Angewandte Chemie International Edition

Cover image for Vol. 44 Issue 28

July 11, 2005

Volume 44, Issue 28

Pages 4271–4411

    1. Cover Picture: Reaction Progress Kinetic Analysis: A Powerful Methodology for Mechanistic Studies of Complex Catalytic Reactions (Angew. Chem. Int. Ed. 28/2005) (page 4271)

      Donna G. Blackmond

      Version of Record online: 4 JUL 2005 | DOI: 10.1002/anie.200590094

      The London Eye moves continuously even as passengers embark and disembark, serving as both a backdrop and a metaphor for a steady-state catalytic cycle. The theme of the Review by D. G. Blackmond on page 4302 ff. is the mechanistic study of complex catalytic reactions using reaction progress kinetic analysis. A new set of graphical tools are described that are based on reaction monitoring in situ with simple data manipulations. Photo:

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      Photo-Cross-Linked Small-Molecule Affinity Matrix for Facilitating Forward and Reverse Chemical Genetics (page 4282)

      Naoki Kanoh, Kaori Honda, Siro Simizu, Makoto Muroi and Hiroyuki Osada

      Version of Record online: 4 JUL 2005 | DOI: 10.1002/anie.200590096

    3. A High-Precision Switch on an RNA Message (pages 4288–4290)

      Bernhard Kräutler

      Version of Record online: 9 JUN 2005 | DOI: 10.1002/anie.200500774

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      The glycine-dependent riboswitch is a high-precision molecular RNA switch to control the use of glycine as a “fuel” (in energy-yielding catabolism) or as a “chemical” (in anabolism and protein biosynthesis).

    4. Recent Advances in Catalytic, Enantioselective α Aminations and α Oxygenations of Carbonyl Compounds (pages 4292–4300)

      Jacob M. Janey

      Version of Record online: 9 JUN 2005 | DOI: 10.1002/anie.200462314

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      Chiral Lewis acids and Lewis bases catalyze the α amination and the α oxygenation of aldehydes, ketones, and esters (see scheme). This is a powerful way to directly introduce a heteroatom adjacent to a carbonyl group, and this reaction provides access to important enantiomerically pure building blocks such as α-amino acids.

    5. Reaction Progress Kinetic Analysis: A Powerful Methodology for Mechanistic Studies of Complex Catalytic Reactions (pages 4302–4320)

      Donna G. Blackmond

      Version of Record online: 4 JUL 2005 | DOI: 10.1002/anie.200462544

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      Intuitive and precise: Kinetic measurements are often considered time-intensive and routine studies required to determine concentration dependences and help distinguish between different proposed reaction mechanisms. This Review describes step by step how this can be achieved from a minimal number of experiments with the help of intuitive “graphical rate equations” (see picture) without prior mechanistic knowledge of a catalytic reaction cycle.

      Corrected by:

      Corrigendum: Reaction Progress Kinetic Analysis: A Powerful Methodology for Mechanistic Studies of Complex Catalytic Reactions

      Vol. 45, Issue 14, 2162, Version of Record online: 17 MAR 2006

    6. Optically Active Conjugated Polymers Prepared from Achiral Monomers by Polycondensation in a Chiral Nematic Solvent (pages 4322–4328)

      Hiromasa Goto and Kazuo Akagi

      Version of Record online: 1 JUN 2005 | DOI: 10.1002/anie.200462859

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      Contagious chirality: A chiral polymer (see image) was obtained from the polycondensation of an achiral monomer by using a chiral nematic liquid crystal (N*-LC) as an inert reaction solvent. The chirality of the polymer is thought to derive from the asymmetry produced by the chiral medium during polymerization.

    7. Single-Crystalline Iron Oxide Nanotubes (pages 4328–4333)

      Chun-Jiang Jia, Ling-Dong Sun, Zheng-Guang Yan, Li-Ping You, Feng Luo, Xiao-Dong Han, Yu-Cheng Pang, Ze Zhang and Chun-Hua Yan

      Version of Record online: 15 JUN 2005 | DOI: 10.1002/anie.200463038

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      Phosphate ions play a crucial role not only for the formation of the spindlelike precursors of the single-crystalline hematite nanotubes that were synthesized by a facile hydrothermal method. They are also important for the adsorption and coordination effects. The mechanism of tube formation was deduced through EM observations as a coordination-assisted dissolution process (see picture).

    8. Aptamer-Directed Self-Assembly of Protein Arrays on a DNA Nanostructure (pages 4333–4338)

      Yan Liu, Chenxiang Lin, Hanying Li and Hao Yan

      Version of Record online: 9 JUN 2005 | DOI: 10.1002/anie.200501089

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      Lined up nicely: The self-assembly of proteins on rationally designed nanostructures into periodic linear arrays has been demonstrated. Triple-crossover DNA tiles 1 containing an aptamer sequence (AS) to which thrombin specifically binds can form linear arrays 2. These direct the ultimate positioning of thrombin proteins (green spheres) in 3. This system should facilitate the construction of other such programmable nanoscale protein arrays.

    9. cyclo-Ti322-C,O)]3: A Side-on-Bonded Polycarbonyl Titanium Cluster with Potentially Antiaromatic Character (pages 4338–4342)

      Qiang Xu, Ling Jiang and Nobuko Tsumori

      Version of Record online: 9 JUN 2005 | DOI: 10.1002/anie.200500364

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      A windmill-like trititanium cluster with side-on-bonded CO ligands (see picture), which may have antiaromatic character, was revealed by FTIR spectroscopy and DFT calculations. It is generated, along with other side-on-bonded mono- and polycarbonyl di- and trititanium clusters, in the reaction of laser-ablated Ti atoms with CO in a solid argon matrix.

    10. Size Tuning, Functionalization, and Reactivation of Au in TiO2 Nanoreactors (pages 4342–4345)

      Jing Li and Hua Chun Zeng

      Version of Record online: 13 JUN 2005 | DOI: 10.1002/anie.200500394

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      Reactor core: Hollow core–shell Au–TiO2 nanocomposites can be prepared by a wet chemical method to form reactors that contain a catalyst core with a shell that is permeable to reactants. The core can be enlarged, and modification of the synthesis produces flowerlike nanostructures (see picture). Catalytic reactions in both the gaseous and liquid phase can be conducted in this type of photosensitized metal–semiconductor nanoreactor.

    11. Multinuclear Copper Triethanolamine Complexes as Selective Catalysts for the Peroxidative Oxidation of Alkanes under Mild Conditions (pages 4345–4349)

      Alexander M. Kirillov, Maximilian N. Kopylovich, Marina V. Kirillova, Matti Haukka, M. Fátima C. Guedes da Silva and Armando J. L. Pombeiro

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200500585

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      Rich activity from a few coppers: Di-, tri-, tetra-, and polynuclear copper triethanolamine complexes are easily prepared and are selective and efficient catalysts for alkane peroxidative oxidation under mild conditions (see picture).

    12. Synthesis and Self-Assembly of Rod–Rod Hybrid Poly(γ-benzyl L-glutamate)-block-Polyisocyanide Copolymers (pages 4349–4352)

      Alexander Kros, Wim Jesse, Gerald A. Metselaar and Jeroen J. L. M. Cornelissen

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/anie.200500877

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      Connecting rods: Rigid rod–rod block copolymers are synthesized from peptide and polyisocyanide blocks (see picture: blue=poly(γ-benzyl L-glutamate); red=poly(methylbenzyl isocyanide) or poly(L-isocyanoalanyl-L-alanine methyl ester). The polyisocyanide helix has side arms organized in a parallel β-sheet (light blue). Some copolymers self-assemble into ordered layers of hollow capsules.

    13. Copper(II) and Zinc(II) Complexes Can Fix Atmospheric Carbon Dioxide (pages 4352–4355)

      Ling-Yan Kong, Zheng-Hua Zhang, Hui-Fang Zhu, Hiroyuki Kawaguchi, Taka-aki Okamura, Mototsugu Doi, Qian Chu, Wei-Yin Sun and Norikazu Ueyama

      Version of Record online: 17 JUN 2005 | DOI: 10.1002/anie.200500587

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      Carbonato bridges from atmospheric carbon dioxide: The copper(II) and zinc(II) complexes of the novel imidazole-containing polyamine ligand N1-(2-aminoethyl)-N1-(2-imidazolethyl)ethane-1,2-diamine are found to fix carbon dioxide by hydration to μ3-carbonate ligands. This is revealed by IR and solid-state 13C NMR spectroscopic and X-ray crystallographic studies of the two-dimensional complexes (see picture).

    14. A DNAzyme That Walks Processively and Autonomously along a One-Dimensional Track (pages 4355–4358)

      Ye Tian, Yu He, Yi Chen, Peng Yin and Chengde Mao

      Version of Record online: 9 JUN 2005 | DOI: 10.1002/anie.200500703

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      Inching its way forward: A DNA nanodevice is presented which can autonomously and processively move on a well-defined track with a 7-nm step size. The moving principle integrates DNAzyme activity and a strand-displacement strategy, which resembles the behavior of a caterpillar eating its way through a row of plants (see picture).

    15. A Free-Running DNA Motor Powered by a Nicking Enzyme (pages 4358–4361)

      Jonathan Bath, Simon J. Green and Andrew J. Turberfield

      Version of Record online: 15 JUN 2005 | DOI: 10.1002/anie.200501262

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      DNA burns its bridges: A unidirectional molecular motor that moves an oligonucleotide cargo along a self-assembled track is powered by restriction endonuclease hydrolysis of the phosphodiester backbone (see scheme). Damage caused to the track by the restriction enzyme prevents the cargo from stepping backwards and therefore imposes directionality.

    16. Bridging Phosphanes: Exotic or Versatile Binucleating Ligands? (pages 4362–4365)

      François Leca, Christophe Lescop, Elena Rodriguez-Sanz, Karine Costuas, Jean-François Halet and Régis Réau

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200500529

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      Newcomers in the family: Pd–Pt heterobimetallic and Cu–Cu homobimetallic species (see picture) bearing bridging phosphane ligands are reported. Their structural arrangement reveals a continuum between semi-bridging and bridging coordination modes.

    17. Direct Catalytic Asymmetric Mannich-Type Reactions of N-(2-Hydroxyacetyl)pyrrole as an Ester-Equivalent Donor (pages 4365–4368)

      Shinji Harada, Shinya Handa, Shigeki Matsunaga and Masakatsu Shibasaki

      Version of Record online: 7 JUN 2005 | DOI: 10.1002/anie.200501180

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      Stretching the limits of the Mannich reaction: A new indium–binol catalyst was used to generate the enolate of the ester-equivalent donor in situ (see scheme). The donor, an N-acylpyrrole, has many similarities to an aromatic ketone, in particular the enolates should have the same coordination mode. Versatile β-amino-α-hydroxy carboxylic acid derivatives were obtained in high yield and ee values.

    18. Star-Shaped Light-Harvesting Polymers Incorporating an Energy Cascade (pages 4368–4372)

      Ming Chen, Kenneth P. Ghiggino, San H. Thang and Gerard J. Wilson

      Version of Record online: 3 JUN 2005 | DOI: 10.1002/anie.200462796

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      A star in the making: Star-shaped block copolymers have been synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization to obtain light-harvesting systems with an energy gradient from the periphery to the core. Excitation-energy transfer in the block copolymers occurs through an energy cascade from the excited acenaphthenyl units to the coumarin chromophores and hence to the RuII complex core (red sphere: see picture).

    19. Total Synthesis of Glycocinnasperimicin D (pages 4372–4375)

      Taihei Nishiyama, Minoru Isobe and Yoshiyasu Ichikawa

      Version of Record online: 14 JUN 2005 | DOI: 10.1002/anie.200500892

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      A three-fragment coupling strategy afforded the antibiotic glycocinnasperimicin D (1). The convergent total synthesis features a Heck reaction to form the cinnamoyl glycoside, the [3,3] sigmatropic rearrangement of an allyl cyanate for the stereoselective synthesis of the allyl amine, and the coupling of a glycosyl isocyanate with an amino sugar for the construction of the urea glycoside linkage.

    20. Aligning Au Nanorods by Using Carbon Nanotubes as Templates (pages 4375–4378)

      Miguel A. Correa-Duarte, Jorge Pérez-Juste, Ana Sánchez-Iglesias, Michael Giersig and Luis M. Liz-Marzán

      Version of Record online: 14 JUN 2005 | DOI: 10.1002/anie.200500581

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      With strings attached: Gold nanorods undergo uniform electrostatic assembly on multiwall carbon nanotubes (MWNTs) to form strings of rods with end-to-end contacts (see picture, PSS=polystyrene sulfonate, PDDA=poly(diallyldimethyl)ammonium chloride). This arrangement results in uniaxial plasmon coupling, and the polarization-dependent optical response has been used to monitor the degree of alignment of carbon nanotubes within polymer films.

    21. Prodrug Activation Gated by a Molecular “OR” Logic Trigger (pages 4378–4381)

      Roey J. Amir, Mikhail Popkov, Richard A. Lerner, Carlos F. Barbas III and Doron Shabat

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200500842

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      Molecules that define logic: A molecular “OR” logic gate trigger has been demonstrated by masking a functional group in a doxorubicin prodrug with a linker that contains two cleavable substrates (input). The prodrug molecule was activated by two different enzymes to release the parent drug (see scheme; input red; output (drug) blue).

    22. Simultaneous Conversion of Methane and Methanol into Gasoline over Bifunctional Ga-, Zn-, In-, and/or Mo-Modified ZSM-5 Zeolites (pages 4381–4385)

      Vasant R. Choudhary, Kartick C. Mondal and Shafeek A. R. Mulla

      Version of Record online: 13 JUN 2005 | DOI: 10.1002/anie.200500694

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      Gasoline from methane: Methane can be activated nonoxidatively and converted into higher hydrocarbons over bifunctional zeolite catalysts at low temperatures (≤600 °C; see scheme). The amount of methane converted per mole of methanol by this process can meet or even exceed 1 mol. This approach could potentially lead to an economically feasible technology for the commercial conversion of methane into liquid hydrocarbons.

    23. Activity of SPANphos Rhodium Dimers in Methanol Carbonylation (pages 4385–4388)

      Zoraida Freixa, Paul C. J. Kamer, Martin Lutz, Anthony L. Spek and Piet W. N. M. van Leeuwen

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200500226

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      Contrary to earlier speculation, mononuclear rhodium species that contain trans diphosphines, such as SPANphos, are inactive towards the oxidative addition of methyl iodide, whereas the corresponding dinuclear species are very reactive. Thus, the active species in methanol carbonylation is most likely the dimeric system (see scheme; P orange, O red, Rh blue, Cl green).

    24. Enantioselective Epoxidation of Allylic Alcohols by a Chiral Complex of Vanadium: An Effective Controller System and a Rational Mechanistic Model (pages 4389–4391)

      Wei Zhang, Arindrajit Basak, Yuji Kosugi, Yujiro Hoshino and Hisashi Yamamoto

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200500938

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      Bishydroxamic acid derivatives are used as ligands for a vanadium catalyst in the preparation of epoxy alcohols (see scheme). The methodology uses aqueous tert-butyl hydroperoxide (TBHP) as an achiral oxidant, low catalyst loading, low reaction temperatures (0 °C to room temperature), and simple workup procedures. The reaction is applied to the kinetic resolution of a secondary allylic alcohol and the preparation of small epoxy alcohols. R1, R2, R3: alkyl, aryl, H.

    25. Self-Assembled Vanadium Pentoxide (V2O5) Hollow Microspheres from Nanorods and Their Application in Lithium-Ion Batteries (pages 4391–4395)

      An-Min Cao, Jin-Song Hu, Han-Pu Liang and Li-Jun Wan

      Version of Record online: 8 JUN 2005 | DOI: 10.1002/anie.200500946

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      Hedgehog” or “nest” microspheres of V2O5 are formed when nanorods of V2O5 are synthesized in a mediated polyol process. When the concentration of the starting material is low, a nest shape is preferred, whereas a high concentration of [V(acac)3] affords hedgehog-shaped microspheres (see picture). The V2O5 microspheres exhibit remarkable electrochemical properties when used as the cathode material in a lithium-ion battery.

    26. Ruthenium-Catalyzed Allylic Alkylation Reactions: Carbonate-Based Catalysts and Intermediates (pages 4397–4400)

      René Hermatschweiler, Ignacio Fernández, Frank Breher, Paul S. Pregosin, Luis F. Veiros and Maria José Calhorda

      Version of Record online: 16 JUN 2005 | DOI: 10.1002/anie.200500967

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      Branching out: A previously unrecognized ruthenium carbonate intermediate is formed during the reaction of an allylic tert-butoxycarbonate with the ruthenium complex [Ru(Cp*)(CH3CN)3]PF6 (1; see scheme). The isolatable carbonate–allyl complex functions very effectively as an allylic alkylation catalyst. These results provide new insights into the mechanism of this ruthenium-catalyzed reaction.

    27. Quantification of Cation–π Interactions in Protein–Ligand Complexes: Crystal-Structure Analysis of Factor Xa Bound to a Quaternary Ammonium Ion Ligand (pages 4400–4404)

      Kaspar Schärer, Martin Morgenthaler, Ralph Paulini, Ulrike Obst-Sander, David W. Banner, Daniel Schlatter, Jörg Benz, Martine Stihle and François Diederich

      Version of Record online: 13 JUN 2005 | DOI: 10.1002/anie.200500883

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      The aromatic box formed by the side chains Phe 174, Tyr 99, and Trp 215 in the S4-pocket of Factor Xa is a very effective onium binding site (see picture; red O, blue N, green Cligand, gray Cprotein). The free enthalpy increment for cation–π interactions between quaternary ammonium ions and aromatic groups in this box is determined to be ΔΔG=2.8 kcal mol−1. Database searches reveal that similar cation binding sites are not uncommon in biological systems.

    28. A Regenerative Chemodosimeter Based on Metal-Induced Dye Formation for the Highly Selective and Sensitive Optical Determination of Hg2+ Ions (pages 4405–4407)

      José V. Ros-Lis, M. Dolores Marcos, Ramón Mártinez-Máñez, Knut Rurack and Juan Soto

      Version of Record online: 9 JUN 2005 | DOI: 10.1002/anie.200500583

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      Into the blue: Hg2+ -ion-triggered formation of a brightly fluorescent squaraine dye is used as a novel approach for the design of highly selective and sensitive chromofluorogenic probes for the analysis of Hg2+ ions down to concentrations below 2 ppb (see picture). Through the adsorption of the sensor on a solid support a prototype reusable test strip is also generated.

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