Angewandte Chemie International Edition

Cover image for Vol. 46 Issue 32

August 13, 2007

Volume 46, Issue 32

Pages 5985–6199

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
    1. Cover Picture: The Tungstogermanate [Ce20Ge10W100O376(OH)4(H2O)30]56−: A Polyoxometalate Containing 20 Cerium(III) Atoms (Angew. Chem. Int. Ed. 32/2007) (page 5985)

      Bassem S. Bassil, Michael H. Dickman, Isabella Römer, Bernd von der Kammer and Ulrich Kortz

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/anie.200790155

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      A gigantic polyoxometalate …… [Ce20Ge10W100O376(OH)4(H2O)30]56− (1) was obtained in a classic one-pot synthesis from CeIII ions and the trilacunary precursor [α-GeW9O34]10− in water, as described by U. Kortz and co-workers in their Communication on page 6192 ff. The cover picture shows a possible mechanism of formation by stepwise self-assembly, beginning with the formation of Ce2GeW10 Keggin units, followed by arrangement of five such units into chiral, enantiomeric {Ce2GeW10}5 species, and then dimerization of the R and S forms to give 1.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
    1. Inside Cover: Pd-Catalyzed Polymerization of Dienes that Involves Chain-Walking Isomerization of the Growing Polymer End: Synthesis of Polymers Composed of Polymethylene and Five-Membered-Ring Units (Angew. Chem. Int. Ed. 32/2007) (page 5986)

      Takeshi Okada, Sehoon Park, Daisuke Takeuchi and Kohtaro Osakada

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/anie.200790156

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      Chain-walking isomerization of the growing polymer end occurs during the cyclopolymerization of 1,6-dienes catalyzed by PdII complexes, and leads to polymers with trans-1,2-disubstituted cyclopentane rings and polar functional groups located regularly along the linear polymer chain, as described by K. Osakada and co-workers in their Communication on page 6141 ff.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
    1. You have free access to this content
      IR Spectra of Protonated Carbonic Acid and Its Isomeric H3O+⋅CO2 Complex (page 5999)

      Horia-Sorin Andrei, Sergey A. Nizkorodov and Otto Dopfer

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/anie.200790158

      This article corrects:

      IR Spectra of Protonated Carbonic Acid and Its Isomeric H3O+⋅CO2 Complex1

      Vol. 46, Issue 25, 4754–4756, Version of Record online: 8 MAY 2007

  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
  6. Obituary

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
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    1. Pierre-Gilles de Gennes (1932–2007) (page 6004)

      Etienne Guyon

      Version of Record online: 3 AUG 2007 | DOI: 10.1002/anie.200702849

  7. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
  8. Highlight

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
    1. Metal Nanoparticles: From “Artificial Atoms” to “Artificial Molecules” (pages 6006–6008)

      Dmitrii F. Perepichka and Federico Rosei

      Version of Record online: 6 JUL 2007 | DOI: 10.1002/anie.200701554

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      Threading nanobeads: Gold nanoparticles (NPs) coated with functional organic ligands are candidate building blocks for the bottom-up fabrication of nanostructured materials. This Highlight describes a recent approach to achieving bidirectional NP–NP connectivity, which is an essential step in the assembly of NP-based polymers (see scheme) and more complex nanoarchitectures.

  9. Essay

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
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    1. Friedrich Asinger (1907–1999): A Mediator between Basic and Applied Research (pages 6010–6013)

      Wilhelm Keim and Heribert Offermanns

      Version of Record online: 12 JUN 2007 | DOI: 10.1002/anie.200700904

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      A double jubilee: This year marks the 50th anniversary of the discovery of the Asinger reaction—the original version a three-component reaction for the direct synthesis of thiazolines from elemental sulfur, ammonia, and a carbonyl component—and the centennial anniversary of the birth of its eponym, Friedrich Asinger (1907–1999).

  10. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
    1. Combinatorial and High-Throughput Materials Science (pages 6016–6067)

      Wilhelm F. Maier, Klaus Stöwe and Simone Sieg

      Version of Record online: 19 JUL 2007 | DOI: 10.1002/anie.200603675

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      Combinatorial discovery: High-throughput techniques are already used routinely for research on complex materials, such as polymers, electronic materials, and catalysts. Remarkable achievements are related to parallel syntheses and analyses, data-mining technologies, modeling approaches, as well as evolutionary strategies for materials development and formulations. The discoveries and success stories document the power of these emerging technologies.

  11. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Obituary
    8. Book Review
    9. Highlight
    10. Essay
    11. Review
    12. Communications
    13. Preview
    1. Metal-Catalyzed Copolymerization of Imines and CO: A Non-Amino Acid Route to Polypeptides (pages 6068–6072)

      Huailin Sun, Jian Zhang, Qiuhua Liu, Lei Yu and Jiangyu Zhao

      Version of Record online: 3 JUL 2007 | DOI: 10.1002/anie.200700646

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      The path less taken: Copolymerization of imines and carbon monoxide has long been highly desirable as a route to synthesize polypeptides, but has been difficult to implement because of the lack of appropriate catalysts. This reaction has now been realized for the first time by using a simple cobalt catalyst (see scheme).

    2. Structural Basis for the Recognition of para-Benzoyl-L-phenylalanine by Evolved Aminoacyl-tRNA Synthetases (pages 6073–6075)

      Wenshe Liu, Lital Alfonta, Antha V. Mack and Peter G. Schultz

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701990

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      Nonnatural interactions: The X-ray crystal structure of a mutant aminoacyl-tRNA synthetase that selectively recognizes para-benozyl-L-phenylalanine has been solved. This structure shows that mutations to the enzyme lead to new hydrophobic binding interactions with the unnatural amino acid, and a loss of specific hydrogen-bonding interactions with tyrosine, without a significant change in the polypeptide backbone conformation.

    3. A “Star” Antiferromagnet: A Polymeric Iron(III) Acetate That Exhibits Both Spin Frustration and Long-Range Magnetic Ordering (pages 6076–6080)

      Yan-Zhen Zheng, Ming-Liang Tong, Wei Xue, Wei-Xiong Zhang, Xiao-Ming Chen, Fernande Grandjean and Gary J. Long

      Version of Record online: 6 JUL 2007 | DOI: 10.1002/anie.200701954

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      Star formation: Polymeric [Fe33-O)(μ-OAc)6(H2O)3][Fe33-O)μ-OAc)7.5]2⋅7 H2O is synthesized by linking triangular {Fe33-O)} clusters through anti-anti bridging acetate ligands (see picture; red and blue: Fe, orange: O). Spin frustration and long-range magnetic order coexist in this compound below 4.5 K (see graph).

    4. Long-Range Magnetic Ordering in a TbIII–MoV Cyanido-Bridged Quasi-One-Dimensional Complex (pages 6081–6084)

      Ferry Prins, Edoardo Pasca, L. Jos de Jongh, Huub Kooijman, Anthony L. Spek and Stefania Tanase

      Version of Record online: 10 JUL 2007 | DOI: 10.1002/anie.200701847

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      One-dimensional polymer [Tb(pzam)3(H2O)Mo(CN)8]⋅H2O (see picture, pzam=pyrazine-2-carboxamide; C black, Mo yellow, N blue, O red, Tb green) has been synthesized and characterized. Its magnetic susceptibility data indicate substantial ferromagnetic superexchange between TbIII and MoV via the cyanido bridge, and the occurrence of long-range magnetic ordering between chains at Tc≈1 K.

    5. Encapsulation of Myoglobin in PEGylated Polyion Complex Vesicles Made from a Pair of Oppositely Charged Block Ionomers: A Physiologically Available Oxygen Carrier (pages 6085–6088)

      Akihiro Kishimura, Aya Koide, Kensuke Osada, Yuichi Yamasaki and Kazunori Kataoka

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701776

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      Take your PIC: Biologically active polyion complex vesicles (PICsomes) with encapsulated myoglobin (Mb) can be prepared by the self-assembly of a pair of oppositely charged block ionomers with polyethylene glycol (PEG) segments (see picture; metMb: metmyoglobin). The loaded Mb maintains reversible oxygenation even in the presence of trypsin.

    6. Functional DNA Nanotube Arrays: Bottom-Up Meets Top-Down (pages 6089–6092)

      Chenxiang Lin, Yonggang Ke, Yan Liu, Michael Mertig, Jian Gu and Hao Yan

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701767

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      Meeting in the middle: Well-organized arrays of self-assembled functional DNA nanotubes can be constructed by combining bottom-up and top-down methods. Such DNA-nanotube arrays allow the construction of arrays of quantum dots, proteins, and DNA targets (see picture; green: DNA nanotube, red: streptavidin–quantum dot conjugate; scale bar: 20 μm).

    7. Preparation of Cyclobis(paraquat-p-phenylene)-Based [2]Rotaxanes Without Flexible Glycol Chains (pages 6093–6097)

      Sune Nygaard, Bo W. Laursen, Thomas S. Hansen, Andrew D. Bond, Amar H. Flood and Jan O. Jeppesen

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701722

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      Completely armless: The efficient synthesis of two sterically confined [2]rotaxanes has shown that oligoethylene glycol arms are not requisites for a clipping reaction to form π-donor/acceptor [2]rotaxanes (see scheme). The rigid nature of the [2]rotaxanes forces the tetracationic cyclophane to encapsulate the initially π-electron-rich station, regardless of its oxidation state, thus generating tunable properties and enhanced stabilities.

    8. Dynamics of Porphyrin Electron-Transfer Reactions at the Electrode–Electrolyte Interface at the Molecular Level (pages 6098–6101)

      Yufan He and Eric Borguet

      Version of Record online: 6 JUL 2007 | DOI: 10.1002/anie.200603822

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      Potential causes: The combination of potential-pulse perturbation and STM has shown that the interfacial oxidation of an adsorbed 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP) monolayer at the Au(111)/0.1 M H2SO4 interface is spacially heterogeneous (see STM image; dark spots: oxidized TPyP, light spots: nonoxidized TPyP). The distribution of the oxidized TPyP molecules on the surface depends on the oxidation potential and varies with time.

    9. Hydrogen-Gas Migration through Clathrate Hydrate Cages (pages 6102–6105)

      Saman Alavi and John A. Ripmeester

      Version of Record online: 10 JUL 2007 | DOI: 10.1002/anie.200700250

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      Escape! Electronic-structure calculations have been used to estimate the energy barriers to the migration of H2 guest molecules from the cages of the structure-II clathrate hydrate (see picture; H green, O red). The escape rates from the cages were calculated using an Arrhenius expression with a tunneling correction.

      Corrected by:

      Corrigendum: Hydrogen-Gas Migration through Clathrate Hydrate Cages

      Vol. 46, Issue 47, 8933, Version of Record online: 23 NOV 2007

    10. Extending the {(Mo)Mo5}12M30 Capsule Keplerate Sequence: A {Cr30} Cluster of S=3/2 Metal Centers with a {Na(H2O)12} Encapsulate (pages 6106–6110)

      Ana Maria Todea, Alice Merca, Hartmut Bögge, Joris van Slageren, Martin Dressel, Larry Engelhardt, Marshall Luban, Thorsten Glaser, Marc Henry and Achim Müller

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200700795

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      Stuck in the middle with you: The spherical cluster {(Mo)Mo5}12Cr30 (1) fills, with its spin, a gap in the series of the analogous Fe (S=5/2) and V (S=1/2) clusters. This allows a deeper understanding of the magnetic properties of the series members, particularly with reference to geometric frustration, also found in the famous Kagomé lattices. The spherical clusters can be considered as coordination polymers with spherical periodicity which contain unique pentagonal molybdenum oxide based ligands.

    11. Polymer-Based Elemental Tags for Sensitive Bioassays (pages 6111–6114)

      Xudong Lou, Guohua Zhang, Isaac Herrera, Robert Kinach, Olga Ornatsky, Vladimir Baranov, Mark Nitz and Mitchell A. Winnik

      Version of Record online: 29 MAY 2007 | DOI: 10.1002/anie.200700796

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      It's elemental: A water-soluble polymer bearing multiple metal-chelating ligands has been used as a tag for bioassays with inductively coupled plasma mass spectrometry. The tag was covalently conjugated to antibodies, and the polymer–antibody constructs were loaded with lanthanide ions (Ln3+) and used for the simultaneous assay of five orthogonally labeled antibodies against cell surface antigens that differ in abundance by more than two orders of magnitude.

    12. Chiralization of Diamond Nets: Stretchable Helices and Chiral and Achiral Nets with Nearly Identical Unit Cells (pages 6115–6118)

      Jian Zhang and Xianhui Bu

      Version of Record online: 24 JUL 2007 | DOI: 10.1002/anie.200701374

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      Stretchable diamond nets: Homochiral and achiral diamond nets with nearly identical unit cells have been found in a family of 3D framework materials containing flexible helical substructures (see picture; Cd green, O red, C gray). Such structures raise intriguing prospects for developing general strategies for the direct conversion of achiral four-connected networks into homochiral networks through ligand substitution.

    13. Single-Site, Single-Component Catalysts for Very High Molecular Weight Polyethylene: A Robust “Ready-To-Go” Vanadium π-Bonded Complex Without a Preformed V[BOND]C Bond (pages 6119–6122)

      Amir Jabri, Ilia Korobkov, Sandro Gambarotta and Robbert Duchateau

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701703

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      On its own: A vanadium(II) bis(pyrrolide) complex with a vanadocene-type structure is a single-component catalyst for the preparation of ultrahigh molecular weight polyethylene (PE; see scheme; Mw=weight-average molecular weight, PDI=polydispersity index).

    14. Dynamic Kinetic Asymmetric Allylic Amination and Acyl Migration of Vinyl Aziridines with Imido Carboxylates (pages 6123–6125)

      Barry M. Trost, Daniel R. Fandrick, Tobias Brodmann and Dylan T. Stiles

      Version of Record online: 10 JUL 2007 | DOI: 10.1002/anie.200700835

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      An atom-economical method has been developed for the preparation of chiral vicinal diamines through a dynamic kinetic asymmetric allylic amination and acyl-group migration of vinyl aziridines with imido carboxylates. Application of the asymmetric transformation enabled the concise synthesis of the azepane core 1 of (+)-balanol and its syn analogue.

    15. Immuno-Polymeric Nanoparticles by Diels–Alder Chemistry (pages 6126–6131)

      Meng Shi, Jordan H. Wosnick, Karyn Ho, Armand Keating and Molly S. Shoichet

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701032

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      Hitting the target: Self-assembled polymeric nanoparticles from an amphiphilic copolymer were prepared with furan groups on the outer polyethylene glycol corona that were accessible for Diels–Alder reactions with maleimide-functionalized antibodies for the preparation of immuno-nanoparticles (see picture). The simple and clean coupling methodology allows facile modification of nanoparticles for use in targeted delivery to cancer cells.

    16. Bis(1,2,3,4-η4-anthracene)ferrate(1−): A Paramagnetic Homoleptic Polyarene Transition-Metal Anion (pages 6132–6136)

      William W. Brennessel, Robert E. Jilek and John E. Ellis

      Version of Record online: 5 JUL 2007 | DOI: 10.1002/anie.200701353

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      Magnetic personalities: [Fe(η4-C14H10)2] is an unprecedented example of an anionic 17-electron homoleptic polyarene transition-metal complex. This species is the first isolable homoleptic polyarene iron complex. It provides “naked” atomic Fe−I in its reaction with 1,3-butadiene to yield the first structurally authenticated homoleptic bis(1,3-butadiene) metal complex, [Fe(η4-C4H6)2] (see structure).

    17. Photoamplification and Multiple Tag Release in a Linear Peptide-Based Array of Dithiane Adducts (pages 6137–6140)

      Kavitha Majjigapu, Janaki R. R. Majjigapu and Andrei G. Kutateladze

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701512

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      Binary encoding and amplification can be achieved in linear polypeptide-based scaffolds of photoactive dithiane adducts. QA masked sensitizer is tethered to lysine and incorporated in a peptide chain terminated with a sensitizer (see picture). When illuminated, the sensitizer induces fragmentation, thus unmasking more sensitizer and resulting in a linear domino photoamplification effect.

    18. Pd-Catalyzed Polymerization of Dienes that Involves Chain-Walking Isomerization of the Growing Polymer End: Synthesis of Polymers Composed of Polymethylene and Five-Membered-Ring Units (pages 6141–6143)

      Takeshi Okada, Sehoon Park, Daisuke Takeuchi and Kohtaro Osakada

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701630

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      Walk the line: Cyclopolymerization of 1,6-dienes with vinyl and vinylene groups catalyzed by PdII–diimine complexes causes chain walking of the growing polymer. This isomerization leads to polymers with trans-1,2-disubstituted cyclopentane groups located regularly along the linear polymer chain (see scheme). The polymerization is applicable for dienes with various functional groups.

    19. Molecular Wire Type Behavior of Polycationic Multinuclear Rack-Type RuII Complexes of Polytopic Hydrazone-Based Ligands (pages 6144–6147)

      Frédérique Loiseau, Francesco Nastasi, Adrian-Mihail Stadler, Sebastiano Campagna and Jean-Marie Lehn

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200700388

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      On the rack: Splitting of the peripheral metal-based oxidation, which indicates a large coupling between the redox sites, has been obtained in polymetallic arrays composed of rack-type complexes containing two, three, four, or six RuII subunits appended to hydrazone-based molecular strands (see picture). The relatively small coupling attenuation parameter calculated for the metal-based, cationic subunit(s) suggests molecular-wire behavior.

    20. A Highly Convergent Chemical Synthesis of Conformational Epitopes of Rhamnogalacturonan II (pages 6148–6151)

      Yu Rao and Geert-Jan Boons

      Version of Record online: 6 JUL 2007 | DOI: 10.1002/anie.200701750

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      Upon careful tuning of the reactivity of glycosyl donors and acceptors, tetra- and hexasaccharide fragments (see structure) of the B chain of rhamnogalacturonan II (RGII) were prepared in a convergent and stereoselective manner. The conformation of the central arabinopyranosyl ring (red) was found to depend on the saccharide substitution pattern. This conformational epitope may influence the biological functions of RGII.

    21. Unsaturated, Mixed-Valence Diiron Dithiolate Model for the Hox State of the [FeFe] Hydrogenase (pages 6152–6154)

      Aaron K. Justice, Thomas B. Rauchfuss and Scott R. Wilson

      Version of Record online: 6 JUL 2007 | DOI: 10.1002/anie.200702224

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      Chemists are closing in on functional and structural models for the [FeFe] hydrogenases. Oxidation of [Fe2(S2C2H4)(CO)3(PMe3)(dppv)] (dppv=cis-1,2-C2H2(PPh2)2) by one electron affords a mixed-valence model for the Hox state of the active site of the [FeFe] hydrogenases. Like the enzyme, this model exhibits the “rotated structure” and binds CO (see scheme). The radical character of the model is confirmed by its ready binding of NO.

    22. Convenient Access to Trifluoromethanol (pages 6155–6158)

      Karl O. Christe, Joachim Hegge, Berthold Hoge and Ralf Haiges

      Version of Record online: 10 JUL 2007 | DOI: 10.1002/anie.200701823

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      From chimera to useful reagent: Easy access to trifluoromethanol in a one-step reaction from readily available inexpensive bulk chemicals opens the door for CF3OH to become a useful general reagent in synthetic chemistry and industrial applications.

    23. Highly Efficient Synthesis of Tricyclic Amines by a Cyclization/Cycloaddition Cascade: Total Syntheses of Aspidospermine, Aspidospermidine, and Quebrachamine (pages 6159–6162)

      Iain Coldham, Adam J. M. Burrell, Laura E. White, Harry Adams and Niall Oram

      Version of Record online: 10 JUL 2007 | DOI: 10.1002/anie.200701943

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      Three in one: Three new rings can be made in one pot with complete control of the regio- and stereochemistry by a tandem cyclization/cycloaddition cascade reaction. Treatment of a chloroaldehyde with an amine gives a cyclic azomethine ylide that undergoes intramolecular cycloaddition onto a tethered alkene. The method was applied to the shortest known synthesis of aspidospermine (see scheme).

    24. Hydration of a Chiral Molecule: The Propylene Oxide⋅⋅⋅(Water)2 Cluster in the Gas Phase (pages 6163–6166)

      Zheng Su and Yunjie Xu

      Version of Record online: 6 JUL 2007 | DOI: 10.1002/anie.200701966

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      Bridging the gap between a binary system and a solute in aqueous solution: Conformers of the ternary cluster propylene oxide (PO)⋅⋅⋅(H2O)2 were studied using rotational spectroscopy and high-level ab initio calculations. The experimental observation shows that the anti conformer is favored over the syn conformer, opposite to what was detected for PO⋅⋅⋅H2O, but in accord with what was predicted for PO in water.

    25. Total Synthesis of (−)-Reidispongiolide A, an Actin-Targeting Marine Macrolide (pages 6167–6171)

      Ian Paterson, Kate Ashton, Robert Britton, Giuseppe Cecere, Gaëlle Chouraqui, Gordon J. Florence and Jonathan Stafford

      Version of Record online: 6 JUL 2007 | DOI: 10.1002/anie.200702178

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      Actin class: A stereoselective synthesis of the microfilament-destabilizing cytotoxic macrolide (−)-reidispongiolide A, isolated from the marine sponge Reidispongia coerulea, uses a convergent aldol-based strategy to construct the 26-membered macrolactone, followed by a coupling with an N-vinylformamide subunit. This constitutes the first synthesis of any member of the reidispongiolide/sphinxolide family.

    26. (N-Heterocyclic Carbene)Gold(I)-Catalyzed Cycloisomerization of Cyclohexadienyl Alkynes to Tetracyclo[3.3.0.02,8.04,6]octanes (pages 6172–6175)

      Soo Min Kim, Ji Hoon Park, Soo Young Choi and Young Keun Chung

      Version of Record online: 10 JUL 2007 | DOI: 10.1002/anie.200702028

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      Biscyclopropanation: Dienynes containing a cyclohexadienyl unit can be converted into tetracyclo[3.3.0.02,8.04,6]octanes by treatment with an (N-heterocyclic carbene)gold catalyst. When the dienynes bear an open-chain diene instead of cyclohexadiene, open-cage compounds, with two sides missing from the cage, are obtained.

    27. DABCO and DMAP—Why Are They Different in Organocatalysis? (pages 6176–6179)

      Mahiuddin Baidya, Shinjiro Kobayashi, Frank Brotzel, Uli Schmidhammer, Eberhard Riedle and Herbert Mayr

      Version of Record online: 12 JUL 2007 | DOI: 10.1002/anie.200701489

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      What makes a good organocatalyst? DABCO (1,4-diazabicyclo[2.2.2]octane) is a thousandfold better nucleophile (k[RIGHTWARDS ARROW]) and at the same time a million times better leaving group (k[LEFTWARDS ARROW]) than DMAP (4-(dimethylamino)pyridine). This apparent contradiction is resolved by consideration of the intrinsic reaction barriers.

    28. Nucleic Acid Binders Activated by Light of Selectable Wavelength (pages 6180–6183)

      Alexandru Rotaru and Andriy Mokhir

      Version of Record online: 10 JUL 2007 | DOI: 10.1002/anie.200700641

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      Let loose in the red-light district: “Caged” DNAs are described that can be activated by light of selectable wavelength. This is possible with, for example, red light, which is significantly less damaging than UV light and can permeate deeply into tissues (see scheme).

    29. Gold-Catalyzed Benzylic C[BOND]H Activation at Room Temperature (pages 6184–6187)

      A. Stephen K. Hashmi, Sascha Schäfer, Michael Wölfle, Cesar Diez Gil, Peter Fischer, Antonio Laguna, M. Carmen Blanco and M. Concepción Gimeno

      Version of Record online: 10 JUL 2007 | DOI: 10.1002/anie.200701521

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      A tale of the unexpected: Coordinating and potentially chelating groups allow gold-catalyzed benzylic C[BOND]H activation at room temperature. Substrates with additional nucleophilic substituents undergo unexpected dimerizations, in which eight new bonds are formed (see scheme).

    30. Self-Assembling Living Systems with Functional Nanomaterials (pages 6188–6191)

      Zoran Popović, Matthias Otter, Gion Calzaferri and Luisa De Cola

      Version of Record online: 3 JUL 2007 | DOI: 10.1002/anie.200701019

      Thumbnail image of graphical abstract

      To catch a bug: Self-assembly of bacteria has been achieved by combining Escherichia coli and synthetic zeolite L. The assembly can be controlled so that the structure possesses either a 1:1 or 2:1 ratio (see schematic representation) between the bacteria and porous nanocontainers.

    31. The Tungstogermanate [Ce20Ge10W100O376(OH)4(H2O)30]56−: A Polyoxometalate Containing 20 Cerium(III) Atoms (pages 6192–6195)

      Bassem S. Bassil, Michael H. Dickman, Isabella Römer, Bernd von der Kammer and Ulrich Kortz

      Version of Record online: 19 JUL 2007 | DOI: 10.1002/anie.200701422

      Thumbnail image of graphical abstract

      Big W: One of the largest polytungstates, the 20 cerium(III) atom tungstogermanate [Ce20Ge10W100O376(OH)4(H2O)30]56− (1), has been synthesized from CeIII ions and [α-GeW9O34]10− in aqueous acidic medium at pH 5.0. Polyanion 1 represents the first lanthanide-substituted tungstogermanate and can be described as a dimer that is linked through long Ce[BOND]O(W) bridges.

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