Angewandte Chemie International Edition

Cover image for Vol. 42 Issue 32

August 18, 2003

Volume 42, Issue 32

Pages 3703–3837

    1. Cover Picture: Templating of Silsesquioxane Cross-Linking Using Unimolecular Self-Organizing Polymers (Angew. Chem. Int. Ed. 32/2003) (page 3703)

      Eric F. Connor, Linda K. Sundberg, Ho-Cheol Kim, Jeroen J. Cornelissen, Teddie Magbitang, Phil M. Rice, Victor Y. Lee, Craig J. Hawker, Willi Volksen, James L. Hedrick and Robert D. Miller

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200390549

      From Nanoscience to Nanotechnology: Sacrificial micellar star-shaped polymers template their image in a thermosetting resin to generate a nanoporous film for the insulation of on-chip metal wiring. The uniform pore size and shape of the pores is solely determined by the molecular weight of the polymer, which is, in turn, controlled by using living polymerization techniques. More about this methodology is given in the Communication by R. D. Miller, J. L. Hedrick, and co-workers on page 3785 ff.

    2. Graphical Abstract: Angew. Chem. Int. Ed. 32/2003 (pages 3706–3713)

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200390550

    3. Dehalogenation of Polyhalogenated Dioxins (pages 3718–3720)

      Karl-Heinz van Pée

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200301662

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      Bacterial combat on dioxins: A bacterial strain detected in a sediment sample from a creek contaminated with dioxins in the Bitterfeld region, Germany, dehalogenates different polyhalogenated dioxins under anaerobic conditions by reductive dehalogenation (see scheme). This reaction is coupled to the generation of energy and to growth (dehalorespiration).

    4. Metal Carbonyls: A New Class of Pharmaceuticals? (pages 3722–3729)

      Tony R. Johnson, Brian E. Mann, James E. Clark, Roberta Foresti, Colin J. Green and Roberto Motterlini

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200301634

      Carbon monoxide is an important signaling molecule in mammals. It is particularly active in the cardiovascular system and has been shown to be important in several areas of medicine, for example, in suppressing organ graft rejection and in reducing the damaging effects of ischemia. The importance of CO provides an opportunity for bioorganometallic chemistry to establish a new class of pharmaceuticals based on metal carbonyls.

    5. Host–Guest Antenna Materials (pages 3732–3758)

      Gion Calzaferri, Stefan Huber, Huub Maas and Claudia Minkowski

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200300570

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      Dyeing Zeolites: Dye-zeolite antenna systems transporting excitation energy over large distances are discussed on the basis of three stages of organization: the supramolecular organization of dye molecules inside the zeolite channels, the organization of stopcock molecules plugging the channel entrances, and the coupling of stopcock-modified antenna systems to an external device (see picture; EnT=energy transfer).

    6. Crystalline-State Reaction with Allosteric Effect in Spin-Crossover, Interpenetrated Networks with Magnetic and Optical Bistability (pages 3760–3763)

      Virginie Niel, Amber L. Thompson, M. Carmen Muñoz, Ana Galet, Andrés E. Goeta and José A. Real

      Article first published online: 28 JUL 2003 | DOI: 10.1002/anie.200351853

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      A net change: A fully reversible ligand substitution involving coordination/uncoordination of gaseous water and pyrimidine induces the repetitive allosteric transformation of three interpenetrated nets into a single three-dimensional net. The transformation does not affect the crystallinity of the sample but alters significantly the spin-crossover transition; the compound shows magnetic and chromatic bistability (see picture).

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      Synthesis and Magnetic Properties of a Metallacryptate that Behaves as a Single-Molecule Magnet (pages 3763–3766)

      Catherine Dendrinou-Samara, Maria Alexiou, Curtis M. Zaleski, Jeff W. Kampf, Martin L. Kirk, Dimitris P. Kessissoglou and Vincent L. Pecoraro

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351246

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      Crypt analysis: The reaction of manganese(II) chloride with sodium hydroxide, di-(2-pyridyl)-ketonoxime, and sodium azide yields a metallacryptate consisting of 26 manganese centers, namely, four MnII (see picture; gold spheres) and 22 MnIII ions (green, aqua, and blue spheres). Results obtained from ac SQUID magnetic studies indicate that this molecule displays single-molecule magnetic behavior.

    8. Single-Molecule Covalent Chemistry with Spatially Separated Reactants (pages 3766–3771)

      Tudor Luchian, Seong-Ho Shin and Hagan Bayley

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351313

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      In a recent study, the reversible covalent chemistry of a simple reaction was monitored at the single-molecule level by observing the current flowing through a protein pore, which acted as a nanoreactor. Now, a multistep reaction has been observed by an improved approach, in which two of the reactants are separated by the membrane that contains the pore and diffuse into the reaction zone (see picture).

    9. From Model Complexes to Metalloprotein Inhibition: A Synergistic Approach to Structure-Based Drug Discovery (pages 3772–3774)

      David T. Puerta, Julie R. Schames, Richard H. Henchman, J. Andrew McCammon and Seth M. Cohen

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351433

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      A happy marriage: The combination of synthetic model chemistry with computational conformational analysis has revealed the binding of an inhibitor to a medically important metalloenzyme. [(TpPh,Me)Zn(mbt)] (TpPh,Me=hydrotris(3,5-phenylmethylpyrazolyl)borate, mbt=2-methoxybenzenethiol) was used to template the conformation of a known inhibitor in the active site of the metalloenzyme, as shown by the green ligand inside the active site of the protein (the ZnII ion is shown in purple).

    10. Preorganization of Achiral Molecules for Asymmetric Synthesis through Crystallization-Induced Immobilization in Homochiral Conformations (pages 3775–3777)

      Brian O. Patrick, John R. Scheffer and Carl Scott

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351609

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      Enantioselective photochemistry: By forming salts with optically pure amines, achiral carboxylic acids can be induced to crystallize in chiral conformations that are preorganized for enantioselective photochemical reactions. Irradiation of crystals of the salt shown leads to selective Norrish type II abstraction of the nearer (green) γ-hydrogen atom, affording a diastereomerically pure cyclobutanol in 84–98 % enantiomeric excess depending on the amine used.

    11. Polyhedral Boranes with Exo Multiple Bonds: Three-Dimensional Inorganic Analogues of Quinones (pages 3777–3781)

      Musiri M. Balakrishnarajan and Roald Hoffmann

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351821

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      Three dimensional aromaticity: Polyhedral boranes with para-O, -NH, -S substituents should exhibit cylindrical π bonding on oxidation (see picture), with structural and reactivity consequences similar to benzoquinones.

    12. Solvothermal Synthesis of a Tetradecametallic FeIII Cluster (pages 3781–3784)

      David M. Low, Leigh F. Jones, Aidan Bell, Euan K. Brechin, Talal Mallah, Eric Rivière, Simon J. Teat and Eric J. L. McInnes

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351865

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      Solvothermal techniques allow the crystallization of high nuclearity products that are otherwise inaccessible by conventional techniques, directly from the reaction mixture. By this method, the reaction of the triangular species [Fe3O(OAc)6(H2O)3]Cl with benzotriazole (BtaH) produces an [Fe14] cluster (depicted) with a very large spin ground state.

    13. Templating of Silsesquioxane Cross-Linking Using Unimolecular Self-Organizing Polymers (pages 3785–3788)

      Eric F. Connor, Linda K. Sundberg, Ho-Cheol Kim, Jeroen J. Cornelissen, Teddie Magbitang, Phil M. Rice, Victor Y. Lee, Craig J. Hawker, Willi Volksen, James L. Hedrick and Robert D. Miller

      Article first published online: 28 JUL 2003 | DOI: 10.1002/anie.200350930

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      Nanopores created by micellar star polymers in amorphous organic silsequioxane thermosets produce morphologically controlled porous materials for semiconductor chip applications (see picture). Pore size is independent of concentration and processing conditions, but depends solely on the size of the polymer molecule.

    14. Nitrogen Inversion as a Diastereomeric Relay in Azasugar Synthesis: The First Synthesis of Adenophorine (pages 3788–3792)

      Michael A. T. Maughan, Ieuan G. Davies, Timothy D. W. Claridge, Steve Courtney, Phil Hay and Benjamin G. Davis

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351002

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      A temperature-dependent relay of chirality is based on the inversion of the nitrogen lone pair in cyclic azasugars. Elimination from the conformation preferred at a given temperature leads to a cyclic imine, and in a subsequent nucleophilic attack the stereochemical information is relayed.

    15. (R)-Binap-Mediated Asymmetric Hydrogenation with a Rhodacarborane Catalyst in Ionic-Liquid Media (pages 3792–3795)

      Zhu Yinghuai, Keith Carpenter, Ching Chi Bun, Stefan Bahnmueller, Chan Pek Ke, Venugopal Shanmugham Srid, Leong Weng Kee and M. Frederick Hawthorne

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351273

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      Unsymmetrical aryl ketones undergo asymmetric hydrogenation in ionic-liquid media in the presence of (R)-binap and a rhodacarborane catalyst derived from the suicide precursor 1 (see scheme). Ketones that are poor substrates for other methods can be hydrogenated in quantitative yields with very high enantioselectivities (97.3–99.5 % ee). The novel ionic liquid (N-n-butylpyridinium)+ (closo-CB11H12) provides a superior medium for these reactions.

    16. Highly Enantioselective Construction of Quaternary Stereocenters on β-Keto Esters by Phase-Transfer Catalytic Asymmetric Alkylation and Michael Reaction (pages 3796–3798)

      Takashi Ooi, Takashi Miki, Mika Taniguchi, Misato Shiraishi, Mifune Takeuchi and Keiji Maruoka

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351469

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      The designer ammonium salt (S,S)-1 catalyzes highly enantioselective phase-transfer alkylation and Michael reaction of β-keto esters. This approach provides a reliable route for the asymmetric synthesis of polyfunctionalized compounds having chiral quaternary carbon atoms.

    17. Metallaoxetanes and Carbenes from Diolates in High-Valent Rhenium Oxo Chemistry: The Importance of the Coordination Number (pages 3798–3801)

      Xueyi Chen, Xiangyang Zhang and Peter Chen

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351496

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      ReVdiolate complexes cleave to form either the ReVII trioxo complex or a rhenium carbene, depending on the coordination number of the original diolate complex (see picture). The carbene complexes, detected by using collision induced mass spectrometry, are the best experimental indication to date for intermediate “metallaoxetanes”, which would be the first-formed intermediate in [2+2] reactions of olefins with a d0 oxo complex. This sharp dichotomy in reactivity can be explained by a qualitative π-strain model.

    18. Synthesis of a 1,3-Diphosphacyclobutane-2,4-diyl from Mes*C[TRIPLE BOND]P (pages 3802–3804)

      Hiroki Sugiyama, Shigekazu Ito and Masaaki Yoshifuji

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351727

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      A very stable biradical, 2, was prepared from 1 (see picture). The deep-blue/violet biradical was stable in the air for several minutes. The sp2-hybridized carbon radical centers of 2 were confirmed by X-ray crystallography and its reversible oxidation was characterized by cyclic voltammetry. Mes*=2,4,6-tBu3C6H2.

    19. Synthesis and Characterization of Iron(III) Phosphonate Cage Complexes (pages 3804–3808)

      Evangelos I. Tolis, Madeleine Helliwell, Stuart Langley, James Raftery and Richard E. P. Winpenny

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351764

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      Sophisticated architectures can be built from oxo-centered carboxylate triangles linked together by phosphonates. This suggests that the phosphonate ligands could function as a means for building larger entities from carboxylate cages. The incorporation of a peroxide unit into the cage structures is also feasible, for example in the hexanuclear cage depicted.

    20. Total Synthesis of the Antipode of Alkaloid 205 B (pages 3808–3810)

      Naoki Toyooka, Ayako Fukutome, Hiroyuki Shinoda and Hideo Nemoto

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351906

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      Forming the tetrasubstituted piperidine ring with stereocontrol in a Michael-type conjugate addition is a key step in the first enantioselective synthesis of the antipode 1 of alkaloid 205 B. The absolute stereochemistry of the natural product could be determined unambiguously by comparison of the optical rotations.

    21. A Well-Defined Complex for Palladium-Catalyzed Aerobic Oxidation of Alcohols: Design, Synthesis, and Mechanistic Considerations (pages 3810–3813)

      David R. Jensen, Mitchell J. Schultz, Jaime A. Mueller and Matthew S. Sigman

      Article first published online: 28 JUL 2003 | DOI: 10.1002/anie.200351997

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      A breath of fresh air: A variety of alcohols are oxidized using 0.5–0.1 mol % of the catalyst, and in some cases the oxidation can simply be carried out open to the air (see scheme). Mechanistic insight into the mechanism is provided by a crystal structure that shows remarkable hydrogen bonds between the coordinated water and acetate ligands and an unprecedented large kinetic isotope effect.

    22. Continuous Coprecipitation of Catalysts in a Micromixer: Nanostructured Cu/ZnO Composite for the Synthesis of Methanol (pages 3815–3817)

      Michael Schur, Bettina Bems, Alina Dassenoy, Igor Kassatkine, Joachim Urban, Hagen Wilmes, Olaf Hinrichsen, Martin Muhler and Robert Schlögl

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200250709

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      A new purpose: Microreactors are commonly used in molecular high-throughput synthesis. Their use for the formation of catalysts through the precipitation of inorganic components is new. The product shows a high degree of nanostructuring (see electron microscopy image), which is at least partly retained in the subsequent production steps.

    23. Gram-Scale Synthesis of Submicrometer-Long Polythiophene Wires in Mesoporous Silica Matrices (pages 3818–3821)

      Guangtao Li, Sheshanath Bhosale, Tianyu Wang, Yang Zhang, Hesun Zhu and Jürgen-Hinrich Fuhrhop

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351158

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      Mesoporous materials get wired: Micelles of the thienyl-substituted ammonium ion 1 in aqueous ammonia solution are applied as matrices for the formation of mesoporous silicate particles from tetraethylorthosilicate. After oxidation with FeCl3 and treatment with HF, polymeric wires with a bimolecular diameter of 3 nm and average lengths of 100–200 nm (see TEM picture) are isolated. The yield of isolated material was consistently above 10% even in gram-scale reactions.

    24. Adaptive Behavior of Dynamic Combinatorial Libraries Generated by Assembly of Different Building Blocks (pages 3821–3825)

      Zacharias Grote, Rosario Scopelliti and Kay Severin

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200351623

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      Democratic behavior: A strong bias for the amplification of assemblies, the composition of which reflects the overall composition of the library, can be observed in selection processes with dynamic combinatorial libraries. As a consequence, it is not necessarily the assembly with the highest affinity to a given target (for example, a substrate, see scheme) that is amplified the most.

    25. Ordering Phenomena and Phase Transitions in a Spin-Crossover Compound—Uncovering the Nature of the Intermediate Phase of [Fe(2-pic)3]Cl2⋅EtOH (pages 3825–3830)

      Dmitry Chernyshov, Marc Hostettler, Karl W. Törnroos and Hans-Beat Bürgi

      Article first published online: 28 JUL 2003 | DOI: 10.1002/anie.200351834

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      From disorder to order and back: Contrary to all earlier studies on [Fe(2-pic)3]Cl2⋅EtOH (pic=picolylamine), an ordered phase (IP) with two crystallographically different iron sites was found between disordered high-spin (HS) and low-spin (LS) phases. The picture shows the average Fe[BOND]N distances of all three phases.

    26. Preview: Angew. Chem. Int. Ed. 32/2003 (page 3837)

      Article first published online: 13 AUG 2003 | DOI: 10.1002/anie.200390554

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