Angewandte Chemie International Edition

Cover image for Vol. 42 Issue 8

February 24, 2003

Volume 42, Issue 8

Pages 839–955

    1. Cover Picture: Structural Color and the Lotus Effect (Angew. Chem. Int. Ed. 8/2003) (page 839)

      Zhong-Ze Gu, Hiroshi Uetsuka, Kazuyuki Takahashi, Rie Nakajima, Hiroshi Onishi, Akira Fujishima and Osamu Sato

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390224

      Learning from nature to design the materials of the future. The cover picture shows the Morpho butterfly, whose wings displays structural color, and lotus leaves, which exhibit hydrophobicity. To mimic these natural products, materials were prepared that utilize the unique structural properties of an inverse opal film, which displays uniform structural colors and a surface with well-ordered bumps that aid hydrophobicity. Modification leads to a superhydrophobic surface with a large water-contact angle. For more information see the Communication by O. Sato et al. on page 894 ff.

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      The 50th Birthday of the Organocuprates (page 849)

      Norbert Krause

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390226

    3. The Electrophilic Substitution of Arenes: Is the π Complex a Key Intermediate and What is Its Nature? (pages 854–857)

      Dieter Lenoir

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390231

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      Aromatic substitution in detail: How does one prove that the intermediate charge-transfer (CT) complex (see scheme, where E=electrophile) is a key intermediate in the electrophilic substitution of arenes, and what is the structure, nature, and significance of this intermediate? On the basis of recent experimental findings these questions and others will be examined.

    4. The Direct Catalytic Asymmetric Cross-Aldol Reaction of Aldehydes (pages 858–860)

      Benito Alcaide and Pedro Almendros

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390232

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      Although the more elegant and most economically attractive way to introduce chirality into a molecule is by using a catalytic amount of chiral controller to induce chiral transformation without the need for any other activation of the starting materials, the first report of chemical catalysis for the direct catalytic asymmetric cross-aldol reaction of aldehydes has only recently appeared (see scheme).

    5. NMR Spectroscopy Techniques for Screening and Identifying Ligand Binding to Protein Receptors (pages 864–890)

      Bernd Meyer and Thomas Peters

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390233

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      Picking the locks of protein binding: NMR spectroscopic techniques for the characterization of binding processes have recently gained much attention. Binding epitopes on the ligands and on the protein can be identified easily without the aid of crystal structures (see scheme). Hereby, rational design of new drugs has become more accessible.

    6. Improved Methanol-to-Olefin Catalyst with Nanocages Functionalized through Ship-in-a-Bottle Synthesis from PH3 (pages 892–894)

      Weiguo Song and James F. Haw

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390234

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      Active phosphate flotsam: Tetramethylphosphonium cations can be prepared in the cages of HSAPO-34 catalysts from PH3 and methanol by using a ship-in-a-bottle approach (see picture). Calcination of this material leaves phosphate debris in some of the cages, which produces an active methanol-to-olefin catalyst with improved ethylene selectivity.

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      Structural Color and the Lotus Effect (pages 894–897)

      Zhong-Ze Gu, Hiroshi Uetsuka, Kazuyuki Takahashi, Rie Nakajima, Hiroshi Onishi, Akira Fujishima and Osamu Sato

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390235

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      Dry and bright: To mimic the wings of the displayed Morpho butterfly, a new decorative material that exhibits both structural color and superhydrophobicity (the “lotus effect”) was developed by taking advantage of the unique structural properties of an inverse opal film, which was fabricated by the self-assembly of polystyrene spheres and silica nanoparticles.

    8. Ionic Quaterrylenebis(dicarboximide): A Novel Mesogen and Long-Wavelength Polarizing Material (pages 897–900)

      Suk-Wah Tam-Chang, Wonewoo Seo, Isaac K. Iverson and Sean M. Casey

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390236

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      An absorbing study: The displayed quaterrylenebis(dicarboximide) was imparted with lyotropic liquid-crystalline properties by molecular design. The ability of the molecule to self-organize in solution allows for the subsequent control of its orientation in thin solid films. Induced orientation of the liquid-crystalline domains of the molecule under a shearing force results in highly anisotropically ordered films that serve as dichroic polarizers of light at wavelengths greater than 600 nm.

    9. Sc3N@C68: Folded Pentalene Coordination in an Endohedral Fullerene that Does Not Obey the Isolated Pentagon Rule (pages 900–903)

      Marilyn M. Olmstead, Hon Man Lee, James C. Duchamp, Steven Stevenson, Daniela Marciu, Harry C. Dorn and Alan L. Balch

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390237

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      Breaking the rule: The structure of Sc3N@C68⋅[NiII(OEP)]⋅2 C6H6 has been determined by single-crystal X-ray diffraction. The fullerene cage exists as an isomer with D3 symmetry (see picture), as initially predicted by density functional calculations. The scandium atoms are located over the centers of three pentalene units within the three-cornered carbon cage, which cannot obey the isolated pentagon rule. OEP=Octaethylporphyrinate.

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      A Three-Dimensional Array for Multiparallel Synthesis (pages 903–905)

      Sergey A. Kozmin and Ying Wang

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390238

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      An operationally simple and general technique for multiparallel organic synthesis is based on the three-dimensional delivery of reactants to an array of interconnected reaction wells. This technology can be readily adapted to the design of substantially large arrays, or multiple copies of interconnected arrays, thus allowing the necessary flexibility for the synthesis and screening of a wide range of chemical libraries.

    11. Hyperstranded DNA Architectures Observed by Cold-Spray Ionization Mass Spectrometry (pages 905–908)

      Shigeru Sakamoto and Kentaro Yamaguchi

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390239

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      Detection and characterization of unstable and complex DNA species, including hyperstranded DNA species such as the forklike structure of replicating DNA (see picture), is made possible by cold-spray ionization mass spectrometry.

    12. Hydrogen from Methane and Supercritical Water (pages 909–911)

      Andrea Kruse and Eckhard Dinjus

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390240

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      More rapidly to the target: Screening experiments in a miniautoclave demonstrate the different effects of catalytically active additives such as Raney nickel and basic alkali-metal compounds on the reaction of methane in supercritical water. Accordingly, this opens up the possibility to convert methane into hydrogen and carbon dioxide with water in a single process step without the need to pass through the intermediate carbon monoxide stage which is currently necessary in industrial set ups (see scheme).

    13. [Ge8{N(SiMe3)2}6]: A Ligand-Stabilized Ge Cluster Compound with Formally Zero-Valent Ge Atoms (pages 911–913)

      Andreas Schnepf and Ralf Köppe

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390241

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      Starting from germanium(I) bromide, which can be obtained by preparative co-condensation, the first polyhedral Ge cluster [Ge8{N(SiMe3)2}6] (see picture) has been synthesized in which the average oxidation state of all the Ge atoms in the cluster core lies between 0 and +1.

    14. Preparation and Asymmetric Hydrogenation of β-Aryl-Substituted β-Acylaminoacrylates (pages 913–916)

      Jingsong You, Hans-Joachim Drexler, Songlin Zhang, Christine Fischer and Detlef Heller

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390242

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      The Rh-catalyzed asymmetric hydrogenation of β-aryl-substituted (E)-β-acylaminoacrylates, which were isolated for the first time, with, for example [Rh{(R,R)-(Et-FerroTANE)}(nbd)]+ as catalyst (see picture) proceeds under very mild conditions (25 °C, normal pressure) and high substrate/catalyst ratios with very good enantioselectivity (Et-FerroTANE=(+)-1,1′-bis(2,4-diethylphosphyltane)ferrocene, nbd=3,5-norbornadiene).

    15. Synthesis of the First Fully Active Lipoteichoic Acid (pages 916–920)

      Andreas Stadelmaier, Siegfried Morath, Thomas Hartung and Richard R. Schmidt

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390243

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      Nature outfoxed! Owing to the sensitivity of lipoteichoic acids (LTAs) to hydrolysis their biological activity could not be ascertained thus far. The chemical synthesis of LTA of Staphylococcus aureus1, which contains hydrolytically labile D-alanine residues in the required ratio with other substituents, resulted in the same activity as exhibited by the natural product obtained by a new isolation procedure. Thus, the biological activity of LTA could be ascertained for the first time.

    16. A Spiro-Fused Triarylaminium Radical Cation with a Triplet Ground State (pages 921–924)

      Akihiro Ito, Masashi Urabe and Kazuyoshi Tanaka

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390244

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      Novel spirobis(radical cation) 12+ was prepared to examine the magnetic interaction between the two radical centers. The dication 12+ was found to be a robust triplet diradical on the basis of the ESR spectrum, magnetic susceptibility measurements, which indicated ferromagnetic interaction between the radical centers (i.e., J>0), and quantum chemical calculations.

      Corrected by:

      Corrigendum: A Spiro-Fused Triarylaminium Radical Cation with a Triplet Ground State

      Vol. 48, Issue 32, 5785, Version of Record online: 22 JUL 2009

    17. [1.1]Diborataferrocenophane: A Highly Efficient Li+ Scavenger (pages 924–927)

      Matthias Scheibitz, Rainer F. Winter, Michael Bolte, Hans-Wolfram Lerner and Matthias Wagner

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390245

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      A naked lithium cation is efficiently trapped within the [1.1]diborataferrocenophane dianion [1]2−, but released upon electrochemical oxidation of the ferrocene moieties. The complex [1-Li]Li([12]crown-4)2 provides the first experimental evidence for a theoretically predicted ferrocene⋅⋅⋅Li+ complex in which the Li+ ion is laterally bound to the Fe atom.

    18. Intercalation of Alkali Metal Cations into Layered Organotitanium Oxides (pages 927–930)

      José Gracia, Avelino Martín, Miguel Mena, María del Carmen Morales-Varela, Josep-M. Poblet and Cristina Santamaría

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390246

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      Deprotonation of the complex [{Ti(η5-C5Me5)(μ-O)}33-CH)] with different alkali metal alkyl and amide reagents provides a method for the intercalation of alkali-metal ions into layered organometallic titanium oxides (see picture). The process and the structures were analyzed by DFT calculations.

    19. Unselective Phenolic Coupling of Methyl 2-Hydroxy-4-methoxy-6-methylbenzoate—A Valuable Tool for the Total Synthesis of Natural Product Families (pages 931–933)

      Daniel Drochner, Wolfgang Hüttel, Martin Nieger and Michael Müller

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390247

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      One monomeric orsellinate (1) suffices for a highly efficient total synthesis of the dimeric coumarins kotanin, isokotanin A, and desertorin C. The reason is the unselective course of its oxidative phenolic coupling, which leads to three regioisomeric biaryls as precursors of the dimers.

    20. A Nanotubular 3D Coordination Polymer Based on a 3d–4f Heterometallic Assembly (pages 934–936)

      Bin Zhao, Peng Cheng, Yan Dai, Cai Cheng, Dai-Zheng Liao, Shi-Ping Yan, Zong-Hui Jiang and Geng-Lin Wang

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390248

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      Large pores comprising 48-membered rings characterize the isostructural lanthanide–transition-metal coordination polymers [{[Ln(dipic)3Mn1.5(H2O)3]⋅n H2O}], H2dipic=pyridine-2,6-dicarboxylic acid; Ln=Pr, n=2 (shown here); Ln=Gd, n=3.5; Ln=Er, n=3. Many water molecules are trapped in the nanotubular structure, and the framework remains intact on removal of the uncoordinated water molecules.

    21. Trinuclear Ruthenium Polyhydride Complexes with a Triply Bridging Ligand: [{(η5-C5Me5)Ru}33-M)(μ-H)33-H)] (M=Li, MgiPr, and ZnEt) and [{(η5-C5Me5)Ru}33-M)(μ-H)3] (M=AlEt and GaMe) (pages 937–940)

      Masato Ohashi, Kouki Matsubara, Takashi Iizuka and Hiroharu Suzuki

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390249

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      The cluster's clever cap: Treatment of 1 with an equimolar amount of diethylzinc yields the cluster 2 together with the elimination of ethane (see scheme). The pentahydride 1 also reacts with metal alkyls, such as MgiPr2, MeLi, AlEt3, and GaMe3, to yield complexes 36 analogous to 2 that contain a triply bridged metal ligand. The effect of these ligands on reactivity is evaluated by means of cyclic voltammetry.

    22. Asymmetric Epoxidation of Homoallylic Alcohols and Application in a Concise Total Synthesis of (−)-α-Bisabolol and (−)-8-epi-α-Bisabolol (pages 941–943)

      Naoya Makita, Yujiro Hoshino and Hisashi Yamamoto

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390250

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      Vanadium triisopropoxide oxide and an α-amino acid-based hydroxamic acid (e.g. 1) form the catalyst for the asymmetric epoxidation of homoallylic alcohols presented here. 3-Substituted alcohols 2 were epoxidized to the corresponding epoxy alcohols 3 with good ee values. In addition, a concise total synthesis of (−)-α- and (−)-8-epi-α-bisabolol was achieved.

    23. Phospholane–Oxazoline Ligands for Ir-Catalyzed Asymmetric Hydrogenation (pages 943–946)

      Wenjun Tang, Weimin Wang and Xumu Zhang

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390251

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      A new class of chiral phospholane–oxazoline ligands P* was developed for Ir-catalyzed asymmetric hydrogenation (see scheme, e.g. R=Ph; Ar=m-CH3C6H4). High enantioselectivities (up to 99 % ee) were obtained for the hydrogenation of methylstilbene derivatives and (E)-β-methylcinnamic esters.

    24. A Highly Practical and Enantioselective Reagent for the Allylation of Aldehydes (pages 946–948)

      Katsumi Kubota and James L. Leighton

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390252

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      Strain at silicon is the key to success of reagent 1 since this strain, which is induced by the diazasilacyclopentane ring, determines its reactivity. This practical and general new reagent for the highly enantioselective allylation of aldehydes is easily prepared as an air-stable solid and may be stored without significant decomposition.

    25. A General Oxidative Cyclization of 1,5-Dienes Using Catalytic Osmium Tetroxide (pages 948–951)

      Timothy J. Donohoe and Sam Butterworth

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390253

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      Dihydroxylation of 1,5-dienes under acidic conditions is sufficient to induce an efficient oxidative cyclization that produces stereochemically defined tetrahydrofurans in one step [Eq. (1)]. This method is very general and efficient for a range of dienes and shows complete stereoselectivity for formation of the 2,5-cis diastereoisomers. Bn=benzyl, CSA=camphorsulfonic acid.

    26. Preview: Angew. Chem. Int. Ed. 8/2003 (page 955)

      Version of Record online: 21 FEB 2003 | DOI: 10.1002/anie.200390254

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