Angewandte Chemie International Edition in English

Cover image for Vol. 36 Issue 23

December 15, 1997

Volume 36, Issue 23

Pages 2537–2695

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 23/1997)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199725351

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      The cover picture shows schematically the catalytic formation of single enantiomers of 3-alkylcyclohexanones starting from cyclohexenones and the appropriate substituted alkenes. The alkenes are initially transformed into organozinc reagents that then add to the enone in a completely stereocontrolled, copper-catalyzed reaction. In the inner circle is a molecular model of a novel phosphoramidite that has been used as chiral ligand (the copper ion is indicated by a dotted sphere) in this 1,4-addition. Since several functionalized organozinc reagents are readily accessible from alkenes, this reaction and also the combined 1,4-addition/aldol reaction provide access to a variety of highly enantiomerically pure cyclohexanones. More about this method, which is also applicable to dienones, is reported by B. L. Feringa et al. on page 2620 ff. The authors thank Dr. J. Esch for the design of this picture.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Understanding Reactivity Patterns of Radical Cations (pages 2550–2589)

      Prof. Dr. Michael Schmittel and Dipl.-Chem. Armin Burghart

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199725501

      A terra incognita with a huge potential for chemical synthesis is opened by activation of organic substrates by one-electron transfer: Reactions of radical cation can be extremely selective when proper control over the primary and secondary reactions is attained. An analysis that combines the observed reactivity patterns of numerous instructive examples with thermodynamic and kinetic data leads to a useful categorization of radical cation reactivity and reveals the principles governing their mode of action. This should facilitate the directed planning of synthetic transformations with these intermediates.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. A Novel Methyltrioxorhenium (MTO)-Catalyzed Epoxidation of Olefins: An Impressive Example of Simplicity, Selectivity, and Efficiency (pages 2591–2592)

      Dr. Andreas Gansäuer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199725911

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      Simply by adding pyridine ligands and using aqueous hydrogen peroxide as stoichiometric oxidant the methyltrioxorhenium (MTO)-catalyzed epoxidation becomes a simple, chemoselective, and highly efficient reaction, as exemplified below. A wide variety of functional groups is tolerated, and the epoxides are obtained in high yield in a short time with low catalyst loading.

    2. Polyamides as Artificial Regulators of Gene Expression (pages 2592–2594)

      Dr. Klaus Weisz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199725921

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      Interference with the transcription of specific genes in vivo can be achieved with artificial, low molecular weight pyrrole-imidazole polyamides, as shown by recent studies by Gottesfeld, Dervan et al. This is possible because these ligands are capable of binding with high affinity and specificity to predetermined DNA sequences in the minor groove of double-stranded DNA (see schematic representation on the right; gray: pyrrole, black: imidazole units).

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Molecule-Sized Gates Based on Surface-Confined Dendrimers (pages 2596–2598)

      Mingqi Zhao, Dr. Hideo Tokuhisa and Prof. Richard M. Crooks

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199725961

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      Behavior as single-molecule gates for certain ions is demonstrated by dendrimers confined on surfaces and within thiol monolayers (see picture). The permeability depends on the chemical state of the dendrimer and the charge on the ion. These composite structures are models of biological membranes in that mass transfer occurs through the interior of the dendrimer in analogy to ion motion through membrane proteins.

    2. Tetrathia- and Tetraoxarubyrins: Aromatic, Core-Modified, Expanded Porphyrins (pages 2598–2601)

      Alagar Srinivasan, Dr. VenkatRam M. Reddy, S. Jeyaprakash Narayanan, Bashyam Sridevi, Simi K. Pushpan, Murugaeson Ravikumar and Prof. Dr. Tavarekere K. Chandrashekar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199725981

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      The remarkably simple synthesis of tetrathia- and tetraoxarubyrins 1 and 2 is achieved by the routes presented here. Spectroscopic, 1H NMR, and electrochemical data suggest that 1, 2, and their protonated derivatives are aromatic 26 π electron systems, and the protonated derivatives form stable complexes in solution with anions such as F, Nmath image, and adenosine 5′-monophosphate.

    3. Submolecularly Resolved Polymerization of Diacetylene Molecules on the Graphite Surface Observed with Scanning Tunneling Microscopy (pages 2601–2603)

      Dr. Petrus C. M. Grim, Steven De Feyter, André Gesquière, Peter Vanoppen, Dr. Markus Rüker, Dr. Suresh Valiyaveettil, Georg Moessner, Prof. Klaus Müllen and Prof. Frans C. De Schryver

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726011

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      The photopolymerization of a monolayer physisorbed on graphite and containing diacetylene derivatives comprising a isophthalic acid head group and a decyl group as nonpolar tail was studied by scanning tunneling microscopy (STM). The submolecularly resolved STM image on the right depicts a domain boundary between an unpolymerized monolayer (lower domain) and a polymerized monolayer (upper domain).

    4. Comparison of the Bioactive Conformations of Sialyl LewisX and a Potent Sialyl LewisX Mimic (pages 2603–2607)

      Dr. Wolfgang Jahnke, Dr. Hartmuth C. Kolb, Dr. Marcel J. J. Blommers, Dr. John L. Magnani and Dr. Beat Ernst

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726031

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      For the rational design of drugs that inhibit the interaction between E-selectin and sialyl LewisX, structural information on bound inhibitors is required. The bioactive conformation of the potent sialyl LewisX mimic 1 was therefore determined by transfer NOE NMR spectroscopic methods.

    5. Steric Stabilization of Nucleophilic Carbenes (pages 2607–2609)

      Prof. Dr. Michael K. Denk, Avinash Thadani, Dr. Ken Hatano and Dr. Alan J. Lough

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726071

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      Two tert-butyl groups at the nitrogen atoms of the cyclic carbene 2, which is accessible from 1 by reduction with potassium, provide sufficient stability to enable it to be stored indefinitely under exclusion of air and moisture. In contrast, sterically less shielded carbenes of type 2 (R = Me, Et, iPr) dimerize slowly at room temperature to olefins 3.

    6. Octaethyltetraselenaporphyrin Dication (pages 2609–2612)

      Prof. Dr. Emanuel Vogel, Dr. Christoph Fröde, Dr. Andreas Breihan, Dr. Hans Schmickler and Dr. Johann Lex

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726091

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      The electronic “umpolung” of the title compound 1 to the dianion 2 is achieved by the uptake of four electrons from potassium in THF. Although the ring skeleton of the 18π 1 deviates significantly from planarity because of the streric requirements of the four selenium atoms, the new macrocycle fulfils the NMR criteria for aromaticity.

    7. Contracted Porphyrins: Octaethylisocorrole (pages 2612–2615)

      Prof. Dr. Emanuel Vogel, Dr. Beate Binsack, Dr. Yvonne Hellwig, Dr. Christoph Erben, Andreas Heger, Dr. Johann Lex and Prof. Dr. Yun-Dong Wu

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726121

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      The most stable of the three possible structural isomers of corrole is, according to theory, isocorrole, for which the title compound 1 is a model compound. The reductive McMurry coupling of the corresponding α,ω-tetrapyrroledialdehyde affords an entry to 1. The isocorrole derivative 1 has, like corrole, the propensity to stabilize metals in high oxidation states. This is exemplified by the CuIII complex 2, which has been isolated as an intermediate in the synthesis of 9-formyloctaethylisocorrole.

    8. Twofold C[BOND]C Single Bond Activation and Cleavage in the Reaction of Octatetraynes with Titanocene and Zirconocene Complexes (pages 2615–2617)

      Dipl.-Ing. Paul-Michael Pellny, Dipl.-Chem. Normen Peulecke, Dr. Vladimir V. Burlakov, Dr. Annegret Tillack, Dr. Wolfgang Baumann, Dr. Anke Spannenberg, Dr. Rhett Kempe and Prof. Dr. Uwe Rosenthal

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726151

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      Cleavage or complexation of octatetraynes occur in the reaction with four titanocene or zirconocene units, depending on the groups R attached to the tetrayne. The structures of the products 1 and 2 have been unequivocally proven by spectroscopy and X-ray structure analysis.

    9. Synthetic, Structural, and Bonding Studies of Indacene Dianions (pages 2618–2620)

      Dr. Douglas R. Cary, Dr. Jennifer C. Green and Dr. Dermot O'Hare

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726181

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      Reduction of the formally antiaromatic compound 1,3,5,7-tetra-tert-butyl-s-indacene to the dianion 1 is achieved with lithium or potassium. Both salts were characterized by NMR spectroscopy and X-ray crystallography, which revealed that the polycyclic hydrocarbon framework exhibits a delocalized π-electron system, as does the neutral compound. The results of density functional theory calculations are in agreement with the experimental findings.

    10. Highly Enantioselective Catalytic Conjugate Addition and Tandem Conjugate Addition–Aldol Reactions of Organozinc Reagents (pages 2620–2623)

      Prof. Dr. Ben L. Feringa, Dr. Mauro Pineschi, Leggy A. Arnold, Rosalinde Imbos and André H. M. de Vries

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726201

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      Complete stereocontrol with the added advantage of functional-group tolerance in copper-catalyzed 1,4-additions of organozinc reagents to enones has been achieved for the first time with the chiral phosphoramidite L* as ligand in the copper complex [Eq. (a), Tf = trifluoromethanesulfonate]. The zinc enolate intermediate of the reaction can be trapped with aldehydes.

    11. Palladium-Catalyzed Cross-Coupling of Organozinc Bromides with Aryl Iodides in Perfluorinated Solvents (pages 2623–2624)

      Dipl.-Chem. Bodo Betzemeier and Prof. Dr. Paul Knochel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726231

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      A remarkable selectivity for iodide is characteristic of the Pd0 catalyst obtained from (F13C6C6H4)3P and [Pd(dba)2] in the cross-coupling of organozinc bromides with aryl iodides in a biphasic perfluorinated solvent [Eq. (a)]. In general, this method provides C[BOND]C coupled products in high yields and requires only a small amount of catalyst (0.15 mol %), which can be separated by simple phase separation and reused several times; dba = dibenzylideneacetone, TIPS = iPr3Si.

    12. Synthesis and Structure of Aluminum-Fluorine-Oxygen Clusters (pages 2625–2626)

      Dipl.-Chem. Said D. Waezsada, Dr. Feng-Quan Liu, Prof. Craig E. Barnes, Prof. Dr. Herbert W. Roesky, Dr. Mavis L. Montero and Dr. Isabel Usón

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726251

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      Depending on the size of the substituents R and R′, the recrystallization of (2,6-R2C6H3)[Si(R′)Me2]-NAlF2 · THF either leads back to the starting products, or to larger clusters. The corners of these clusters are occupied by aluminum atoms, the edges by fluorine atoms (a partial view of a cluster in the crystal is depicted on the right). An oxygen atom is located at the center of the tetrakishexahedron surrounded by six aluminum atoms. In molecular compounds this type of structure was only known for d-and f-block elements until now.

    13. A Sequential Photoinduced Electron Relay Accelerated by Fullerene in a Porphyrin-Pyromellitimide-C60 Triad (pages 2626–2629)

      Dr. Hiroshi Imahori, Koji Yamada, Masato Hasegawa, Seiji Taniguchi, Prof. Tadashi Okada and Prof. Yoshiteru Sakata

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726261

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      A model for the reaction center of photosynthesis is the porphyrin-imide-C60 triad 1. The C60 unit accelerates quenching of the excited singlet state of the porphyrin group. Thus, electron transfer can proceed either by a two-step process through the imide spacer with formation of a long-lived intermediate with seperated charge or directly through space.

    14. Detection of Scalar 6Li, 15N Coupling across Coordinative Li[BOND]N Bonds (pages 2629–2631)

      Dipl.-Chem. Dietmar Hüls, Prof. Dr. Harald Günther, Prof. Dr. Gerard van Koten, P. Wijkens and Dr. J. T. B. H. Jastrzebski

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726291

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      With natural abundance of 15N in the sample, scalar 6Li,15N spin–spin couplings across coordinative Li[BOND]N bonds were detected for the tetrameric organolithium compound 1 in solution and in the solid state. The coupling constants of 3.6 and 4.2 Hz correlate with the Li[BOND]N distances determined in the crystal structure analysis.

    15. Novel Alkyne Carbene Tungsten Complexes (pages 2631–2632)

      Rong-Zhi Ku, Der-Yi Chen, Gene-Hsiang Lee, Prof. Shie-Ming Peng and Prof. Shiuh-Tzung Liu

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726311

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      Only alkyne and carbene ligands surround the tungsten atom in complexes 1 and 2. Complex 1, which has been characterized by X-ray crystallography, catalyzes the polymerization of diphenylacetylene (see below). L [DOUBLE BOND] PhC [TRIPLE BOND] CPh.

    16. A Convergent Synthesis of (+)-Parviflorin, (+)-Squamocin K, and (+)-5S-Hydroxyparviflorin (pages 2632–2635)

      Prof. Dr. Barry M. Trost, Dr. Trevor L. Calkins and Dr. Christian G. Bochet

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726321

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      Thirty of the thirty-five carbon atoms of the acetogenin (+)-parviflorin (3, also named squamocin E) in this highly convergent synthesis derive from one building block, the readily accessible alcohol 1. The remaining five have their origin in an alkyne obtained from lactic acid. The key step of this general strategy to bis(tetrahydrofuran) acetogenins is a Ru-catalyzed Alder–ene coupling of the alkyne with a bis(tetrahydrofuran) made from two units of 1.

    17. Catalytic Asymmetric Alkylation of Nucleophiles: Asymmetric Synthesis of α-Alkylated Amino Acids (pages 2635–2637)

      Prof. Dr. Barry M. Trost and Dr. Xavier Ariza

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726351

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      The synthesis of modified peptides depends to a large extent on α-alkylated amino acids. Such amino acids can be prepared in a novel asymmetric synthesis with readily available azlactones: the allylic alkylations of a variety of azlactones catalyzed by palladium proceeds with excellent diastereo- and enantioselectivities [Eq. (a)].

    18. A Highly Efficient Aminohydroxylation Process (pages 2637–2640)

      A. Erik Rubin and Prof. K. Barry Sharpless

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726371

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      In the absence of external ligands α,β-unsaturated amides represent one of the few olefin classes which exhibit excellent rates and yields in osmium-catalyzed aminohydroxylation. The scope of the reaction was examined, and a one-pot method for the conversion of the hydroxysulfonamides 2 and 3 into the corresponding aziridines 4 developed. Ts = p-MeC6H4SO2.

    19. Di-, Tri-, and Tetranuclear Alkoxyaluminum Hydrides (pages 2640–2643)

      Prof. Dr. Heinrich Nöth, Dipl.-Chem. Andreas Schlegel, Dipl.-Chem. Jörg Knizek and Dr. Holger Schwenk

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726401

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      O- and/or H-bridged aluminum centers are found in the multinuclear alanes presented here. A peculiarity is the cage compound 1 (crystal structure shown on the right), in which all Al atoms are pentacoordinated. This is the first molecular compound with a tetracoordinated hydride ion.

      • equation image
    20. Synthesis and Structure of a Tetragallane [R4Ga4I3] and a Polyhedral Nonagallane [R6Ga9] (pages 2644–2646)

      Dipl.-Chem. Wolfgang Köstler and Dr. Gerald Linti

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726441

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      A doubly edge-bridged pentagonal bipyramid of gallium atoms (depicted on the right) occurs in the gallium cluster [R6Ga9] (1). Anion 1, like the electron-precise [(RGa)4I3], which has a heterocubane framework, is accessible from “GaI” and RLi(thf)3. R = Si(SiMe3)3.

    21. Atomically Resolved Structure of Fracture Surfaces of a Ba/Si/O/C Glass with Atomic Force Microscopy (pages 2646–2648)

      Dipl. Phys. Wolfgang Raberg, Dipl.-Chem. Volker Lansmann, Prof. Dr. Martin Jansen and Prof. Dr. Klaus Wandelt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726461

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      No periodic structures can be observed in the topographical scanning tunneling microscopy image of the fracture surface of a Ba/Si/O/C glass (see picture). The results reveal the enormous potential of this young method for the determination of characteristic structural elements in solids without translational symmetry.

    22. Sergeants-and-Soldiers Principle in Chiral Columnar Stacks of Disc-Shaped Molecules with C3 Symmetry (pages 2648–2651)

      Anja R. A. Palmans, Dr. Jef A. J. M. Vekemans, Dr. Edsko E. Havinga and Prof. Dr. E. W. Meijer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726481

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      Extremely effective cooperative effects operate during the formation of chiral stacks of C3-symmetrical molecules in alkane solvents (a molecule is depicted on the right). The sergeants-and-soldiers principles as well as chiral solvation lead to a preferred helical sense in the columnar aggregates. The amplification of chirality in dynamic systems shows the precision in aggregation.

    23. Ba2Nd7Si11N23—A Nitridosilicate with a Zeolite-Analogous Si–N Structure (pages 2651–2652)

      Dipl.-Chem. Hubert Huppertz and Prof. Dr. Wolfgang Schnick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726511

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      A synthetic access to novel nitridozeolites has been opened by the formal exchange of oxygen for nitrogen in microporous oxozeolites. Ba2Nd7Si11N23 is the first example of a network structure containing corner-sharing SiN4 tetrahedra with wide channels. In sharp contrast to conventional oxidic zeolites, this nitridozeolite is stable up to 1600 °C.

    24. Alkylrhenium Oxides from Perrhenates: A New, Economical Access to Organometallic Oxide Catalysts (pages 2652–2654)

      Prof. Dr. Wolfgang A. Herrmann, Roland M. Kratzer and Dr. Richard W. Fischer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726521

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      Methyltrioxorhenium in an Erlenmeyer flask: An in situ activation with chloroalkylsilanes converts readily available perrhenates into organorhenium(VII) oxides (as depicted below), which are valuable and diverse homogeneous catalysts. Reaction intermediates are trimethylsilyl perrhenate, dirhenium heptoxide, and chlorotrioxorhenium. The application of methyltrioxorhenium CH3ReO3 (1) in industrial processes might become feasible, particularly since the catalyst can be recycled.

    25. Repetitive Construction of Macrocyclic Oligophenylenes (pages 2654–2656)

      Dipl.-Chem. Volker Hensel, Dipl.-Chem. Karola Lützow, Prof. Dr. Arnulf-Dieter Schlüter, Dipl.-Krist. Joel Jacob, Dr. Katrin Gessler and Prof. Wolfram Saenger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726541

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      Suzuki cross-coupling has again proved itself as the method of choice for the formation of complex hydrocarbons. Macrocycles 1 could be synthesized from preformed oligophenylene modules. The crystal structure of 1a shows that each macrocycle contains a chloroform molecule, which is fixed in its position through a CH[BOND]π interaction.

    26. Solvation and the Synthesis of Self-Assembled Capsules (pages 2656–2659)

      Dr. Yuji Tokunaga, Dr. Dmitry M. Rudkevich and Prof. Julius Rebek Jr.

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726561

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      The solvent is the template! Reaction intermediates recognize solvent molecules S and encapsulate them (shown schematically on the right). The formation of covalent bonds could often proceed via noncovalently preassembled building blocks.

    27. Synthesis and Structure of ITQ-3, the First Pure Silica Polymorph with a Two-Dimensional System of Straight Eight-Ring Channels (pages 2659–2661)

      Dr. Miguel A. Camblor, Prof. Dr. Avelino Corma, Dr. Philip Lightfoot, Luis A. Villaescusa and Dr. Paul A. Wright

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726591

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      Hydrothermal syntheses in fluoride medium readily yield very open materials, as the example of ITQ-3 demonstrates. This new polymorph of silica with the formula [SiO2]64 has a framework characterized by a low density (16.3 SiO4 tetrahedra per 1000 Å3), a very large void volume (0.23 cm3 g−1), and a two-dimensional system of straight channels whose intersection defines a large cage (picture on the right).

    28. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene Immobilized in MCM-41: A Strongly Basic Porous Catalyst (pages 2661–2663)

      Dr. Yarlagadda V. Subba Rao, Dr. Dirk E. De Vos and Prof. Dr. Pierre A. Jacobs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726611

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      Michael additions, Knoevenagel condensations, and epoxidation of enones with H2O2 can be catalyzed under mild conditions with a new mesoporous base. Equation (a) shows the principle for a Michael addition (X = CN, Y = CO2Et); the catalyst is obtained by immobilization of a guanidine base in MCM-41.

    29. Absorption/Electron Transfer/Absorption— An Efficient Pathway to Hydrated Electrons in Laser Flash Photolysis (pages 2664–2666)

      Dr. Valentin Zubarev and Prof. Dr. Martin Goez

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726641

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      With quite high efficiency the route described here leads to solvated electrons (see below). In this pathway the second photon of a two-photon ionization is absorbed by a radical ion. The studies were conducted with the anthraquinone-1,5-disulfonate/methionine (A/D) system in water. Analogous results were obtained with triethylamine or sulfite ions in place of methionine.

    30. The Organic Chemsitry of Coordination Compounds: Unprecedented Substitution Reactions of Functionalized Polypyridine Complexes (pages 2666–2668)

      Dimitrios Tzalis and Prof. Dr. Yitzhak Tor

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726661

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      The increased electrophilicity of the complexed phenanthroline ring and the resonance stabilization of the “anionic” addition intermediate account for the unprecedented reactivity of the RuII and OSII coordination compounds shown in reaction (1), bpy = 2,2′-bipyridine: M = Ru, Os; X = SCH3, OCH3, F.

    31. The Linking of Two Acetylide Units through a Plane of Four Iron Atoms (pages 2668–2669)

      Dr. John E. Davies, Dr. Martin J. Mays, Dr. Paul R. Raithby and Koshala Sarveswaran

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726681

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      An unprecedented coordiantion mode for a diyne ligand is present in the Fe4 complex 2, which is accessible by thermolysis of the alkyne complex 1 in toluene at 373 K. In 2 the μ42 acetylide ligands on each Fe4 face are linked together by a C[BOND]C bond through the plane of four metal atoms.

    32. Enantioselective Diels–Alder Cycloaddition by Preorganization on a Chiral Lewis Acid Template (pages 2670–2673)

      Dr. Hugues Bienaymé

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726701

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      The key to success in asymmetric Diels–Alder cycloadditions may be the preorganization of the reactants through combined covalent and coordinative bonds (dative O[BOND]Ti interactions). Even reactions with the difficult, monodentate, C2v-symmetric maleimide dienophiles give the desired adducts in high yields and respectable enantioselectivities [Eq. (a)]. R1 = H, CH3; R2 = CH3, PhCH2, p-BrC6H4CH2, (R)-PhCH2(CH3).

    33. Cluster Assembly by Hydrogen Bonds: Channel Structure of Cu4L4 Cubanes (pages 2673–2675)

      Prof. Hiroki Oshio, Yuki Saito and Prof. Tasuku Ito

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726731

      A high-spin ground state characterizes the cubane complex, which was obtained from copper(II) acetate monohydrate and the bridging ligand 2-(4-hyroxysalicylidenamino)ethanol. In the crystal these cubane clusters are arranged to give a channel structure (depicted on the right), which is attributed to a hydrogen-bonding network formed between hydroxyl groups and water molecules.

    34. Synthesis of a Small-Pore Microporous Material Using a Computationally Designed Template (pages 2675–2677)

      Dr. Dewi W. Lewis, Dr. Gopinathan Sankar, Joanna K. Wyles, Prof. Sir John Meurig Thomas, Prof. C. Richard A. Catlow and Dr. David J. Willock

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726751

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      About four hours reaction time is all that is needed to synthesize the Chabazitic cobalt aluminophosphate (DAF-5) with 4-piperidinopiperidine as template. The template was designed with computer modeling techniques (resulting model shown on the right), after the desired properties of the microporous material had been identified. The work demonstrates the viability of such an approach for the synthesis of new microporous solids.

    35. Rapid and Highly Selective Cleavage of Ribonucleoside 2′,3′-Cyclic Monophosphates by Dinuclear CuII Complexes (pages 2678–2680)

      Dr. Shanghao Liu, Zhiyong Luo and Prof. Andrew D. Hamilton

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726781

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      Two characteristics that never before appeared together are combined in complexes 1 and 2, which show high activity and high selectivity in the hydrolysis of cyclic nucleoside 2′,3′-monophosphates as model compounds for RNA. In the case of 1 the regioselectivity is exceptional, and, in the case of 2, the base selectivity.

    36. A Calixarene with Four Peptide Loops: An Antibody Mimic for Recognition of Protein Surfaces (pages 2680–2683)

      Dr. Yoshitomo Hamuro, Dr. Mercedes Crego Calama, Dr. Hyung Soon Park and Prof. Andrew D. Hamilton

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726801

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      Four constrained cyclic peptides containing the sequence Gly-Asp-Gly-Asp are linked to a central calixarene scaffold (see diagram below) to form a large surface area for interaction with proteins. These antibody mimics not only bind strongly to the surface of cytochrome c but also disrupt its interaction with reducing agents.

    37. BaSn3: A Superconductor at the Border of Zintl Phases and Intermetallic Compounds. Real-Space Analysis of Band Structures (pages 2683–2686)

      Dr. Thomas F. Fässler and Christian Kronseder

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726831

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      Molecular wires 2 are formed by the stacking of Snmath image triangles 1 in BaSn3. The balanced interplay of interactions between localized and delocalized structural components is responsible for the super-conductivity of 2. The “fingerprint” in the band structure of this superconductor is discussed with the help of partial electron density (PED) introduced here as well as the electron localization function (ELF).

    38. Carbohydrates Coordinated to Platinum(IV) through Hydroxyl Groups: A New Class of Platinum Complexes with Bioactive Ligands (pages 2686–2688)

      Prof. Dr. Dirk Steinborn, Dipl.-Chem. Henrik Junicke and Dr. Clemens Bruhn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199726861

      Thumbnail image of graphical abstract

      In the first carbohydrate complexes of platinum(II). 1,2-O-isopropylidene-α-D-gluco- and -α-D-allofuranose are coordinated to the trimethylplatinum cation only by three OH groups. These are also the only complexes of platinum that contain neutral carbohydrate ligands without anchor groups. The structure of the glucofuranose complex cation [PtMe3(C9H16O6)] is depicted on the right.

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