Angewandte Chemie International Edition

Cover image for Vol. 42 Issue 26

July 7, 2003

Volume 42, Issue 26

Pages 2921–3051

    1. Cover Picture: Structure and Bonding of Pd@[Bi10]4+ in the Subbromide Bi14PdBr16 (Angew. Chem. Int. Ed. 26/2003) (page 2921)

      Michael Ruck, Vitaly Dubenskyy and Tilo Söhnel

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200390506

      Endohedral clusters are more common in chemistry than expected, such as the inclusion compounds of fullerene (e.g., He@C60, left) and the recently discovered W@Au12 icosahedron (right). In the Communication by M. Ruck et al. on page 2978 ff., the Pd@[Bi10]4+ polycation (above) is presented, which has a pentagonal antiprismatic structure, a semiregular polyhedron first described by Archimedes. The relative weakness of the interaction between the Pd center and the arachno-[Bi10]4+ unit is discussed.

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    3. Inhibitors of Endocannabinoid Degradation: Potential Therapeutics for Neurological Disorders (pages 2938–2941)

      Michaela Wendeler and Thomas Kolter

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200301641

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      Joint benefits: Selective inhibitors of endocannabinoid degradation have been developed, among them the shown carbamate, which exhibit anxiolytic and analgesic properties in laboratory animals.

    4. Bioinorganic Reaction Mechanisms: From High-Valent Iron to Bioorganometallic Chemistry (pages 2942–2945)

      Leonardo D. Slep and Frank Neese

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200301649

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      Important aspects of the mechanisms of fundamental bioinorganic reactions have been revealed in recent studies, which have shed light on the structure and properties of high-valent nonheme Fe centers (left structure) as well as on the biosynthetic formation of the Fe[BOND]CN bond in Ni–Fe hydrogenases (right).

    5. Chemistry and Biology of DNA Repair (pages 2946–2974)

      Orlando D. Schärer

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200200523

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      First aid: Several pathways for DNA repair protect the genome from internal and external damaging agents and conditions. Our current understanding of the more important mechanisms is discussed, with an emphasis on the molecular basis of damage recognition/repair and on chemical approaches that have been used to study these processes.

    6. Chiral Molecular Motors Driven by a Nonhelical Laser Pulse (pages 2976–2978)

      Kunihito Hoki, Masahiro Yamaki and Yuichi Fujimura

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200250872

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      A turn for the better? The unidirectional rotation of chiral molecular motors, driven by a nonhelical laser pulse, can be explained by both quantum and classical mechanical calculations. The aldehyde group of the molecule is the rotor engine. The motor dynamics consists of three regimes: ignition, acceleration, and rotation. The results serve as a guiding principle for the control of molecular motors, such as braking and gears, by using pulsed lasers.

    7. Structure and Bonding of Pd@[Bi10]4+ in the Subbromide Bi14PdBr16 (pages 2978–2982)

      Michael Ruck, Vitaly Dubenskyy and Tilo Söhnel

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200250801

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      Pd@[Bi10]4+is the appropriate representation of the first heteronuclear polycation of bismuth and a transition element. The pentagonal Archimedean antiprism [PdBi10]4+ (see picture) is a transition-metal-containing variant of the predicted arachno-cluster [Bi10]4+, in which there are almost no observed host–guest interactions.

    8. Design of a Solid Inclusion Compound with Optimal Properties as a Linear Dichroic Filter for X-ray Polarization Analysis (pages 2982–2985)

      Mao-Hsun Chao, Benson M. Kariuki, Kenneth D. M. Harris, Steven P. Collins and David Laundy

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200350891

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      A new molecular material—the 1-bromoadamantane/thiourea inclusion compound (the guest substructure of which is depicted)—has been designed as a dichroic filter for X-ray polarization analysis, based on theoretical predictions of the required structural characteristics. Measurements of X-ray linear dichroism show that this material exhibits essentially optimal performance in such applications.

    9. Carbon Tetraoxide: Theoretically Predicted and Experimentally Detected (pages 2985–2990)

      Fulvio Cacace, Giulia de Petris, Marzio Rosi and Anna Troiani

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200350936

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      CO4, the proof: Although theoretically predicted to be detectable, CO4 has proved so far experimentally elusive. We report its discovery as a result of a mass spectrometric and theoretical study showing that CO4 does exist as a metastable molecule in the gas phase, with a lifetime=1 μs (see picture showing the neutralization–reionization MS of CO4+ with arrows indicating the recovery peaks).

    10. A High-Yield Approach to the Sulfonation of Methane to Methanesulfonic Acid Initiated by H2O2 and a Metal Chloride (pages 2990–2993)

      Sudip Mukhopadhyay and Alexis T. Bell

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200350976

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      Low temperatures and low pressures suffice for the sulfonation of methane with a suitable free-radical initiator and promoter [Eq. (1)]. Since the RhCl3 promoter can be recycled, and the initiator complex is stable and easy to handle, development of this reaction into an industrial process is promising. MSA=methanesulfonic acid.

    11. Is log P a Convenient Criterion to Guide the Choice of Solvents for Biphasic Enzymatic Reactions? (pages 2993–2996)

      Murillo Villela Filho, Thomas Stillger, Michael Müller, Andreas Liese and Christian Wandrey

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351089

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      It depends on the choice. The conciliation of the high chemo- and enantioselectivity of the alcohol dehydrogenase(ADH)-catalyzed reduction of ketones and the poor water solubility of substrates can be achieved in aqueous–organic biphasic systems (see picture). But how should the organic phase be chosen?

    12. Selective Detection of Zinc Ions with Novel Luminescent Lanthanide Probes (pages 2996–2999)

      Kenjiro Hanaoka, Kazuya Kikuchi, Hirotatsu Kojima, Yasuteru Urano and Tetsuo Nagano

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351122

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      A remarkable enhancement of luminescence is observed in a solution of the TbIII complex 1 upon adding ZnII ions (see picture). Complex 1 has a high selectivity for ZnII and a long luminescence lifetime of the order of milliseconds, thus is an excellent lead compound for the development of ZnII-sensitive luminescent chemosensors with long luminescence lifetimes. A=light absorption, ET=energy transfer, E=light emission.

    13. Solid-State Supramolecular Organization of Supermolecules into a Truly Molecular Zeolite (pages 2999–3001)

      Kom-Bei Shiu, Hong-Chan Lee, Gene-Hsiang Lee, Bao-Tsan Ko, Yu Wang and Chu-Chieh Lin

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351149

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      Letting out the guests: The hexagonal closest packing of discrete triangular-tube-shaped organometallic supermolecules of eclipsed-[{Ru2(CO)4(PPh3)2}(μ-4,4′-O2CC6H4C6H4CO2)]3 in the solid state (see picture) permits the production of a microporous material that is not only thermally stable up to 181 °C, but also allows diffusion at room temperature of molecular guests without the framework collapsing.

    14. Phenyl versus Ethyl Transfer in the Addition of Organozinc Reagents to Aldehydes: A Theoretical Study (pages 3002–3005)

      Jens Rudolph, Torben Rasmussen, Carsten Bolm and Per-Ola Norrby

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351150

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      The dramatic improvement in diphenylzinc addition to aldehydes that is obtained by adding diethylzinc was investigated by DFT methods. The strong preference for phenyl over ethyl transfer can be understood in terms of overlap with the phenyl π system in the transition state (see picture). Reasons for the high ee value in the presence of Et2Zn are discussed.

    15. Controlling the Oxygenation Level of Hemoglobin by Using a Synthetic Receptor for 2,3-Bisphosphoglycerate (pages 3005–3008)

      Zhenlin Zhong and Eric V. Anslyn

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351165

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      A designed synthetic receptor (1), which has guanidinium groups and a CuII center, is highly effective and selective for binding 2,3-bisphosphoglycerate (2,3-BPG) in physiological media (see picture). The affinity is high enough that the receptor can deprive hemoglobin of available 2,3-BPG, and thus control the active level of 2,3-BPG and the related oxygenation level of hemoglobin. Cu=Green, N=blue, C=gray, P=yellow, O=red.

    16. Nickel(0)-Mediated [3+2+2] and [2+2+2+1] Cyclization Reactions of Chromium Fischer Carbene Complexes and Alkynes (pages 3008–3011)

      José Barluenga, Pablo Barrio, Luis A. López, Miguel Tomás, Santiago García-Granda and Carmen Alvarez-Rúa

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351216

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      Dramatic changes in Fischer carbene reactivity occur in the presence of [Ni(cod)2]. Thus, instead of Dötz [3+2+1] benzannulation giving substituted phenols, alkenyl carbene complexes incorporate two equivalents of alkyne in a [3+2+2] cyclization, while simple chromium carbene complexes undergo a [2+2+2+1] cyclization (see scheme). These cyclizations are regio- and diastereoselective. cod=1,5-cyclooctadiene.

    17. A Near-Infrared Electrochromic Window Based on an Sb-Doped SnO2 Electrode Modified with a Ru–Dioxolene Complex (pages 3011–3014)

      Jorge García-Cañadas, Andrew P. Meacham, Laurence M. Peter and Michael D. Ward

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351338

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      A window of opportunity: The ligand-centred redox activity of complex 1 (depicted) is exploited to make an electrochromic window, which demonstrates rapid and reversible changes in optical transmission at 940 nm. The window is made by adsorbing 1 onto a nanocrystalline Sb-doped SnO2 film attached to a transparent conducting substrate and cycling the applied potential through the catecholate/semiquinone redox couple.

    18. pH-Responsive Molecularly Imprinted Polymers (pages 3014–3016)

      Yasumasa Kanekiyo, Ryuichi Naganawa and Hiroaki Tao

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351381

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      The molecular-recognition ability of molecularly imprinted polymers (MIPs) changes in response to solution acidity (see scheme). The MIPs are created by the copolymerization of an acryloylamylose-template inclusion complex with acrylic acid.

    19. Total Synthesis and Structural Elucidation of (−)-Delactonmycin (pages 3017–3020)

      Ivan R. Corrêa Jr. and Ronaldo A. Pilli

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351347

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      The key steps in the total synthesis of delactonmycin (1) involved a Wittig olefination, a Negishi coupling, and an aldol reaction. The polyketide, which was isolated from Streptomyces sp., displays potent inhibitory activity of the nucleo-cytoplasmic translocation of the HIV-1 regulatory protein Rev.

    20. Introducing Branches into a Self-Assembling Peptide Fiber (pages 3021–3023)

      Maxim G. Ryadnov and Derek N. Woolfson

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351418

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      The special branch: The design of novel T-shaped peptides that coassemble with linear peptides to produce branched fibers is described (see picture). The bottom-up assembly of peptide-based nanostructures of this type holds promise for the development of novel scaffolds for applications in nanobiotechnology.

    21. A Homo [3+2] Dipolar Cycloaddition: The Reaction of Nitrones with Cyclopropanes (pages 3023–3026)

      Ian S. Young and Michael A. Kerr

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351573

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      Pole-to-pole: Cyclopropanediesters when treated with nitrones in the presence of catalytic ytterbium triflate undergo a dipolar homo [3+2] cycloaddition to form tetrahydro-1,2-oxazines diastereoselectively (see scheme). This new process has been used in a two-step preparation of the tricyclic core of FR-900482.

    22. ZnSe Semiconductor Hollow Microspheres (pages 3027–3030)

      Qing Peng, Yajie Dong and Yadong Li

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200250695

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      Magic bubbles: ZnSe semiconductor microspheres aggregated from nanocrystals of tunable size have been successfully synthesized for the first time by use of gas bubbles. Based on the interior nanocrystal size and structure, the as-obtained samples exhibit different colors.

    23. Low-Temperature Wafer-Scale Production of ZnO Nanowire Arrays (pages 3031–3034)

      Lori E. Greene, Matt Law, Joshua Goldberger, Franklin Kim, Justin C. Johnson, Yanfeng Zhang, Richard J. Saykally and Peidong Yang

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351461

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      Homogeneous and dense arrays of ZnO nanowires were synthesized on silicon wafers (and many other substrates) using a mild solution process at 90 °C. Uniform ZnO nanocrystals were deposited to act as seeds for subsequent hydrothermal nanowire growth, which yielded single-crystalline ZnO nanowires grown along the [0001] direction and oriented perpendicular to the wafer surface (see picture; scale bar=1μm). The photoluminescence and lasing behavior of the arrays has been studied as a function of annealing treatment conditions.

    24. Site Occupation and Activity of Catalyst Nanoparticles Monitored by In Situ Vibrational Spectroscopy (pages 3035–3038)

      Viktor Johánek, Swetlana Schauermann, Mathias Laurin, Jörg Libuda and Hans-Joachim Freund

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351228

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      On the edge? The distribution of reactants and products over regular and edge sites of well-shaped palladium nanocrystallites is monitored during catalytic NO decomposition by using a combination of molecular beam techniques and in situ vibrational spectroscopy (see scheme, TR-IRAS=time-resolved IR reflection absorption spectroscopy, QMS=quadrupole mass spectrometer). Atomic nitrogen and oxygen species preferentially occupy edge sites on the catalyst particles. The presence of these co-adsorbates controls the NO dissociation activity.

    25. The Room-Temperature Stabilization of Bicyclo[2.2.2]oct-1-ene and Bicyclo[3.2.1]oct-1-ene (pages 3039–3042)

      Paul Roach and Ralf Warmuth

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351120

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      Retardation through incarceration: The highly strained anti-Bredt bridgehead olefin bicyclo[2.2.2]oct-1-ene (1) is remarkably stable at 60 °C, if generated photochemically inside the hemicarcerand 2 (see picture). The surrounding host not only prevents the dimerization of 1, but also retards strongly its intramolecular retro-Diels–Alder reaction by several orders of magnitude.

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      A Flexible and Catalytic One-Pot Procedure for the Synthesis of Indoles (pages 3042–3044)

      Holger Siebeneicher, Igor Bytschkov and Sven Doye

      Version of Record online: 2 JUL 2003 | DOI: 10.1002/anie.200351345

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      One pot, two bonds, three rings: A clever combination of a [Cp2TiMe2]-catalyzed hydroamination of alkynes with a Pd-catalyzed N-arylation of imines results in a new and general method for the synthesis of indoles. Impressively, two new C[BOND]N bonds are formed during the one-pot procedure (see scheme).