Angewandte Chemie International Edition

Cover image for Vol. 49 Issue 48

November 22, 2010

Volume 49, Issue 48

Pages 9013–9293

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Cover Picture: A Double-Switching Multistable Fe4 Grid Complex with Stepwise Spin-Crossover and Redox Transitions (Angew. Chem. Int. Ed. 48/2010) (page 9013)

      Dipl.-Chem. Benjamin Schneider, Dr. Serhiy Demeshko, Dr. Sebastian Dechert and Prof. Dr. Franc Meyer

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201005440

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      A [2×2] Fe4grid complex featuring two orthogonal switching modes, namely stepwise spin-crossover and sequential redox processes, is presented by F. Meyer and co-workers in their Communication on page 9274 ff. Of particular interest are the resulting twofold-degenerate configurations [HS-LS-HS-LS] and [FeII2FeIII2], where two identical metal centers occupy opposite corners of the Fe4 square. Such an arrangement qualifies this new grid complex as a potential building block for quantum cellular automata.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Inside Cover: Generation and Reactions of an Unsubstituted N-Heterocyclic Carbene Boryl Anion (Angew. Chem. Int. Ed. 48/2010) (page 9014)

      Dr. Julien Monot, Andrey Solovyev, Dr. Hélène Bonin-Dubarle, Dr. Étienne Derat, Prof. Dennis P. Curran, Prof. Marc Robert, Prof. Louis Fensterbank, Prof. Max Malacria and Dr. Emmanuel Lacôte

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201005438

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      Easy access to a new carbene boryl anion has been discovered by a collaborative team of three research groups, from Paris and Pittsburgh. In their Communication on page 9166 ff., M. Malacria, D. P. Curran et al. describe the preparation of an N-heterocyclic carbene boryl anion through reductive lithiation of a boryl iodide. This anion can be trapped at boron with a variety of electrophiles to give unusual carbene borane products.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
  4. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
  5. Author Profile

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Hsiang-Rong Tseng (page 9036)

      Article first published online: 26 OCT 2010 | DOI: 10.1002/anie.201005362

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      “My favorite subjects at school were chemistry and physics. When I wake up I check my e-mails …” This and more about Hsiang-Rong Tseng can be found on page 9036.

  6. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
  7. Obituary

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Marc Julia (1922–2010) (pages 9038–9039)

      Jean-Claude Chottard, Jean-Yves Lallemand, Daniel Mansuy and Jean-Noël Verpeaux

      Article first published online: 20 OCT 2010 | DOI: 10.1002/anie.201006207

  8. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Silver in Organic Chemistry. Edited by Michael Harmata. (page 9040)

      Pedro J. Pérez

      Article first published online: 9 NOV 2010 | DOI: 10.1002/anie.201006002

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      John Wiley & Sons Inc., 2010. 402 pp., hardcover, € 95.90.—ISBN 978-0470466117

  9. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Protein Chemistry

      Carpe Diubiquitin (pages 9042–9044)

      Dr. Langdon J. Martin and Prof. Ronald T. Raines

      Article first published online: 4 NOV 2010 | DOI: 10.1002/anie.201005946

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      Chained melody: Ubiquitination is forged through the nonstandard isopeptide bond between the ε-nitrogen atom of a lysine residue on a target protein and the C-terminal carboxy group of ubiquitin. Several complementary synthetic approaches have led to designated diubiquitin chains in quantities useful for structure–function analyses, culminating in the total chemical synthesis of all seven diubiquitin chains.

    2. Boron Chemistry

      BO Chemistry Comes Full Circle (pages 9045–9046)

      Prof. Stephen A. Westcott

      Article first published online: 28 SEP 2010 | DOI: 10.1002/anie.201003379

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      No BO problem! Low-coordinate boron centers can be stabilized by using late transition metals, for example a platinum bisphosphine fragment. [Pt(PCy3)2] reacts with Br2BOSiMe3 to give trans-[(PCy3)2PtBr(BO)], which contains an unprecedented thermally stable B[TRIPLE BOND]O bond (see picture, Cy= cyclohexyl).

    3. Nobel Prize in Chemistry 2010

      From Noble Metal to Nobel Prize: Palladium-Catalyzed Coupling Reactions as Key Methods in Organic Synthesis (pages 9047–9050)

      Xiao-Feng Wu, Dr. Pazhamalai Anbarasan, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

      Article first published online: 28 OCT 2010 | DOI: 10.1002/anie.201006374

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      Building bridges: Palladium-catalyzed cross-coupling reactions of aryl halides and related compounds allow the expeditious and controlled synthesis of important carbon-based scaffolds (see scheme). Their essential role in organic chemistry has resulted in such reactions being recognized by the Nobel Prize for Chemistry 2010.

  10. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Oxetanes

      Oxetanes as Versatile Elements in Drug Discovery and Synthesis (pages 9052–9067)

      Johannes A. Burkhard, Dr. Georg Wuitschik, Dr. Mark Rogers-Evans, Prof. Dr. Klaus Müller and Prof. Dr. Erick M. Carreira

      Article first published online: 28 OCT 2010 | DOI: 10.1002/anie.200907155

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      Small but powerful: In recent years oxetanes have received newly gained attention in medicinal chemistry and by the synthetic community since it has been found that the introduction of an oxetane unit in the molecular scaffold of a compound can significantly modify its properties. This Minireview summarizes the advantages of oxetanes in drug discovery and outlines chemical transformations involving oxetanes.

  11. Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Rylene Dyes

      The Rylene Colorant Family—Tailored Nanoemitters for Photonics Research and Applications (pages 9068–9093)

      Prof. Dr. Tanja Weil, Prof. Dr. Tom Vosch, Prof. Dr. Johan Hofkens, Kalina Peneva and Prof. Dr. Klaus Müllen

      Article first published online: 25 OCT 2010 | DOI: 10.1002/anie.200902532

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      Live and let dye: Rylene dyes, such as those shown in the picture together with their absorption spectra (R=tert-octylphenyl, R'=diisopropylphenyl) have outstanding optical properties and can be modified in a site-directed fashion. In recent years, several novel applications of these functional materials have emerged, such as in photonics, single-molecule spectroscopy, as well as for biological investigations.

    2. Synthetic Methods

      Isocyanides in the Synthesis of Nitrogen Heterocycles (pages 9094–9124)

      Dr. Alexander V. Lygin and Prof. Dr. Armin de Meijere

      Article first published online: 4 NOV 2010 | DOI: 10.1002/anie.201000723

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      “Aromatic compounds”: The pungent odor of volatile isocyanides is by far compensated by the unique properties of the isocyano group. Since their discovery some 150 years ago, isocyanides have found numerous applications in the synthesis of nitrogen heterocycles. Apart from various multicomponent processes, many other alternatives exist to build such ring systems from isocyanides.

  12. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Review
    10. Highlights
    11. Minireview
    12. Reviews
    13. Communications
    14. Preview
    1. Protein Synthesis

      Total Chemical Synthesis of Di-ubiquitin Chains (pages 9126–9131)

      Dr. K. S. Ajish Kumar, Liat Spasser, Lesly A. Erlich, Dr. Sudhir N. Bavikar and Dr. Ashraf Brik

      Article first published online: 2 SEP 2010 | DOI: 10.1002/anie.201003763

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      Building the chains: A general and effective approach for the total chemical synthesis of all the di-ubiquitin chains (see picture) is presented. The behavior of the synthetic chains in the presence of isopeptidase T, an enzyme responsible for the disassembly of the majority of unanchored polyubiquitin in vivo, was examined.

    2. Gold Catalysis

      The [4+2], not [2+2], Mechanism Occurs in the Gold-Catalyzed Intramolecular Oxygen Transfer Reaction of 2-Alkynyl-1,5-Diketones (pages 9132–9135)

      Dr. Le-Ping Liu, Deepika Malhotra, Dr. Robert S. Paton, Prof. Dr. K. N. Houk and Prof. Dr. Gerald B. Hammond

      Article first published online: 28 OCT 2010 | DOI: 10.1002/anie.201005514

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      [2+2] or [4+2]? Mechanistic studies on the gold-catalyzed intramolecular oxygen transfer of 2-alkynyl-1,5-diketones were performed using isotopic experiments and quantum chemical calculations. The results demonstrate that the transformation follows a [4+2] pathway instead of the previously proposed [2+2] path (see scheme). Various substrates were employed in the reaction and the corresponding products were obtained in excellent yields.

    3. Polymers on Surfaces

      Conformation and Packing of Porphyrin Polymer Chains Deposited Using Electrospray on a Gold Surface (pages 9136–9139)

      Alex Saywell, Johannes K. Sprafke, Dr.  Louisa J. Esdaile, Andrew J. Britton, Anna Rienzo, Prof. Harry L. Anderson, Dr. James N. O'Shea and Prof. Peter H. Beton

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201004896

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      Molecular worms: Porphyrin polymers and oligomers are deposited on a Au(111) surface using electrospray deposition and are shown to adopt an arrangement where chains from neighboring molecules are interdigitated. Although the flexible nature of the polymers gives rise to sharp kinks and the crossing of polymer strands (see scheme), a longer correlation length as compared with solvated oligomers is observed.

    4. Living Polymerization

      Programmable Modulation of Co-monomer Relative Reactivities for Living Coordination Polymerization through Reversible Chain Transfer between “Tight” and “Loose” Ion Pairs (pages 9140–9144)

      Jia Wei, Wei Zhang, Rennisha Wickham and Prof. Lawrence R. Sita

      Article first published online: 27 OCT 2010 | DOI: 10.1002/anie.201004709

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      Not leaving anything to chance: Rapid and reversible exchange between “tight” and “loose” ion pairs was used to modulate the relative reactivities of ethene and 1-hexene or cyclopentene in a programmed fashion for living coordination chain-transfer polymerization. Thus, different grades of a monodisperse polyolefin copolymer, such as the poly(ethene-co-1-hexene) samples shown, could be obtained with a single cationic transition-metal catalyst.

    5. Surface Chemistry

      Direct Three-Dimensional Imaging of the Buried Interfaces between Water and Superhydrophobic Surfaces (pages 9145–9148)

      Dr. Chan Luo, Hua Zheng, Dr. Lei Wang, Prof. Haiping Fang, Prof. Jun Hu, Prof. Chunhai Fan, Prof. Yong Cao and Prof. Jian Wang

      Article first published online: 7 OCT 2010 | DOI: 10.1002/anie.201002470

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      Walking on air: Confocal laser scanning microscopy can be used to provide distinct 3D images of air at buried superhydrophobic interfaces (see picture, bright area). Two hydrophobic states, Wenzel and Cassie states, have been quantitatively visualized and distinctly identified. The 10 μm thick air cushion drastically decreases water adhesion, thus making water droplets roll off the surface and readily remove surface contaminants (self-cleaning).

    6. Fuel Cells

      Ternary Heterostructured Nanoparticle Tubes: A Dual Catalyst and Its Synergistic Enhancement Effects for O2/H2O2 Reduction (pages 9149–9152)

      Dr. Chun-Hua Cui, Hui-Hui Li, Jin-Wen Yu, Dr. Min-Rui Gao and Prof. Dr. Shu-Hong Yu

      Article first published online: 21 OCT 2010 | DOI: 10.1002/anie.201003261

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      ORR things bright and beautiful: A new kind of unsupported Pd-Au-Cu (PdAuCu) ternary heterostructured nanoparticle-tube catalyst was synthesized (see TEM image and dispersive X-ray spectroscopy maps). The incorporation of Au into a PdCu system gives a synergistic enhancement of the oxygen reduction reaction (ORR) and of the H2O2 reduction reaction. The approach provides a promising route to the development of gas/liquid oxidant fuel cells with ultrahigh electrical power output.

    7. Indole Oxidation

      Oxaziridine-Mediated Oxyamination of Indoles: An Approach to 3-Aminoindoles and Enantiomerically Enriched 3-Aminopyrroloindolines (pages 9153–9157)

      Tamas Benkovics, Dr. Ilia A. Guzei and Prof. Tehshik P. Yoon

      Article first published online: 21 OCT 2010 | DOI: 10.1002/anie.201004635

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      A radical solution: A highly regioselective copper(II)-catalyzed oxyamination of N-acyl indoles with oxaziridines gave aminal products that could be converted in a single step into 3-aminoindoles and 3-aminopyrroloindolines (see scheme). When a chiral N-acyl group was used, the core fragment of some architecturally fascinating pyrroloindoline alkaloids was formed with 91 % ee. Bs=benzenesulfonyl, Moc=methoxycarbonyl.

    8. Lithium Ion Batteries

      Ionic-Liquid-Tethered Nanoparticles: Hybrid Electrolytes (pages 9158–9161)

      Dr. Surya S. Moganty, Dr. N. Jayaprakash, Jennifer L. Nugent, Dr.  J. Shen and Prof. Lynden A. Archer

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201004551

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      A new class of solventless electrolytes was created by tethering ionic liquids to hard inorganic ZrO2 nanostructures (see picture; NIM=nanoscale ionic material). These hybrid fluids exhibit exceptional redox stability windows, excellent thermal stability, good lithium transference numbers, long-term interfacial stability in the presence of a lithium anode and, when doped with lithium salt, reasonable ionic conductivities.

    9. Block Copolymers

      Block Copolymers Comprising π-Conjugated and Liquid Crystalline Subunits: Induction of Macroscopic Nanodomain Orientation (pages 9162–9165)

      Dehui Han, Xia Tong, Yi Zhao and Prof. Yue Zhao

      Article first published online: 19 OCT 2010 | DOI: 10.1002/anie.201004445

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      Block party: A block copolymer comprises both regioregular poly(3-hexylthiophene) (P3HT) and a side-chain liquid-crystalline polymer (SCLCP) bearing azobenzene mesogens. The SCLCP block has a clearing temperature above the high crystal-melting temperature of P3HT, therefore surface- and photoinduced orientation of mesogens in the SCLCP block can be used to align stripelike P3HT nanodomains on the macroscopic scale (see picture for AFM images).

    10. N-Heterocyclic Carbenes

      Generation and Reactions of an Unsubstituted N-Heterocyclic Carbene Boryl Anion (pages 9166–9169)

      Dr. Julien Monot, Andrey Solovyev, Dr. Hélène Bonin-Dubarle, Dr. Étienne Derat, Prof. Dennis P. Curran, Prof. Marc Robert, Prof. Louis Fensterbank, Prof. Max Malacria and Dr. Emmanuel Lacôte

      Article first published online: 17 SEP 2010 | DOI: 10.1002/anie.201004215

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      Lying low: A lithiated unsubstituted N-heterocyclic carbene (NHC) boryl anion can be generated by reduction, and trapped by electrophiles (see scheme; dipp=2,6-diisopropylphenyl) to provide new substituted NHC boranes. It is yet another example of a low-valent boron compound or boron-containing reactive intermediate stabilized by an NHC, thereby extending the scope of NHC borane chemistry.

    11. Molecular Recognition

      Acid/Base- and Anion-Controllable Organogels Formed From a Urea-Based Molecular Switch (pages 9170–9173)

      Sheng-Yao Hsueh, Chun-Ting Kuo, Tsan-Wen Lu, Prof. Chien-Chen Lai, Yi-Hung Liu, Prof. Hsiu-Fu Hsu, Prof. Shie-Ming Peng, Prof. Chun-hsien Chen and Prof. Sheng-Hsien Chiu

      Article first published online: 15 OCT 2010 | DOI: 10.1002/anie.201004090

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      A switch in time: Gel–sol transitions of a urea-based [2]rotaxane gelator are controlled by the degree of solvent exposure of the hydrogen-bond-donating urea station and the orientation of the hydrogen-bond-accepting C[DOUBLE BOND]O groups of the interlocked ethylene glycol based macrocycle (N blue, O and macrocycle red, phenyl green). Both acid/base and anion-exchange control can be used to reversibly transition the rotaxane in 1-pentanol between solution and gel states.

    12. Organocatalysis

      Asymmetric Bromolactonization Catalyzed by a C3-Symmetric Chiral Trisimidazoline (pages 9174–9177)

      Dr. Kenichi Murai, Tomoyo Matsushita, Akira Nakamura, Shunsuke Fukushima, Masato Shimura and Prof. Dr. Hiromichi Fujioka

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201005409

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      A productive alliance: In an enantioselective organocatalytic bromolactonization of 5-substituted hex-5-enoic acids (see scheme), it appears that the formation of an ion pair through interaction of the trisimidazoline catalyst 1 with the substrate both creates a chiral environment and promotes the cyclization by activating the carboxylic acid. DBDMH=1,3-dibromo-5,5-dimethylhydantoin.

    13. Nitrogen Heterocycles

      A Modular, Efficient, and Stereoselective Synthesis of Substituted Piperidin-4-ols (pages 9178–9181)

      Dr. Li Cui, Dr. Chaoqun Li and Prof. Dr. Liming Zhang

      Article first published online: 15 OCT 2010 | DOI: 10.1002/anie.201004712

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      The pied piper-idinol of Hamelin: The one-pot synthesis of piperidin-4-ols by sequential gold-catalyzed cyclization, chemoselective reduction, and spontaneous Ferrier rearrangement has a broad substrate scope and shows excellent diastereoselectivity in the ring-formation step. This chemistry was employed in the six-step enantioselective synthesis of (+)-subcosine II.

    14. Olefination

      Catalytic Intermolecular Tail-to-Tail Hydroalkenylation of Styrenes with α Olefins: Regioselective Migratory Insertion Controlled by a Nickel/N-Heterocyclic Carbene (pages 9182–9186)

      Dr. Chun-Yu Ho and Lisi He

      Article first published online: 17 SEP 2010 | DOI: 10.1002/anie.201001849

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      Making head or tail of it: The first single-operation, highly selective intermolecular tail-to-tail hetero-hydroalkenylation from two readily available monosubstituted alkenes is described (see scheme; IPr=1,3-Bis(2,6-di-isopropylphenyl)imidazol-2-ylidene). The reaction is catalyzed by the proposed [(IPr)NiH]OTf species. The method allows the use of more common and structurally diverse α olefins as substrates, which were previously not compatible with known methods.

    15. Gas-Phase Conformations

      Conformations of γ-Aminobutyric Acid (GABA): The Role of the n[RIGHTWARDS ARROW]π* Interaction (pages 9187–9192)

      Prof. Susana Blanco, Prof. Juan C. López, Santiago Mata and Prof. José L. Alonso

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201002535

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      Conformation confirmation: The nine conformers of the neurotransmitter γ-aminobutyric acid (GABA) identified in the gas phase can serve as a basis to represent the shape of GABA. An n[RIGHTWARDS ARROW]π* interaction guided by the Bürgi–Dunitz trajectory of nucleophilic addition is thought to be relevant in the stabilization of two of the folded conformers (gG1 and gG3 in the picture).

    16. Spectroscopy

      On the Intrinsic Photophysics of Fluorescein (pages 9193–9196)

      Peter D. McQueen, Sandeep Sagoo, Huihui Yao and Prof. Rebecca A. Jockusch

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201004366

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      Not so bright: Ion trap mass spectrometry is used in conjunction with optical excitation and detection to study the intrinsic spectroscopic properties of the fluorescein cation, monoanion, and dianion in the gas phase. The dianion, which is a fluorescence quantum yield standard in solution, does not fluoresce significantly in the absence of solvent (see picture) because electron detachment is the favored deactivation pathway in the gas phase.

    17. Enantioselective Carbonylation

      Highly Enantioselective Hydroxycarbonylation and Alkoxycarbonylation of Alkenes using Dipalladium Complexes as Precatalysts (pages 9197–9200)

      Tina M. Konrad, Dr. José A. Fuentes, Prof. Alexandra M. Z. Slawin and Dr. Matthew L. Clarke

      Article first published online: 26 OCT 2010 | DOI: 10.1002/anie.201004415

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      Joined at Pd: Novel palladium catalysts like 1, in which the planar-chiral phosphine acts as a bridging ligand, have been developed. These dimetallic complexes are highly enantioselective catalysts in the hydroxycarbonylation of alkenes, a reaction that has proven problematic over the years. PTSA=para-toluenesulfonic acid.

    18. Photochemistry

      Ordering, Interaction, and Reactivity of the Low-Lying nπ* and ππ* Excited Triplet States of Acetophenone Derivatives (pages 9201–9205)

      Dr. Sohshi Yabumoto, Prof. Shinsuke Shigeto, Prof. Yuan-Pern Lee and Prof. Hiro-o Hamaguchi

      Article first published online: 15 OCT 2010 | DOI: 10.1002/anie.201004571

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      Lay low for a while: The low-lying nπ* and ππ* triplet states of substituted acetophenones have been directly observed by time-resolved near-infrared spectroscopy. The apparent reactivities of the ππ* T1 states of acetophenones have been shown to arise from the thermal population of the higher nπ* T2 states. Thermal equilibrium also occurs between the T1 and T2 states of the acetophenones.

    19. Photophysics

      Where is the Heavy-Atom Effect? Role of the Central Ligand in Tetragold(I) Ethynyl Complexes (pages 9206–9209)

      Dr. Glenna So Ming Tong, Pui Keong Chow and Prof. Dr. Chi-Ming Che

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201004601

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      He ain't heavy: The heavy-atom effect is not the sole factor that determines the efficiency of intersystem crossing and triplet radiative decay rates. Theoretical calculations along with experimental evidence show that the central ligand plays a decisive role in the luminescence behavior of tetragold(I) ethynyl complexes (see structures and representations of the highest occupied molecular orbitals).

    20. Heterocycle Synthesis

      Three-Component Assembly and Divergent Ring-Expansion Cascades of Functionalized 2-Iminooxetanes (pages 9210–9214)

      Weijun Yao, Lianjie Pan, Yiping Zhang, Gang Wang, Xiaoqin Wang and Prof. Cheng Ma

      Article first published online: 20 OCT 2010 | DOI: 10.1002/anie.201004685

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      A bold diversification strategy: Aromatic alkynes, p-toluenesulfonyl azide, and aromatic 2-oxobut-3-ynoates underwent a copper(I)-catalyzed multicomponent reaction to provide functionalized 2-iminooxetanes 1, which could be converted selectively into five-membered nitrogen-containing heterocycles of two different sorts, depending on the reaction conditions (see scheme; Tf=trifluoromethanesulfonyl; R=Et, iPr).

    21. Solid-State NMR Spectroscopy

      Rapid Three-Dimensional MAS NMR Spectroscopy at Critical Sensitivity (pages 9215–9218)

      Dr. Yoh Matsuki, Matthew T. Eddy, Prof. Dr. Robert G. Griffin and Prof. Dr. Judith Herzfeld

      Article first published online: 18 OCT 2010 | DOI: 10.1002/anie.201003329

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      Sensitive SIFTing: Multidimensional non-uniform sampling (NUS) NMR spectroscopy is extended to the severely sensitivity-limited regime typical of MAS NMR of biomacromolecules by the use of spectroscopy by the integration of frequency and time domain information (SIFT). A three-dimensional MAS NMR experiment is expedited (here 3.4-fold) without losing sensitivity or resolution.

    22. Olefin Functionalization

      Strategy Towards Olefin Carbohydroxylation: Transmetalation of 2-Rhodaoxetanes with Organoboron Nucleophiles (pages 9219–9224)

      Alexander Dauth and Prof. Jennifer A. Love

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201003348

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      Taking the first step: A 2-rhodaoxetane undergoes efficient transmetalation with a variety of functionalized aryl- and alkenyl boronic acids (see scheme). This process exhibits excellent functional-group compatibility and constitutes the first step in a proposed catalytic oxidative olefin functionalization.

    23. Catalyst Design

      Towards Selective Ethylene Tetramerization (pages 9225–9228)

      Dr. Sebastiano Licciulli, Indira Thapa, Khalid Albahily, Dr. Ilia Korobkov, Prof. Dr. Sandro Gambarotta, Dr. Robbert Duchateau, Dr. Reynald Chevalier and Dr. Katrin Schuhen

      Article first published online: 20 OCT 2010 | DOI: 10.1002/anie.201003465

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      And the magic number is … 4! A large amount of oligomer-free 1-octene (99.9 %) was produced from ethylene by a catalytic system based on chromium during the formation of polyethylene wax [see GC–MS chromatogram; the other three significant peaks are methanol (quenching agent), ethyl acetate (needle-rinsing agent), and toluene (solvent)].

    24. Natural Product Synthesis

      Total Synthesis of Nominal Banyaside B: Structural Revision of the Glycosylation Site (pages 9229–9232)

      Corinna S. Schindler, Louis Bertschi and Prof. Dr. Erick M. Carreira

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201004047

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      The total synthesis of the tripeptide nominal banyaside B relies on nonstandard peptide-bond-forming reactions. A key outcome of these synthetic studies is the proposal of a revised structure for natural banyaside B, in which the glycoside is indeed linked to the Abn core at the axial C-9 OH and not C-7 as in nominal banyaside B.

    25. Polyoxometalates

      Smart Self-Assemblies Based on a Surfactant-Encapsulated Photoresponsive Polyoxometalate Complex (pages 9233–9236)

      Yi Yan, Huanbing Wang, Dr. Bao Li, Guangfeng Hou, Zhendong Yin, Prof. Dr. Lixin Wu and Prof. Dr. Vivian W. W. Yam

      Article first published online: 18 OCT 2010 | DOI: 10.1002/anie.201004143

      Thumbnail image of graphical abstract

      Smart POMs: A surfactant-encapsulated organic-grafted polyoxometalate (POM) is synthesized by grafting a photoresponsive azobenzene group to an Anderson-type POM cluster. Self-assemblies of the hybrid complexes exhibit photocontrolled reversible aggregation and morphological change as a result of photoisomerization-induced structural alternation (see figure).

    26. Hollow Microspheres

      Hollow Ferrocenyl Coordination Polymer Microspheres with Micropores in Shells Prepared by Ostwald Ripening (pages 9237–9241)

      Dr. Jia Huo, Prof. Li Wang, Dr. Elisabeth Irran, Dr. Haojie Yu, Jingming Gao, Dengsen Fan, Bao Li, Jianjun Wang, Wenbing Ding, Abid Muhammad Amin, Chao Li and Liang Ma

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201004745

      Thumbnail image of graphical abstract

      From the inside out: Hollow ferrocenyl coordination polymer microspheres with microporous shells were prepared by a convenient and template-free approach. An Ostwald ripening mechanism is responsible for the formation of hollow cavities. The hierarchically hollow coordination polymer microspheres have potential applications in catalysis, drug delivery, and hydrogen storage.

    27. Voltammetry

      Cyclic Voltammetry in the Absence of Excess Supporting Electrolyte Offers Extra Kinetic and Mechanistic Insights: Comproportionation of Anthraquinone and the Anthraquinone Dianion in Acetonitrile (pages 9242–9245)

      Stephen R. Belding, Juan G. Limon-Petersen, Edmund J. F. Dickinson and Prof. Richard G. Compton

      Article first published online: 21 OCT 2010 | DOI: 10.1002/anie.201004874

      Thumbnail image of graphical abstract

      Less is more: The use of voltammetry in the total or partial absence of supporting electrolyte provides kinetic and mechanistic information beyond that available from familiar fully supported voltammetry. For example, unsupported voltammetry demonstrates that the comproportionation of anthraquinone and anthraquinone dianion proceeds at a diffusionally controlled rate in acetonitrile, a result which could not be determined from “diffusion-only” voltammetry.

    28. Enzyme Mimics

      A Chemical Model for the Inner-Ring Deiodination of Thyroxine by Iodothyronine Deiodinase (pages 9246–9249)

      Debasish Manna and Prof. Dr. Govindasamy Mugesh

      Article first published online: 12 OCT 2010 | DOI: 10.1002/anie.201005235

      Thumbnail image of graphical abstract

      The I of the beholder: The presented chemical model for the inner-ring deiodination of thyroxine (T4) and 3,5,3′-triiodothyronine (T3) by iodothyronine deiodinase (see scheme) highlights the importance of an in-built thiol group in proximity to the selenium atom. The effective removal of iodine in the case of T4 indicates that an enol–keto tautomerism is not required for deiodination.

    29. Natural Products

      Synthesis of (±)-Merrilactone A and (±)-Anislactone A (pages 9250–9253)

      Lei Shi, Karsten Meyer and Dr. Michael F. Greaney

      Article first published online: 21 OCT 2010 | DOI: 10.1002/anie.201005156

      Thumbnail image of graphical abstract

      A concise synthesis of each of the sesquiterpenoids merrilactone A and anislactone A is described using a common route. Reductive cleavage of an epoxide using TiIII and radical cyclization is used to install the C9 quaternary center at the heart of the BC bicycle (see scheme). Selective lactonization sequences then define regiodivergent pathways to both merrilactone A (formal synthesis) and anislactone A (total synthesis).

    30. Synthetic Methods

      Solvent-Dependent Enantiodivergent Mannich-Type Reaction: Utilizing a Conformationally Flexible Guanidine/Bisthiourea Organocatalyst (pages 9254–9257)

      Dr. Yoshihiro Sohtome, Shinji Tanaka, Keisuke Takada, Takahisa Yamaguchi and Prof. Dr. Kazuo Nagasawa

      Article first published online: 26 OCT 2010 | DOI: 10.1002/anie.201005109

      Thumbnail image of graphical abstract

      Flex control: Malonate and tert-butoxycarbonyl (Boc)-protected imines react in the presence of the flexible catalyst 1 to furnish the S or the R adduct depending upon the solvent used. Kinetic analyses in this enantiodivergent organocatalysis show that enthalpy–entropy compensation explains this behavior.

    31. Protein Microspheres

      Pure Protein Microspheres by Calcium Carbonate Templating (pages 9258–9261)

      Dr. Dmitry V. Volodkin, Prof. Dr. Regine von Klitzing and Prof. Dr. Helmuth Möhwald

      Article first published online: 22 OCT 2010 | DOI: 10.1002/anie.201005089

      Thumbnail image of graphical abstract

      Swapping spheres: Monodisperse protein microspheres can be fabricated by templating on porous CaCO3 microcores (see picture; CaCO3 gray, insulin orange). The CaCO3 cores decompose upon variation of pH from 9.0 to 5.0, whereas the insulin model protein precipitates. The method requires mild conditions, no additives, and minimal processing.

    32. Natural Products Synthesis

      Total Synthesis of Tryprostatins A and B (pages 9262–9265)

      Takayuki Yamakawa, Eiji Ideue, Jun Shimokawa and Prof. Dr. Tohru Fukuyama

      Article first published online: 28 OCT 2010 | DOI: 10.1002/anie.201004963

      Thumbnail image of graphical abstract

      A reasonable approach to the radical: The establishment of reliable conditions for the radical-mediated construction of indoles enabled the highly efficient synthesis of tryprostatins A and B. Use of the radical initiator 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) has allowed to carry out the radical cyclization at just 30 °C, thereby suppressing the formation of by-products.

      Corrected by:

      Corrigendum: Corrigendum: Total Synthesis of Tryprostatins A and B

      Vol. 53, Issue 34, 8808, Article first published online: 13 AUG 2014

    33. Organocatalysis

      NHC-Catalyzed Michael Addition to α,β-Unsaturated Aldehydes by Redox Activation (pages 9266–9269)

      Suman De Sarkar and Prof. Dr. Armido Studer

      Article first published online: 21 OCT 2010 | DOI: 10.1002/anie.201004593

      Thumbnail image of graphical abstract

      Through oxidative carbene catalysis the reactivity of enals can be reversed at the β position from the typical electrophilic to nucleophilic (homoenolate chemistry) further to electrophilic reactivity by two consecutive umpolung processes. These redox-activated Michael acceptors show higher reactivity at the β position than that for the starting enals. Their reactions with β-dicarbonyl compounds provide dihydropyranones in good to excellent yields under mild conditions.

    34. Domino Reactions

      Concise Synthesis of Tetrahydropyrans by a Tandem Oxa-Michael/Tsuji–Trost Reaction (pages 9270–9273)

      Liang Wang, Dr. Pengfei Li and Prof. Dr. Dirk Menche

      Article first published online: 26 OCT 2010 | DOI: 10.1002/anie.201003304

      Thumbnail image of graphical abstract

      A novel domino sequence facilitates the rapid assembly of polysubstituted tetrahydropyrans. The one-pot relay process generates up to three new stereogenic centers, including a tetrasubstituted carbon center, in a highly concise and convergent fashion from simple starting materials.

    35. Molecular Switches

      A Double-Switching Multistable Fe4 Grid Complex with Stepwise Spin-Crossover and Redox Transitions (pages 9274–9277)

      Dipl.-Chem. Benjamin Schneider, Dr. Serhiy Demeshko, Dr. Sebastian Dechert and Prof. Dr. Franc Meyer

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201001536

      Thumbnail image of graphical abstract

      Gridlock! A [2×2] Fe4 grid complex (see picture) with unprecedented stability features two orthogonal switching modes: spin-crossover and redox processes. Oxidation also switches between antiferromagnetic and ferromagnetic coupling. The [HS-LS-HS-LS] FeII4 and [FeII2FeIII2] forms are both twofold degenerate, with identical metal ions located at diagonal vertices of the grid, making the system an attractive component for quantum cellular automata.

    36. Peptidic Inhibitors

      Conformational Control of Integrin-Subtype Selectivity in isoDGR Peptide Motifs: A Biological Switch (pages 9278–9281)

      Dr. Andreas O. Frank, Dipl.-Chem. Elke Otto, Dr. Carlos Mas-Moruno, Dr. Herbert B. Schiller, Prof. Dr. Luciana Marinelli, Dr. Sandro Cosconati, Dipl.-Chem. Alexander Bochen, Dr. Dörte Vossmeyer, Dr. Grit Zahn, Dr. Roland Stragies, Prof. Dr. Ettore Novellino and Prof. Dr. Horst Kessler

      Article first published online: 18 OCT 2010 | DOI: 10.1002/anie.201004363

      Thumbnail image of graphical abstract

      The rearrangement of asparagine to isoaspartate (isoD) is responsible for the deactivation of many functional proteins. However, the isoDGR motif, which is optimally presented as a conformationally controlled cyclic pentapeptide, binds selectively to α5β1 integrin (see the docking model) with an affinity comparable to that of the peptidic antitumor agent Cilengitide.

    37. Titanocene Carbene

      [Cp2TiIII(NCy)2C[BOND]TiIIICp2]: A Transient Titanocene Carbene Complex? (pages 9282–9285)

      Dr. Oliver Theilmann, Martin Ruhmann, Dr. Alexander Villinger, Prof. Dr. Axel Schulz, Prof. Dr. Wolfram W. Seidel, Katharina Kaleta, Dr. Torsten Beweries, Dr. Perdita Arndt and Prof. Dr. Uwe Rosenthal

      Article first published online: 21 OCT 2010 | DOI: 10.1002/anie.201004145

      Thumbnail image of graphical abstract

      Carbene or not carbene? By utilizing [Cp2Ti(η2-Me3SiC2SiMe3)] (Cp=C5H5) as both a reducing and a quenching agent in the reaction with R[BOND]N[DOUBLE BOND]C[DOUBLE BOND]N[BOND]R, the first paramagnetic dinuclear titanocene(III) carbene-like complex is prepared in good yield. The complex features the topology of a four-membered N-heterocyclic carbene species but with a TiIII center as part of the heterocycle.

    38. Molecular Machines

      A Metal-Ion-Driven Supramolecular Chirality Pendulum (pages 9286–9289)

      Prof. Dr. Gebhard Haberhauer

      Article first published online: 21 OCT 2010 | DOI: 10.1002/anie.201004460

      Thumbnail image of graphical abstract

      Tick tock: The arms of a chirality pendulum can be completely and reversibly moved forward and backward like the pendulum of a clock by coordination and removal of a metal center (see picture). Each motion leads to a complete inversion of the configuration (swinging forth: P[RIGHTWARDS ARROW]M and swinging back: M[RIGHTWARDS ARROW]P).

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      Article first published online: 17 NOV 2010 | DOI: 10.1002/anie.201090152

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