Angewandte Chemie International Edition

Cover image for Vol. 43 Issue 2

December 29, 2003

Volume 43, Issue 2

Pages 131–259

    1. Cover Picture: Supramolecular Construction of Molecular Ladders in the Solid State (Angew. Chem. Int. Ed. 2/2003) (page 131)

      Xiuchun Gao, Tomislav Friščić and Leonard R. MacGillivray

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200390642

      A supramolecular approach to covalent synthesis allows the photoconversion of polyenes into ladderanes, which are challenging synthetic targets discovered in the lipid membranes of the anammox bacteria that participate in the oceanic nitrogen cycle. In their Communication on page 232 ff. X. Gao, T. Friščić, and L. R. MacGillivray explain how solid-state synthesis directed by molecular templates can provide gram quantities of the ladderanes in quantitative yield. Thus, ladderanes bridge a gap between conventional synthesis, supramolecular chemistry, and biology.

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      Anion–π Interactions: Do They Exist? (page 141)

      David Quiñonero, Carolina Garau, Carmen Rotger, Antonio Frontera, Pablo Ballester, Antonio Costa and Pere M. Deyà

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200390644

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      Silynes (RC≡SiR′) and Disilynes (RSi≡SiR′): Why Are Less Bonds Worth Energetically More? (page 141)

      David Danovich, François Ogliaro, Miriam Karni, Yitzhak Apeloig, David L. Cooper and Sason Shaik

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200390646

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      Conductive Organic Plastic Crystals Based on Pyrazolium Imides (page 141)

      Yaser Abu-Lebdeh, Pierre-Jean Alarco and Michel Armand

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200390647

    5. Binary Superlattices of Nanoparticles: Self-Assembly Leads to “Metamaterials” (pages 148–149)

      Andrey L. Rogach

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200301704

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      A simple bottom-up approach allows the aggregation of nanoparticles to a variety of superlattices with controlled collective properties. For example, monodisperse magnetic Fe2O3 nanocrystals (blue) and PbSe semiconductor quantum dots (red) form a binary three-dimensional AB13-type superlattice by self-assembly (see picture).

    6. Bioinspired Molecular Design of Light-Harvesting Multiporphyrin Arrays (pages 150–158)

      Myung-Seok Choi, Tomoko Yamazaki, Iwao Yamazaki and Takuzo Aida

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200301665

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      Coming to the point: Light-harvesting multiporphyrin arrays can be seen as molecular models for photochemical events in biological photosynthesis. This Minireview examines the structural parameters that enable the design of arrays with a large absorption cross-section for visible light and allow a vectorial transfer of the excitation energy to a designated point (see picture).

    7. Comments on Recent Achievements in Biomimetic Organic Synthesis (pages 160–181)

      María C. de la Torre and Miguel A. Sierra

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200200545

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      Inspiration or imitation? A biomimetic strategy pursues the development of synthetic methodology that imitates a natural biogenetic process. Not all biosyntheses can be mimicked in vitro. A biomimetic route to a natural product is more likely to be successful when the involvement of enzymes in the biological route being mimicked is low.

    8. Synthesis and Reactivity of a 1,8-Bis(methylium)naphthalenediyl Dication (pages 184–187)

      Huadong Wang and François P. Gabbaï

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200353011

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      A voracious appetite for electrons is displayed by the 1,8-bis(methylium)naphthalenediyl dication (see picture). Cooperative effects arising from the proximity of the methylium centers intensify the electron affinity of this molecule and make it very sensitive to reduction.

    9. NMR Spectroscopic Determination of the Solution Structure of a Branched Nucleic Acid from Residual Dipolar Couplings by Using Isotopically Labeled Nucleotides (pages 187–192)

      Bernd N. M. van Buuren, Jürgen Schleucher, Valentin Wittmann, Christian Griesinger, Harald Schwalbe and Sybren S. Wijmenga

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200351632

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      Only a small set of magnetic-field-induced residual dipolar couplings is required to determine the global structure of branched nucleic acids. This is demonstrated for the example of the Holliday junction (shown schematically) after 13C labeling in the ribose of specific thymine residues. Accurate calculation of the magnetic-field-induced alignment tensor for any nucleic acid conformation allows the reduction in the required number of parameters.

    10. A Neutral 3D Copper Coordination Polymer Showing 1D Open Channels and the First Interpenetrating NbO-Type Network (pages 192–195)

      Xian-He Bu, Ming-Liang Tong, Ho-Chol Chang, Susumu Kitagawa and Stuart R. Batten

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352024

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      Being bulky is good: The use of a bulky multifunctional ligand is key to the successful construction of a neutral 3D copper coordination polymer that shows 1D open channels and the first interpenetrating NbO-type network (see picture). The absorption properties of the complex are investigated.

    11. A Tetraguanidinium Ligand Binds to the Surface of the Tetramerization Domain of Protein P53 (pages 196–198)

      Xavier Salvatella, Marc Martinell, Margarida Gairí, Mauricio G. Mateu, Miguel Feliz, Andrew D. Hamilton, Javier de Mendoza and Ernest Giralt

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352115

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      A key therapeutic target in the fight against cancer, the tetramerization domain of the tumor suppressor protein P53 binds a tetraguanidinium ligand at its surface. A specific interaction involving four salt bridges was detected by two NMR-based techniques (see figure). The design of protein-surface ligands is a major challenge because of competition between the ligand and water molecules.

    12. Dynamics of Ordered-Domain Formation of DNA fragments on Au(111) with Molecular Resolution (pages 198–203)

      Hainer Wackerbarth, Mikala Grubb, Jingdong Zhang, Allan G. Hansen and Jens Ulstrup

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352146

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      Binding of single-strand oligonucleotides with ten adenine bases to single-crystal Au(111) through hexamethylene thiol has been studied by cyclic voltammetry and in situ scanning tunneling microscopy. The high surface coverage is in keeping with adsorption in the upright position. Strongly negative potentials give long-range ordered-adsorbate domains, which are characterized to single-molecule resolution (see picture).

    13. A Better Understanding of the Self-Structuration of Bridged Silsesquioxanes (pages 203–206)

      Joël J. E. Moreau, Benoît P. Pichon, Michel Wong Chi Man, Catherine Bied, Hans Pritzkow, Jean-Louis Bantignies, Philippe Dieudonné and Jean-Louis Sauvajol

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352485

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      The best solution? A highly crystalline hybrid silica has been obtained through the hydrolysis of a precursor in the solution phase. The self-organized structure of the lamellar material consists of diureido–phenylene bridging units (see picture); structural comparisons of this material and its molecular precursor show the existence of similar hydrogen-bonding interactions in both structures.

    14. Two Unprecedented 3-Connected Three-Dimensional Networks of Copper(I) Triazolates: In Situ Formation of Ligands by Cycloaddition of Nitriles and Ammonia (pages 206–209)

      Jie-Peng Zhang, Shao-Liang Zheng, Xiao-Chun Huang and Xiao-Ming Chen

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352627

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      One-pot synthesis of 1,2,4-triazoles: Hydrothermal treatment of copper(II) ions, ammonia, and nitriles yielded two copper(I) triazolate coordination polymers, the structures of which have unearthed the unprecedented formation of triazolates through the cycloaddition of NH3 and RC[TRIPLE BOND]N. The polymers exhibit novel network topologies based on trigonal nodes (see picture).

    15. Hexanuclear Manganese(III) Single-Molecule Magnets (pages 210–212)

      Constantinos J. Milios, Catherine P. Raptopoulou, Aris Terzis, Francesc Lloret, Ramon Vicente, Spyros P. Perlepes and Albert Escuer

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200351079

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      Clusters of magnets: The first examples of manganese single-molecule magnets (SMMs) consisting exclusively of trivalent metal centers are reported. These are hexanuclear clusters containing the [MnIII63-O)22-OR)2]12+ core (see picture, Mn yellow, O red) and have an S=4 ground state. Variation of the oxygen-containing ligands allows a potentially large family of SMMs to be prepared.

    16. Activation of C[BOND]Cl and C[BOND]H Bonds by Ligated S22− Ions: Conversion of Organic Chlorides into Organosulfur Compounds in cis-[(IrCp*)2(μ-CH2)2(μ-S2R)]+ (pages 213–215)

      Tarlok Singh Lobana, Kiyoshi Isobe, Hiroaki Kitayama, Takanori Nishioka and Isamu Kinoshita

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200351792

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      Cleaning up with sulfur: The multiple C[BOND]Cl bonds of toxic, polychlorinated organic compounds can be activated by the coordinated S2 ligand of complex 1. For example, reaction of 1 with C6H5-CHCl2 or C6H5-CCl3 in methanol forms a dithiobenzoate complex, which on addition of NaBPh4 provides complex 2; Cp*=C5Me5.

    17. Highly Enantioselective Construction of a Chiral Tertiary Carbon Center by Alkynylation of a Cyclic N-Acyl Ketimine: An Efficient Preparation of HIV Therapeutics (pages 216–218)

      Biao Jiang and Yu-Gui Si

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352301

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      Second-generation nonnucleoside reverse transcriptase inhibitors can now be efficiently prepared. Alkynylation of the ketimine (see scheme; PMB=p-methoxybenzyl) leads to the synthesis of tertiary amines in excellent yield and with high enantioselectivity. The ligand used in the reaction is a derivative of chloramphenicol base.

    18. Hydrido(hydrosilylene)tungsten Complexes with Strong Interactions between the Silylene and Hydrido Ligands (pages 218–221)

      Takahito Watanabe, Hisako Hashimoto and Hiromi Tobita

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352383

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      A hydrido ligand bridging a W[DOUBLE BOND]Si bond is present in a novel hydrido(hydrosilylene)–tungsten complex (see picture) and its η5-C5Me5 analogue, which were synthesized by photolysis of [Cp′W(CO)3Me] (Cp′=η5-C5Me4Et, η5-C5Me5) in the presence of H3SiC(SiMe3)3. This strong hydrido–silylene interligand interaction was revealed by NMR spectroscopic and X-ray structural analyses.

    19. Direct Evidence for Extremely Facile 1,2- and 1,3-Group Migrations in an FeSi2 System (pages 221–224)

      Hiromi Tobita, Akihisa Matsuda, Hisako Hashimoto, Keiji Ueno and Hiroshi Ogino

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352519

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      Facile 1,2- and 1,3-group migrations: The first donor-free silyl(silylene)–iron complex 1 has been prepared and structurally characterized (see scheme). This complex reacts with tBuNC under mild heating to give a disilanyl complex 2 through 1,3-alkyl and aryl migration and 1,2-silyl migration processes. Complex 2 is an example of how organosilicon species bound to transition-metal centers can change their form in a dynamic fashion (Mes=2,4,6-trimethylphenyl).

    20. Synthesis and Biological Evaluation of an Indomethacin Library Reveals a New Class of Angiogenesis-Related Kinase Inhibitors (pages 224–228)

      Claudia Rosenbaum, Patrick Baumhof, Ralf Mazitschek, Oliver Müller, Athanassios Giannis and Herbert Waldmann

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352582

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      Capture and release: Indomethacin has served as a lead compound for the synthesis of a library that revealed a new class of kinase inhibitors. A synthetic approach termed “resin-capture-release” was developed (see scheme) that allowed a large library to be synthesized easily. Six of the library compounds were found to be inhibitors of angiogenesis-related receptor tyrosine kinases.

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      Noble-Metal Nanotubes (Pt, Pd, Ag) from Lyotropic Mixed-Surfactant Liquid-Crystal Templates (pages 228–232)

      Tsuyoshi Kijima, Takumi Yoshimura, Masafumi Uota, Takayuki Ikeda, Daisuke Fujikawa, Shinji Mouri and Shinji Uoyama

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352630

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      Platinum, palladium, and silver nanotubes of 6–7-nm outer diameters are synthesized by the reduction of metal salts confined to lyotropic mixed-surfactant liquid crystals (see picture). The lyotropic liquid crystals act as a template and are formed by the 1:1 combination of medium and large surfactant molecules into a hexagonal array of cylindrical rodlike micelles.

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      Supramolecular Construction of Molecular Ladders in the Solid State (pages 232–236)

      Xiuchun Gao, Tomislav Friščić and Leonard R. MacGillivray

      Article first published online: 5 NOV 2003 | DOI: 10.1002/anie.200352713

      Thumbnail image of graphical abstract

      Steps in supramolecular chemistry: Molecules in the form of linear templates have been used to preorganize polyenes in the solid state through hydrogen-bonding interactions. The polyenes can then undergo [2+2] photocycloaddition reactions to produce [3]- and [5]ladderanes in gram quantities and 100 % yield. (The picture shows the obtained [5]ladderane.)

    23. A Titanosilicate That Is Structurally Analogous to an MWW-Type Lamellar Precursor (pages 236–240)

      Weibin Fan, Peng Wu, Seitaro Namba and Takashi Tatsumi

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352723

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      With an analogous structure to an MWW lamellar precursor, a titanosilicate (denoted Ti-YNU-1) has been developed by using a postsynthetic acid-treatment and calcination procedure (see scheme). The material behaves as a large-pore zeolite, showing high activity, selectivity, and stability towards the liquid-phase epoxidation of bulky cycloalkenes using H2O2 as an oxidant.

    24. Three-Level Synthetic Strategy Towards Mixed-Valence and Heterometallic [2×2] Gridlike Arrays (pages 240–243)

      Lindsay H. Uppadine and Jean-Marie Lehn

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200352937

      Thumbnail image of graphical abstract

      Regioselective, redox, and chiroselective features were used in a three-tiered synthesis to construct Coequation imageMequation image [2×2] grid-type arrays (MII=CoII, ZnII, FeII; see picture). The assemblies are based on a bis(hydrazone) ligand containing ionizable and non-ionizable compartments. This route allows the cobalt oxidation state to be selectively modified according to the charge on the hydrazone moiety.

    25. Self-Assembly in a Bipolar Phosphocholine–Water System: The Formation of Nanofibers and Hydrogels (pages 245–247)

      Karen Köhler, Günter Förster, Anton Hauser, Bodo Dobner, Ulrich F. Heiser, Friederike Ziethe, Walter Richter, Frank Steiniger, Markus Drechsler, Heiko Stettin and Alfred Blume

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200351731

      Thumbnail image of graphical abstract

      The bolaamphiphile PC-C32-PC with two phosphocholine headgroups and one long C32 alkyl chain (see the space-filling model, left) forms nanofibrils in aqueous solution at room temperature solely by hydrophobic interactions. The gels that result were studied by electron microscopy (image on the right), differential scanning calorimetry, and FT-IR spectroscopy. At higher temperatures the fibers “melt” and small aggregates form.

    26. Ligand-Supported Homology Modeling of G-Protein-Coupled Receptor Sites: Models Sufficient for Successful Virtual Screening (pages 248–251)

      Andreas Evers and Gerhard Klebe

      Article first published online: 2 DEC 2003 | DOI: 10.1002/anie.200352776

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      Virtual proteins: A computer method is described that uses ligand information in the homology modeling of proteins. This method was used to construct a model of a G-protein-coupled receptor, which was successfully used as a basis for structure-based drug design by virtual computer screening (see picture).

    27. Farnesyltransferase Inhibitors Inhibit the Growth of Malaria Parasites In Vitro and In Vivo (pages 251–254)

      Jochen Wiesner, Katja Kettler, Jacek Sakowski, Regina Ortmann, Alejandro M. Katzin, Emília A. Kimura, Katrin Silber, Gerhard Klebe, Hassan Jomaa and Martin Schlitzer

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200351169

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      The inhibition of farnesyltransferase was recently suggested as a new strategy for malaria therapy. A class of farnesyltransferase inhibitors such as 1 has been prepared which have in vivo activity in a murine malaria model. These inhibitors significantly reduce the farnesylation of parasite proteins.

    28. Preview: Angew. Chem. Int. Ed. 2/2003 (page 259)

      Article first published online: 19 DEC 2003 | DOI: 10.1002/anie.200390645

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