clusters is convenient and efficient, and this method may be used to synthesize organic nanoparticles.

    10. Ultrafine Hydrogel Nanoparticles: Synthetic Approach and Therapeutic Application in Living Cells (pages 2224–2227)

      De Gao, Hao Xu, Martin A. Philbert and Raoul Kopelman

      Article first published online: 20 FEB 2007 | DOI: 10.1002/anie.200603927

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      Licensed to kill: A method for obtaining ultrafine hydrophilic polyacrylamide-based nanoparticles that encapsulate meta-tetra(hydroxyphenyl)chlorin (mTHPC) has been developed. Rat C6 glioma cells exposed to infrared light were killed (red) in the presence of the mTHPC-encapsulating nanoparticles while the cells without exposure to light were still alive (green).

    11. Fluorescence-Lifetime Imaging of DNA–Dye Interactions within Continuous-Flow Microfluidic Systems (pages 2228–2231)

      Richard K. P. Benninger, Oliver Hofmann, Björn Önfelt, Ian Munro, Chris Dunsby, Daniel M. Davis, Mark A. A. Neil, Paul M. W. French and Andrew J. de Mello

      Article first published online: 23 JAN 2007 | DOI: 10.1002/anie.200604112

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      Light across the channel: The utility of time-resolved fluorescence imaging as a detection modality for microfluidic systems has been extended by a study of DNA–dye binding interactions. The combination of time-resolved fluorescence imaging and continuous-flow microfluidics provides a powerful route to the resolution and quantification of multistate biological systems with precise spatial and temporal reaction control.

      Corrected by:

      Corrigendum: Fluorescence-Lifetime Imaging of DNA–Dye Interactions within Continuous-Flow Microfluidic Systems

      Vol. 46, Issue 45, 8536, Article first published online: 8 NOV 2007

    12. Elastic Properties of Photoswitchable Azobenzene Polymers from Molecular Dynamics Simulations (pages 2232–2237)

      Lars V. Schäfer, E. Matthias Müller, Hermann E. Gaub and Helmut Grubmüller

      Article first published online: 15 FEB 2007 | DOI: 10.1002/anie.200604595

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      Promising future nanoscopic devices: Azobenzene polypeptides can be switched between an elongated trans and a compact cis conformation. Molecular dynamics simulations have been carried out to probe their elastic properties and to explain recent scanning probe microscopy experiments at the atomic level. The results should enable the rational design of photoswitchable polymers, as demonstrated by a first example.

    13. Filling Helical Nanotubes with C60 (pages 2238–2240)

      G. Dan Pantoş, Jean-Luc Wietor and Jeremy K. M. Sanders

      Article first published online: 19 FEB 2007 | DOI: 10.1002/anie.200604891

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      Pack them in: The complexation of C60 molecules within self-assembled helical nanotubes (see picture) represents a new strategy for solubilizing C60. The C60 molecules in this supramolecular assembly are closely packed in a one-dimensional array and experience the helicity of their environment.

    14. Installing Dynamic Molecular Photomechanics in Mesopores: A Multifunctional Controlled-Release Nanosystem (pages 2241–2244)

      Yingchun Zhu and Masahiro Fujiwara

      Article first published online: 13 FEB 2007 | DOI: 10.1002/anie.200604850

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      Kicking out cholesterol: The release of guest molecules (cholesterol) included in the pores of mesoporous silica is promoted by simultaneous irradiation with UV and visible light. The reversible cistrans photoisomerization of azobenzene substituents on the pore surface causes a stirring action, which accelerates the diffusion of the guest from the pores (see picture), thus providing an intelligent controlled-release method.

    15. Lithiation-Induced Migrations from Nitrogen to Carbon in Terminal Aziridines (pages 2245–2248)

      David M. Hodgson, Philip G. Humphreys, Zhaoqing Xu and John G. Ward

      Article first published online: 15 FEB 2007 | DOI: 10.1002/anie.200604920

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      Benefiting from deprotection: Lithium 2,2,6,6-tetramethylpiperidide induces N-Boc or N-phosphonate terminal aziridines to undergo regio- and stereoselective N-to-C migration of the protecting group, giving synthetically valuable trans-aziridinylesters and trans-aziridinylphosphonates.

    16. Disaccharides as Sialic Acid Aldolase Substrates: Synthesis of Disaccharides Containing a Sialic Acid at the Reducing End (pages 2249–2253)

      Shengshu Huang, Hai Yu and Xi Chen

      Article first published online: 19 FEB 2007 | DOI: 10.1002/anie.200604799

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      Synthesis with an unfussy enzyme: Escherichia coli sialic acid aldolase has been found to be unusually flexible in accepting disaccharides containing a mannose (Man) or N-glycolylmannosamine (ManNGc) at the reducing end as substrates for synthesizing disaccharides containing deaminoneuraminic acid (KDN)or N-glycolylneuraminic acid (Neu5Gc) at the reducing end (see scheme; Gal: galactose; Glc: glucose). The chemoenzymatic method is general and efficient.

    17. Notoamides A–D: Prenylated Indole Alkaloids Isolated from a Marine-Derived Fungus, Aspergillus sp. (pages 2254–2256)

      Hikaru Kato, Takushi Yoshida, Takanori Tokue, Yuka Nojiri, Hiroshi Hirota, Tomihisa Ohta, Robert M. Williams and Sachiko Tsukamoto

      Article first published online: 16 FEB 2007 | DOI: 10.1002/anie.200604381

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      Mussel power: The structures and configurations have been determined of four new indole alkaloids, notoamides A–D, which were isolated from mussel-derived Aspergillus sp. Notoamides A–C show moderate cytotoxicity against cancer cell lines. The relationship between these and other metabolites suggests that the fungus uses a diverse biosynthetic pathway.

      Corrected by:

      Corrigendum: Corrigendum: Notoamides A–D: Prenylated Indole Alkaloids Isolated from a Marine-Derived Fungus, Aspergillus sp.

      Vol. 52, Issue 31, 7909, Article first published online: 23 JUL 2013

    18. A Concise Total Synthesis of the Notoamides C and D (pages 2257–2261)

      Alan W. Grubbs, Gerald D. Artman III, Sachiko Tsukamoto and Robert M. Williams

      Article first published online: 16 FEB 2007 | DOI: 10.1002/anie.200604377

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      A unique oxidation: The first total synthesis of the prenylated indole alkaloids notoamide C and D was accomplished by using a biomimetic oxidation pathway. Oxidation of the putative biosynthetic precursor 1 was achieved in a one-pot reaction to afford notoamide C, its epimer, and notoamide D (see scheme).

    19. A Concise, Biomimetic Total Synthesis of Stephacidin A and Notoamide B (pages 2262–2265)

      Thomas J. Greshock, Alan W. Grubbs, Sachiko Tsukamoto and Robert M. Williams

      Article first published online: 16 FEB 2007 | DOI: 10.1002/anie.200604378

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      Copying nature: A biomimetic total synthesis of stephacidin A has been accomplished using an intramolecular Diels–Alder reaction. Stephacidin A was then converted into notoamide B in a single step by oxaziridine-mediated oxidation to provide the first biomimetic total synthesis of notoamide B (see scheme).

    20. An Intermolecular Double [2+2] Cyclodimerization of a Tetraalkyne (pages 2266–2268)

      James E. Taylor, Mary F. Mahon and John S. Fossey

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200604259

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      Double take: An intermolecular double [2+2] cyclodimerization of vinylidene bisalkynes gives an air-stable organometallic complex with an extraordinary ligand motif (see scheme). The central six-membered ring has all sp2-hybridized carbon atoms and two exocyclic double bonds, and is a stable de-aromatized analogue of p-xylene.

    21. H/D Exchange at Aromatic and Heteroaromatic Hydrocarbons Using D2O as the Deuterium Source and Ruthenium Dihydrogen Complexes as the Catalyst (pages 2269–2272)

      Martin H. G. Prechtl, Markus Hölscher, Yehoshoa Ben-David, Nils Theyssen, Rebekka Loschen, David Milstein and Walter Leitner

      Article first published online: 15 FEB 2007 | DOI: 10.1002/anie.200603677

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      Getting heavy: At temperatures as low as 50 °C, D2O can serve as a cheap and readily available deuterium source for the efficient deuteration of aromatic and heteroaromatic substrates if nonclassical ruthenium hydride complexes are used as catalysts (see scheme). DFT calculations support a catalytic cycle comprising σ-bond metathesis as the key step for the exchange processes.

    22. Borate Esters as Alternative Acid Promoters in the Palladium-Catalyzed Methoxycarbonylation of Ethylene (pages 2273–2275)

      Alta C. Ferreira, Renier Crous, Linette Bennie, Anna M. M. Meij, Kevin Blann, Barend C. B. Bezuidenhoudt, Desmond A. Young, Mike J. Green and Andreas Roodt

      Article first published online: 14 FEB 2007 | DOI: 10.1002/anie.200603751

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      Out with convention! The use of borosalicylic acid, derived from boric and salicylic acids, as the acid promoter in the methoxycarbonylation of ethylene to give methyl propionate has been investigated (see scheme). Not only was moderate catalyst activity observed, but much lower formation of phosphonium salts occurred than with conventional acids.

    23. Lock-and-Key Principle on a Microscopic Scale: The Case of the Propylene Oxide⋅⋅⋅Ethanol Complex (pages 2276–2279)

      Nicole Borho and Yunjie Xu

      Article first published online: 17 NOV 2006 | DOI: 10.1002/anie.200603809

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      Molecular recognition: The binding between propylene oxide (PO) and ethanol resembles the lock-and-key principle, with (R)-PO as a rigid lock and G−, G+, and T conformers of EtOH as different keys (see picture; C yellow, O red). Six hydrogen-bonded PO⋅⋅⋅EtOH conformers were studied using rotational spectroscopy and ab initio calculations, revealing which EtOH key fits best into the PO lock.

    24. A Germanium Alkoxide Supported by a C3-Symmetric Ligand for the Stereoselective Synthesis of Highly Heterotactic Polylactide under Solvent-Free Conditions (pages 2280–2283)

      Amanda J. Chmura, Christopher J. Chuck, Matthew G. Davidson, Matthew D. Jones, Matthew D. Lunn, Steven D. Bull and Mary F. Mahon

      Article first published online: 14 FEB 2007 | DOI: 10.1002/anie.200603944

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      Ge whiz: Highly stereoselective bulk ring-opening polymerization of rac-lactide to afford a heterotactic polymer was achieved for the first time through the use of a single-site germanium alkoxide initiator. The C3 symmetry of the ligand may play an important role in controlling stereoselective chain propagation from the racemic monomer.

    25. Gold- and Indium-Catalyzed Synthesis of 3- and 6-Sulfonylindoles from ortho-Alkynyl-N-sulfonylanilines (pages 2284–2287)

      Itaru Nakamura, Uichiro Yamagishi, Dschun Song, Sayaka Konta and Yoshinori Yamamoto

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200604038

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      Consecutive formation of C[BOND]N and C[BOND]S bonds: The gold-catalyzed intramolecular aminosulfonylation of 2-alkynyl-N-sulfonylanilines 1 (R1=H) produces 3-sulfonylindoles 2 in good to high yields, whereas the indium-catalyzed aminosulfonylation of 2-alkynyl-6-methoxy-N-sulfonylanilines 1 (R1=MeO) affords 6-sulfonylindoles 3 as the major products (see scheme).

    26. Homologation of Propane Catalyzed by Oxide-Supported Zirconium Dihydride and Dialkyl Complexes (pages 2288–2290)

      Chloé Thieuleux, Alexandrine Maraval, Laurent Veyre, Christophe Copéret, Daravong Soulivong, Jean-Marie Basset and Glenn J. Sunley

      Article first published online: 14 FEB 2007 | DOI: 10.1002/anie.200604158

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      Under supercritical conditions and at moderate temperatures, propane is transformed into higher-branched homologues in the presence of a zirconium–dihydride catalyst supported on an oxide material such as silica. Products are formed by a reaction similar to Ziegler–Natta olefin polymerization. Olefinic units generated on one alkyl branch are inserted into the other branch to make a longer alkyl chain (see scheme).

    27. Experimental and Theoretical Evidence for Nonheme Iron(III) Alkylperoxo Species as Sluggish Oxidants in Oxygenation Reactions (pages 2291–2294)

      Mi Sook Seo, Takashi Kamachi, Tomohisa Kouno, Koji Murata, Mi Joo Park, Kazunari Yoshizawa and Wonwoo Nam

      Article first published online: 16 FEB 2007 | DOI: 10.1002/anie.200604219

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      The active oxidant that oxygenates organic substrates is an iron(IV) oxo intermediate, namely, [(tpa)FeIV(O)(CH3CN)]2+ (2), which is formed through O[BOND]O bond homolysis, according to experimental and computational studies on the reactivity of nonheme iron(III) alkylperoxo complex [(tpa)FeIII(OOtBu)(CH3CN)]2+ (1), which was shown to be a sluggish electrophilic oxidant that is incapable of oxygenating organic substrates. tpa=tris(2-pyridylmethyl)amine.

    28. Direct Synthesis of 2-(Aminomethyl)indoles through Copper(I)-Catalyzed Domino Three-Component Coupling and Cyclization Reactions (pages 2295–2298)

      Hiroaki Ohno, Yusuke Ohta, Shinya Oishi and Nobutaka Fujii

      Article first published online: 15 FEB 2007 | DOI: 10.1002/anie.200604342

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      Tying up loose ends: A copper(I)-catalyzed three-component reaction has been developed that leads to the formation of 2-(aminomethyl)indole derivatives. Water is the sole theoretical by-product in this reaction in which two C[BOND]N bonds and one C[BOND]C bond are formed. This route to the indole nucleus in combination with a palladium-catalyzed functionalization of a C[BOND]H bond is also useful for the synthesis of polycyclic indoles (see scheme).

    29. Monitoring the Nucleation of Zeolites by Mass Spectrometry (pages 2299–2302)

      Stefan A. Pelster, Rainer Kalamajka, Wolfgang Schrader and Ferdi Schüth

      Article first published online: 14 FEB 2007 | DOI: 10.1002/anie.200604513

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      Mass production: A combination of mass spectrometry and dynamic light scattering has been used to monitor the nucleation and crystallization of all-silica MFI and MEL zeolites from aqueous solution. The formation of the crystals involves hydrolysis of the alkoxysilane, oligomerization of the silicates, nucleation of amorphous Si colloids, and transformation of these colloids to crystal structures (see picture).

    30. Total Synthesis of (±)-trans-Dihydronarciclasine through a Highly endo-Selective Diels–Alder Cycloaddition of 3,5-Dibromo-2-pyrone (pages 2303–2305)

      In-Ji Shin, Eun-Sil Choi and Cheon-Gyu Cho

      Article first published online: 15 FEB 2007 | DOI: 10.1002/anie.200604612

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      All essential functional groups in the natural product (±)-trans-dihydronarciclasine (1) were introduced with the correct relative configuration in a highly endo-selective Diels–Alder cycloaddition of 3,5-dibromo-2-pyrone with a styrene dienophile (see scheme). The total synthesis of 1 from these starting materials was completed in 11 steps and 15.8 % overall yield.

    31. Synthesis of Calix[3]dipyrrins by a Modified Lindsey Protocol (pages 2306–2309)

      Mitsunori Inoue, Chusaku Ikeda, Yuji Kawata, Sundararaman Venkatraman, Ko Furukawa and Atsuhiro Osuka

      Article first published online: 19 FEB 2007 | DOI: 10.1002/anie.200604882

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      Bowled over: Calix[3]dipyrrins were synthesized from pyrrole and aryl aldehyde precursors by the Lindsey protocol, modified by the presence of a small amount of water. These bowl-shaped macrocycles can accommodate three metal (M) ions such as NiII and CuII in a hexagonal M3O3 manner (see structure; Cu green, N blue, O red, C black).

    32. Catalyzed Tandem Reaction of 3-Silyloxy-1,5-enynes Consisting of Cyclization and Pinacol Rearrangement (pages 2310–2313)

      Stefan F. Kirsch, Jörg T. Binder, Benedikt Crone, Alexander Duschek, Timm T. Haug, Clémence Liébert and Helge Menz

      Article first published online: 20 FEB 2007 | DOI: 10.1002/anie.200604544

      Thumbnail image of graphical abstract

      Au-spicious! Under silver-free conditions, simple 3-silyloxy-1,5-enynes were converted into complex cyclopentenes by a gold(I)-catalyzed sequence that likely proceeds through a carbocyclization followed by a pinacol rearrangement. For the final demetalation step, isopropyl alcohol and N-iodosuccinimide are effectively utilized, and the resulting products are set up for a wealth of further reactions.

    33. Asymmetric Nucleophilic Glyoxylation through a Metalated α-Aminonitrile Derivative in Michael Additions to Nitroalkenes (pages 2314–2316)

      Dieter Enders, Maurice Hubert Bonten and Gerhard Raabe

      Article first published online: 15 FEB 2007 | DOI: 10.1002/anie.200604802

      Thumbnail image of graphical abstract

      Efficient and selective: An asymmetric nucleophilic glyoxylation has been achieved for the first time using a metalated glyoxylate aminonitrile derivative in Michael additions to nitroalkenes. After conversion of the aminonitrile back into the keto function with removal of the chiral auxiliary, the γ-nitro α-keto esters were available in good yields and excellent enantiomeric excesses (see scheme).

    34. Optical Sensing and Imaging of Trace Oxygen with Record Response (pages 2317–2319)

      Stefan Nagl, Carlos Baleizão, Sergey M. Borisov, Michael Schäferling, Mário N. Berberan-Santos and Otto S. Wolfbeis

      Article first published online: 26 FEB 2007 | DOI: 10.1002/anie.200603754

      Thumbnail image of graphical abstract

      Ultratrace quantities of oxygen can be determined at single spots as well as spatially resolved, and over a temperature range of more than 100 K, by exploiting the extremely efficient quenching of the delayed fluorescence of the fullerene C70 incorporated into matrices of organosilica or ethyl cellulose.

    35. Structural Assignment of Tetrabromostyloguanidine: Does the Relative Configuration of the Palau'amines Need Revision? (pages 2320–2324)

      Achim Grube and Matthias Köck

      Article first published online: 23 FEB 2007 | DOI: 10.1002/anie.200604076

      Thumbnail image of graphical abstract

      Products of the Caribbean: The palau'amine derivative tetrabromostyloguanidine 1 was isolated from the sponge Stylissa caribica and the elucidation of its structure with the focus on the relative configuration is discussed in detail. Results from NMR studies and molecular calculations suggest that the relative configuration for members of the palau'amine family differs from that earlier reported.

    36. Synthesis of the Transfer-RNA Nucleoside Queuosine by Using a Chiral Allyl Azide Intermediate (pages 2325–2327)

      Florian Klepper, Eva-Maria Jahn, Volker Hickmann and Thomas Carell

      Article first published online: 20 FEB 2007 | DOI: 10.1002/anie.200604579

      Thumbnail image of graphical abstract

      Chilled out: Chiral allyl azides are rarely used in natural product synthesis because of their tendency to undergo a [3.3] sigmatropic rearrangement (see scheme, top). In allylic cyclopentenyl azides, this rearrangement can be suppressed at just 0 °C, enabling a short convergent synthesis of the hypermodified transfer-RNA nucleoside queuosine.

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      Preview: Angew. Chem. Int. Ed. 14/2007 (page 2331)

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200790049

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