Angewandte Chemie International Edition

Cover image for Vol. 48 Issue 43

October 12, 2009

Volume 48, Issue 43

Pages 7941–8149

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Cover Picture: Expedient Synthesis of N-Fused Indoles: A C[BOND]F Activation and C[BOND]H Insertion Approach (Angew. Chem. Int. Ed. 43/2009) (page 7941)

      Kohei Fuchibe, Tsukasa Kaneko, Keiji Mori and Takahiko Akiyama

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200904020

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      N-Fused indoles appear in the structures of various biologically active molecules, but synthesis of the fused-ring substructure has proved difficult. T. Akiyama and co-workers describe in their Communication on page 8070 ff. a new route in which a niobium carbenoid is generated by niobium-catalyzed activation of the normally inactive C–F bonds of a CF3 group. The carbenoid then undergoes insertion into a neighboring C(sp3)[BOND]H bond adjacent to a nitrogen atom to furnish the N-fused indole skeleton.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Inside Cover: Snapshots of the Al[BOND]Al σ-Bond Formation Starting from {AlR2} Units: Experimental and Computational Observations (Angew. Chem. Int. Ed. 43/2009) (page 7942)

      Patrick Henke, Tobias Pankewitz, Wim Klopper, Frank Breher and Hansgeorg Schnöckel

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200904023

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      Snapshots of the formation of a σ bond in Al2R4 isomers are obtained by structural and quantum chemical investigations, as described by H. Schnöckel, W. Klopper, and co-workers in their Communication on page 8141 ff. By employing R=PtBu2, they succeeded in isolating a triplet molecule exhibiting a long Al[BOND]Al separation as a first step. A bicyclic butterfly molecule rather than the unbridged R2AlAlR2 isomer represents the ground state. The ring-inversion isomers are separated by a “wing beat” and a transition state.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Gerhard Hilt (page 7964)

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200904969

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      “The most significant advances in chemistry of this century have been the advances made in organocatalysis. The biggest challenge facing chemists is to regain acceptance in the general public. …” This and more about Gerhard Hilt can be found on page 7964.

  6. Book Reviews

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Strained Hydrocarbons. Beyond the van′t Hoff and Le Bel Hypothesis. Edited by Helena Dodziuk. (pages 7965–7966)

      Lawrence T. Scott, Brian D. Steinberg, Jennifer M. Quimby, Eric H. Fort, Allison K. Greene, Natalie J. Smith and Maria N. Eliseeva

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/anie.200903810

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      Wiley-VCH, Weinheim 2009. 471 pp., hardcover € 159.00.—ISBN 978-3527317677

    2. Metallothioneins and Related Chelators. Metal Ions in Life Sciences Vol. 5. Edited by Astrid Sigel, Helmut Sigel and Roland K. O. Sigel. (pages 7966–7967)

      Kelly Duncan

      Version of Record online: 7 OCT 2009 | DOI: 10.1002/anie.200903833

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      Royal Society of Chemistry, Cambridge 2009. 514 pp., hardcover $ 299.00.—ISBN 978-1847558992

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. 1,3-Dipolar Cycloadditions

      What Controls the Reactivity of 1,3-Dipolar Cycloadditions? (pages 7968–7970)

      Bernd Engels and Manfred Christl

      Version of Record online: 16 SEP 2009 | DOI: 10.1002/anie.200902263

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      Reaction rates of 1,3-dipolar cycloadditions correlate closely with the energy required to distort the 1,3-dipole and dipolarophile to the transition-state geometry (see scheme). A bridge can be built connecting these new findings to the traditional frontier molecular orbital theory, which was and still is enormously successful in the rationalization of 1,3-dipolar cycloadditions.

    2. Stereoselective Synthesis

      Creating Aldols Differently: How to Build up Aldol Products with Quaternary Stereocenters Starting from Alkynes (pages 7971–7973)

      Dennis C. Koester and Daniel B. Werz

      Version of Record online: 4 SEP 2009 | DOI: 10.1002/anie.200903773

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      New approaches! Sometimes there is no harm in questioning established protocols and to think about completely new strategies. Here a new method makes possible the construction of all-carbon quaternary stereocenters within aldol patterns in a sequential, one-pot procedure starting from simple compounds such as alkynes (see scheme).

    3. C[BOND]F Bond Activation

      Niobium-Catalyzed Activation of Aryl Trifluoromethyl Groups and Functionalization of C[BOND]H Bonds: An Efficient and Convergent Approach to the Synthesis of N-Heterocycles (pages 7974–7976)

      Tom G. Driver

      Version of Record online: 24 SEP 2009 | DOI: 10.1002/anie.200904344

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      Activate that bond! The functionalization of the CF3 groups is an ongoing synthetic challenge owing to the inert nature of the C[BOND]F bond. The aryl trifluoromethyl group can be reduced by a low-valent niobium catalyst to produce a carbenoid that inserts into a C(sp3)[BOND]H bond to produce complex, functionalized N-fused indoles (see scheme).

  8. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Poly(2-oxazoline)s

      Poly(2-oxazoline)s: A Polymer Class with Numerous Potential Applications (pages 7978–7994)

      Richard Hoogenboom

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200901607

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      Versatile polymers: Poly(2-oxazoline)s have recently gained renewed interest because of their potential use as biomaterials, their thermoresponsive behavior, and the easy access to amphiphilic structures for self-assembly studies. These new trends are discussed together with recent efforts to combine poly(2-oxazoline)s with click chemistry.

  9. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Reviews
    8. Highlights
    9. Review
    10. Communications
    11. Preview
    1. Natural Product Synthesis

      An Efficient Formal Synthesis of the Human Telomerase Inhibitor (±)-γ-Rubromycin (pages 7996–8000)

      Dominea C. K. Rathwell, Sung-Hyun Yang, Kit Y. Tsang and Margaret A. Brimble

      Version of Record online: 30 JUL 2009 | DOI: 10.1002/anie.200903316

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      Balancing act: The correct balance of electronic factors in the naphthazarin and isocoumarin fragments facilitates the acid-mediated spiroketalization step to afford the key densely functionalized spiroketal (see picture; EOM=ethoxymethyl) in the formal synthesis of (±)-γ-rubromycin. A novel regioselective allyloxylation/Claisen rearrangement of 2-azido-1,4-naphthoquinone provides access to the highly oxygenated naphthazarin fragment.

    2. Signal Transduction

      Entirely Artificial Signal Transduction with a Primary Messenger (pages 8001–8005)

      Kai Bernitzki and Thomas Schrader

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200902973

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      I saw the sign: An artificial system allows messenger-induced transmembrane signaling. External addition of a primary messenger molecule (DET, see picture) leads to formation of a heterodimeric complex of transmembrane units bearing tryptophan–dansyl (Trp–Dan) donor–acceptor pairs, which in turn stimulates a strong FRET on the opposite side of the membrane.

    3. Surface Structures

      Resolving the Atomic Structure of Vanadia Monolayer Catalysts: Monomers, Trimers, and Oligomers on Ceria (pages 8006–8009)

      Martin Baron, Heather Abbott, Oleksandr Bondarchuk, Dario Stacchiola, Alexander Uhl, Shamil Shaikhutdinov, Hans-Joachim Freund, Cristina Popa, Maria Veronica Ganduglia-Pirovano and Joachim Sauer

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200903085

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      On top of old ceria: Vanadyl-terminated monomers, trimers (see picture), and oligomers form on a CeO2(111) surface, and their atomic structure is resolved using a combination of high-level experimental and theoretical results. Ceria surfaces stabilize vanadia species in a +5 oxidation state, which wet and chemically reduce the ceria surface and probably play a crucial role in the reactivity of ceria-supported vanadia in oxidation reactions.

    4. Ion Transfer

      Fast Ion-Transfer Processes at Nanoscopic Liquid/Liquid Interfaces (pages 8010–8013)

      Qing Li, Shubao Xie, Zhongwei Liang, Xin Meng, Shujuan Liu, Hubert H. Girault and Yuanhua Shao

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200903143

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      Keeping up: The fastest kinetic data for ion transfer at a liquid/liquid interface were evaluated by nanopipette voltammetry. The steady-state voltammograms can be explained by theoretical models. In previous electrochemical measurements the systematic underestimation of k0 is probably a result of inefficient mass transfer to the relatively large interface.

    5. Liquid Crystals

      Liquid-Crystalline Triangle Honeycomb Formed by a Dithiophene-Based X-Shaped Bolaamphiphile (pages 8014–8017)

      Xiaohong Cheng, Xing Dong, Guanghui Wei, Marko Prehm and Carsten Tschierske

      Version of Record online: 15 SEP 2009 | DOI: 10.1002/anie.200903247

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      Soft supramolecular triangles: The molecule shown displays a new liquid-crystalline phase formed by a periodic array of triangular cylinders. The cylinders are fused to form a honeycomb by hydrogen-bonding networks running along the vertices, and the cells are filled by molten alkyl chains. The thickness of the walls separating the compartments is equal to the width of the π-conjugated rods.

    6. Click Chemistry

      Copper(I)-Catalyzed Cycloaddition of Organic Azides and 1-Iodoalkynes (pages 8018–8021)

      Jason E. Hein, Jonathan C. Tripp, Larissa B. Krasnova, K. Barry Sharpless and Valery V. Fokin

      Version of Record online: 22 SEP 2009 | DOI: 10.1002/anie.200903558

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      High fidelity: 1-Iodoalkynes react rapidly and selectively with organic azides in the presence of copper(I) catalysts (see scheme; TTTA=tris((1-tert-butyl-1H-1,2,3-triazolyl)methyl)amine). The reaction is compatible with many functional groups and solvents, and 5-iodotriazole products were usually obtained in excellent yield. These products can be further functionalized to give fully substituted 1,2,3-triazoles.

    7. Catalytic Hydrogenation

      Supramolecular Catalyst for Aldehyde Hydrogenation and Tandem Hydroformylation–Hydrogenation (pages 8022–8026)

      Lisa Diab, Tomáš Šmejkal, Jens Geier and Bernhard Breit

      Version of Record online: 22 SEP 2009 | DOI: 10.1002/anie.200903620

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      The chemoselective reduction of aldehydes and the tandem hydroformylation–hydrogenation of terminal alkenes are possible with a supramolecular catalyst that operates by a novel mechanism involving substrate activation by hydrogen bonding and subsequent metal–ligand bifunctional hydrogenation (see scheme).

    8. Fluorescent Probes

      A Two-Photon Tracer for Glucose Uptake (pages 8027–8031)

      Yu Shun Tian, Hyang Yeon Lee, Chang Su Lim, Jongmin Park, Hwan Myung Kim, Yoo Na Shin, Eun Sun Kim, Hoon Jae Jeon, Seung Bum Park and Bong Rae Cho

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200901175

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      It takes two: Two-photon tracers (AG1, AG2) have been developed that can be excited by 780 nm fs laser pulses, can be easily loaded into cancer cells and tissues, show high photostability and negligible toxicity, and can visualize glucose uptake in living cells and tissues by two-photon microscopy (TPM). Moreover, AG2 can screen anticancer agents in cancer cells and cancer tissues at 75–150 mm depth by TPM.

    9. Electron Transfer

      Modulating Electronic Interactions between Closely Spaced Complementary π Surfaces with Different Outcomes: Regio- and Diastereomerically Pure Subphthalocyanine–C60 Tris Adducts (pages 8032–8036)

      David González-Rodríguez, Esther Carbonell, Dirk M. Guldi and Tomás Torres

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200902767

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      Tightly coupled, regio- and diastereomerically pure subphthalocyanine–C60 dyads (see space-filling depiction; B orange, C light blue, H gray, N blue, O red), tethered by means of a tris-addition reaction, can follow different mechanisms on photoexcitation (electron transfer or energy transfer), depending on the spacing between the two complementary π surfaces.

    10. Asymmetric Catalysis

      Catalytic Enantioselective Stereoablative Alkylation of 3-Halooxindoles: Facile Access to Oxindoles with C3 All-Carbon Quaternary Stereocenters (pages 8037–8041)

      Sandy Ma, Xiaoqing Han, Shyam Krishnan, Scott C. Virgil and Brian M. Stoltz

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200902943

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      From 2 to 1! Racemic tertiary halooxindoles proceed to enantioenriched oxindoles bearing all-carbon quaternary stereocenters as a result of a catalytic enantioselective stereoablative process (see scheme). The application of this procedure allows for the rapid asymmetric construction of biologically significant alkaloid core motifs.

    11. Myosin Inhibition

      Total Synthesis of Pentabromo- and Pentachloropseudilin, and Synthetic Analogues—Allosteric Inhibitors of Myosin ATPase (pages 8042–8046)

      René Martin, Anne Jäger, Markus Böhl, Sabine Richter, Roman Fedorov, Dietmar J. Manstein, Herwig O. Gutzeit and Hans-Joachim Knölker

      Version of Record online: 8 SEP 2009 | DOI: 10.1002/anie.200903743

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      Stopping myo: The total syntheses of the title compounds have been achieved using a highly efficient silver(I)-catalyzed cyclization of N-tosyl-homopropargylamines. The pseudilin derivatives represent a novel class of myosin inhibitors. A new allosteric binding pocket of the Dictyostelium myosin-2 motor domain has been identified for pentabromopseudilin (1) by using an X-ray crystal structure determination of the inhibitor–protein complex.

    12. Heterogeneous Catalysis

      Water-Gas Shift Reaction on a Highly Active Inverse CeOx/Cu(111) Catalyst: Unique Role of Ceria Nanoparticles (pages 8047–8050)

      José A. Rodriguez, Jesús Graciani, Jaime Evans, Joon B. Park, Fan Yang, Dario Stacchiola, Sanjaya D. Senanayake, Shuguo Ma, Manuel Pérez, Ping Liu, Javier Fdez. Sanz and Jan Hrbek

      Version of Record online: 24 SEP 2009 | DOI: 10.1002/anie.200903918

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      CeO takes charge: Ceria grows forming small islands on terraces (2–5 nm, CeOx-I) and large islands on steps of a copper substrate (30–50 nm, CeOx-II; see scheme; 100×100 nm2). The resulting CeOx/Cu(111) systems display an extraordinary water-gas shift activity and illustrate the role that an oxide can play in improving the performance of copper-based catalysts.

    13. Nanoscale Assemblies

      A Spherical 24 Butyrate Aggregate with a Hydrophobic Cavity in a Capsule with Flexible Pores: Confinement Effects and Uptake–Release Equilibria at Elevated Temperatures (pages 8051–8056)

      Christian Schäffer, Hartmut Bögge, Alice Merca, Ira A. Weinstock, Dieter Rehder, Erhard T. K. Haupt and Achim Müller

      Version of Record online: 22 SEP 2009 | DOI: 10.1002/anie.200903910

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      Forced interaction: The encapsulation of a large assembly of organic species—the 24 butyrate unit, which exhibits a remarkable central spherical hydrophobic cavity spanned by 72 H atoms—in a porous capsule (see picture) leads to interesting interactions between the butyrates under the confined conditions. The quarantine for the guests is lifted upon temperature increase: guests can easily leave and return.

    14. Synthetic Methods

      Asymmetric Synthesis of β-Alkynyl Aldehydes by Rhodium-Catalyzed Conjugate Alkynylation (pages 8057–8059)

      Takahiro Nishimura, Takahiro Sawano and Tamio Hayashi

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200904486

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      To the point: The rhodium-catalyzed asymmetric conjugate alkynylation of α,β-unsaturated aldehydes with triisopropylsilyl acetylene proceeded efficiently in methanol to give the β-alkynyl aldehydes in high yields with high enantioselectivity (see Scheme).

    15. Asymmetric Catalysis

      Cationic-Oxazaborolidine-Catalyzed Enantioselective Diels–Alder Reaction of α,β-Unsaturated Acetylenic Ketones (pages 8060–8062)

      Joshua N. Payette and Hisashi Yamamoto

      Version of Record online: 22 SEP 2009 | DOI: 10.1002/anie.200904339

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      Yne also a good dienophile: The cationic oxazaborolidine 1 promoted the formation of Diels–Alder adducts between acetylenic ketones and both cyclic and acyclic dienes in excellent yield with 99 % ee (see scheme; Tf=trifluoromethanesulfonyl, TMS=trimethylsilyl). Importantly, high levels of asymmetric induction were also observed with dienophiles that lacked the typical hydrogen-bonding motif required for other oxazaborolidinium-mediated reactions.

    16. Microreactors

      Nitro-Substituted Aryl Lithium Compounds in Microreactor Synthesis: Switch between Kinetic and Thermodynamic Control (pages 8063–8065)

      Aiichiro Nagaki, Heejin Kim and Jun-ichi Yoshida

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200904316

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      Be quick or take your time, depending on your goal: A microflow method for the generation and transformation of o-, m-, and p-nitro-substituted aryl lithium compounds enabled the selective use of either the kinetically or the thermodynamically preferred intermediate. In the example pictured, a residence time of 0.06 s at −48 °C led to the formation of 1, whereas 2 was obtained exclusively when the residence time was extended to 63 s.

    17. Annulated Rings

      Catalytic Enantioselective Synthesis of Chiral Tetraphenylenes: Consecutive Inter- and Intramolecular Cycloadditions of Two Triynes (pages 8066–8069)

      Takanori Shibata, Tatsuya Chiba, Hiroyuki Hirashima, Yasunori Ueno and Kohei Endo

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200903715

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      Triynes having a phenylene-bridged 1,5-diyne moiety were transformed into substituted tetraphenylenes by the title sequence. A cationic Rh–ligand species catalyzed this highly enantioselective reaction. This protocol is a new and easy approach to the construction of the tetraphenylene skeleton and enables an efficient asymmetric synthesis (see scheme; R=H; Z=NTs, C(CO2Me)2, O).

    18. Synthetic Methods

      Expedient Synthesis of N-Fused Indoles: A C[BOND]F Activation and C[BOND]H Insertion Approach (pages 8070–8073)

      Kohei Fuchibe, Tsukasa Kaneko, Keiji Mori and Takahiko Akiyama

      Version of Record online: 3 JUL 2009 | DOI: 10.1002/anie.200901986

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      Easy does it: A wide range of N-fused indole skeletons, which are core structures of many biologically potent molecules, are successfully furnished by a niobium-catalyzed C(sp3)[BOND]H insertion reaction (see picture). The precursors are readily prepared by a palladium-catalyzed amination reaction of bromotrifluorotoluenes with cyclic amines.

    19. Siloxane Chemistry

      From the Selective Cleavage of the Si-O-Si Bond in Disiloxanes to Zwitterionic, Water-Stable Zinc Silanolates (pages 8074–8077)

      Christian Däschlein, Jonathan O. Bauer and Carsten Strohmann

      Version of Record online: 24 SEP 2009 | DOI: 10.1002/anie.200902318

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      Zinc salts do Si[BOND]O's: Organosilicon chemistry is crucially determined by the high stability and chemical resistance of the Si-O-Si bond. The formation and structural existence of water-stable metallasilanolates demonstrate both the possibility to cleave the Si-O-Si bond with simple zinc compounds under mild conditions as well as the existence of such molecular metallasilanolates in the presence of water.

    20. Synthesis Design

      Copper-Catalyzed C[BOND]C Bond Formation through C[BOND]H Functionalization: Synthesis of Multisubstituted Indoles from N-Aryl Enaminones (pages 8078–8081)

      Roberta Bernini, Giancarlo Fabrizi, Alessio Sferrazza and Sandro Cacchi

      Version of Record online: 22 SEP 2009 | DOI: 10.1002/anie.200902440

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      A variety of functionalities, including the whole range of halogen substituents, are tolerated in the title reaction, an intramolecular approach for the construction of a multisubstituted indole skeleton from readily available enaminones (see scheme; phen=1,10-phenanthroline). The indole products are also prepared directly in high yield from α,β-ynones and primary amines.

    21. Trienes

      Photoisomerization of All-cis-1,6-diphenyl-1,3,5-hexatriene in the Solid State and in Solution: A Simultaneous Three-Bond Twist Process (pages 8082–8085)

      Jack Saltiel, Dimitrios Papadimitriou, Tallapragada S. R. Krishna, Zhen-Nian Huang, Govindarahan Krishnamoorthy, Somchoke Laohhasurayotin and Ronald J. Clark

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200902724

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      Disrotatory bicycle pedals: Irradiation of the title compound in the solid state gives the all-trans isomer directly in a crystal-to-crystal reaction. This threefold cistrans photoisomerization is proposed to proceed by a two-stage mechanism that is consistent with two simultaneous bicycle-pedal processes occurring in disrotatory fashion about the central bond.

    22. Expanded Porphyrins

      T-Shaped Three-Coordinate Copper(II) Heptaphyrin Complexes (pages 8086–8089)

      Shohei Saito, Ko Furukawa and Atsuhiro Osuka

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200902901

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      T for two: The use of [32]heptaphyrin ligands allows the synthesis of T-shaped three-coordinate copper(II) complexes. For a relatively flexible nonfused [32]heptaphyrin ligand, a copper(II)–arene interaction supplements the coordination deficiency, whereas a highly rigid quadruply N-fused heptaphyrin ligand allows the formation of a three-coordinate copper(II) complex with T-shaped planar symmetry (see picture).

    23. Protein Modifications

      Highly Efficient and Chemoselective Peptide Ubiquitylation (pages 8090–8094)

      K. S. Ajish Kumar, Mahmood Haj-Yahya, Diana Olschewski, Hilal A. Lashuel and Ashraf Brik

      Version of Record online: 24 SEP 2009 | DOI: 10.1002/anie.200902936

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      Loving kiss of death: A highly efficient and chemoselective method for ubiquitylation of peptides using δ-mercaptolysine to assist isopeptide formation between the ε-NH2 of the lysine residue and the activated C-terminal glycine of ubiquitin (Ub) is presented.

    24. Nanowire Solar Cells

      Tantalum-Doped Titanium Dioxide Nanowire Arrays for Dye-Sensitized Solar Cells with High Open-Circuit Voltage (pages 8095–8098)

      Xinjian Feng, Karthik Shankar, Maggie Paulose and Craig A. Grimes

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200903114

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      Nanowires in the sun: Hydrothermal synthesis yields homogeneously tantalum-doped titania nanowire arrays on transparent conducting oxide substrates. The methodology should allow doping of titania nanowires with different transition metals. This advance in materials synthesis translates into enhanced device performance, as demonstrated by dye-sensitized solar cells with very high open-circuit photovoltage (see picture).

    25. Olefin Polymerization

      [ONSR]TiCl3-Catalyzed Copolymerization of Ethylene with Functionalized Olefins (pages 8099–8102)

      Xiao-Hong Yang, Chun-Rong Liu, Cong Wang, Xiu-Li Sun, Yang-Hui Guo, Xin-Ke Wang, Zheng Wang, Zuowei Xie and Yong Tang

      Version of Record online: 15 SEP 2009 | DOI: 10.1002/anie.200903334

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      All zipped up: Titanium complexes are designed as efficient catalysts for the copolymerization of ethylene with polar olefins, such as ω-alkenol and ω-alkenoic acid. An organophosphine catalyst can be zippered on the polyethylene (see scheme; TBS=tert-butyldimethylsilyl, FG=functional group, MMAO=modified methylaluminoxane) to form an efficient and recoverable initiator for [3+2] cycloaddition.

    26. Host–Guest Systems

      pH-Switchable Helicity of DNA-Templated Assemblies (pages 8103–8106)

      Pim G. A. Janssen, Amparo Ruiz-Carretero, David González-Rodríguez, E. W. Meijer and Albertus P. H. J. Schenning

      Version of Record online: 15 SEP 2009 | DOI: 10.1002/anie.200903507

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      Coming together: Oligothymine is used as a template to self-assemble complementary nonchiral naphthalene guests. Depending on the protonated state of the guest, left- or right-handed DNA-templated self-assemblies are formed (see picture). The templated assembly processes were studied in detail with temperature-dependent circular dichroism and UV/Vis spectroscopy.

    27. Dioxygen Activation

      O[BOND]O Bond Activation in Heterobimetallic Peroxides: Synthesis of the Peroxide [LNi(μ,η22-O2)K] and its Conversion into a Bis(μ-Hydroxo) Nickel Zinc Complex (pages 8107–8110)

      Shenglai Yao, Yun Xiong, Matthias Vogt, Hansjörg Grützmacher, Christian Herwig, Christian Limberg and Matthias Driess

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200903772

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      O2takes activation lessons: O[BOND]O bond activation can be achieved depending on the nature of the heterometal M in [LNi(μ,η22-O2)M] complexes. The reduction of the nickel(II) superoxide 1 with potassium affords the peroxide 2, which, upon replacement of the K+ ion in 2 by the non-redox-active L′Zn+ ion, leads to transient 3, which subsequently abstracts two solvent hydrogen atoms to give the heterobimetallic complex 4. L, L′=β-diketiminates.

    28. Dianion Chemistry

      Isolation, Structural Characterization, and Synthetic Application of Oxycyclopentadienyl Dianions (pages 8111–8114)

      Lantao Liu, Wen-Xiong Zhang, Chao Wang, Congyang Wang and Zhenfeng Xi

      Version of Record online: 22 SEP 2009 | DOI: 10.1002/anie.200904298

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      A new building block? Lithium complexes of novel oxycyclopentadienyl dianions were isolated in high yield and characterized by X-ray crystallography. Cyclopentadienes and transition-metal complexes could be prepared from these intriguing intermediates (see scheme).

    29. Synthetic Methods

      Olefin Cyclopropanation by a Sequential Atom-Transfer Radical Addition and Dechlorination in the Presence of a Ruthenium Catalyst (pages 8115–8119)

      Katrin Thommes, Gregor Kiefer, Rosario Scopelliti and Kay Severin

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200904278

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      Without diazo: The reductive coupling of olefins with dichloro compounds in the presence of a ruthenium catalyst and magnesium gives cyclopropanes in good yield (see scheme).

    30. Organozirconate Chemistry

      Coupling Reactions of Zirconate Complexes Induced by Carbonyl Compounds (pages 8120–8123)

      Chanjuan Xi, Xiaoyu Yan, Wei You and Tamotsu Takahashi

      Version of Record online: 23 SEP 2009 | DOI: 10.1002/anie.200904255

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      Multifaceted organozirconate: The novel coupling reaction of organozirconates 1 and carbonyl compounds (through intermediate 2) selectively affords highly substituted allene 3 and dienol 4 derivatives.

    31. Oligopeptides

      Mapping the Landscape of Potentially Primordial Informational Oligomers: Oligo-dipeptides Tagged with Orotic Acid Derivatives as Recognition Elements (pages 8124–8128)

      Xuejun Zhang and Ramanarayanan Krishnamurthy

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200904188

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      Partner up! Base-pairing properties of oligo-dipeptides tagged with orotic acid and its 2,4-diamino counterpart (see structure) are found to be consistent with previously observed correlations between ΔpKa values and the pairing strength of complementary bases. The combined results provide a general justification for anticipating the base-pairing propensity of a recognition element based on its pKa value and the pH of the medium.

    32. Asymmetric Catalysis

      Synthesis of Chiral Tetrasubstituted Alkenes by an Asymmetric Cascade Reaction Catalyzed Cooperatively by Cationic Rhodium(I) and Silver(I) Complexes (pages 8129–8132)

      Daiki Hojo, Keiichi Noguchi and Ken Tanaka

      Version of Record online: 22 SEP 2009 | DOI: 10.1002/anie.200904024

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      Fantastic four: Tetrasubstituted alkenes have been prepared with high enantioselectivity by the title transformation. This reaction was successfully applied to the enantio- and diastereoselective synthesis of tetrasubstituted helical alkenes possessing both central and helical chirality (see scheme).

    33. Reactive Intermediates

      A Formal Carbon–Sulfur Triple Bond: H[BOND]C[TRIPLE BOND]S[BOND]O[BOND]H (pages 8133–8136)

      Peter R. Schreiner, Hans Peter Reisenauer, Jaroslaw Romanski and Grzegorz Mloston

      Version of Record online: 19 SEP 2009 | DOI: 10.1002/anie.200903969

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      Extremely rare: A CS triple bond can be assigned to HCSOH, a new molecule prepared from H2C[DOUBLE BOND]S[DOUBLE BOND]O by a photochemical [1,3]H-shift. But does this formal description agree with analyses on the basis of IR vibrations, bond lengths, bond orders, molecular orbitals, and compliance constants? Molecules like this challenge and refine our current understanding of chemical bonding.

      Corrected by:

      Corrigendum: A Formal Carbon–Sulfur Triple Bond: H[BOND]C[TRIPLE BOND]S[BOND]O[BOND]H

      Vol. 49, Issue 12, 2083, Version of Record online: 10 MAR 2010

    34. Natural Products

      Aza-Wittig-Supported Synthesis of the A Ring of Nosiheptide (pages 8137–8140)

      Jin-Yong Lu, Matthias Riedrich, Martin Mikyna and Hans-Dieter Arndt

      Version of Record online: 25 SEP 2009 | DOI: 10.1002/anie.200903477

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      An array of aza-Wittig reactions: In the unique synthesis of the A ring of the potent thiopeptide antibiotic nosiheptide, mild aza-Wittig thiazole ring closure, a ScIII-mediated regioselective ester hydrolysis, and a highly efficient macrolactam formation have enabled the assembly of the fully functionalized scaffold, with its 3-hydroxypyridine nucleus orthogonally protected (see scheme).

      Corrected by:

      Corrigendum: Aza-Wittig-Supported Synthesis of the A Ring of Nosiheptide

      Vol. 48, Issue 49, 9211, Version of Record online: 17 NOV 2009

    35. Al[BOND]Al σ Bonds

      Snapshots of the Al[BOND]Al σ-Bond Formation Starting from {AlR2} Units: Experimental and Computational Observations (pages 8141–8145)

      Patrick Henke, Tobias Pankewitz, Wim Klopper, Frank Breher and Hansgeorg Schnöckel

      Version of Record online: 25 AUG 2009 | DOI: 10.1002/anie.200901754

      Thumbnail image of graphical abstract

      The approach of two atoms with an unpaired electron each results in the formation of a σ bond. Snapshots of the primary step with a large atom-to-atom distance and a parallel spin of both electrons and of the final product, consisting of a butterfly structure with a short Al[BOND]Al σ bond, have been identified for a [R2P[BOND]Al(PR2)Al[BOND]PR2] compound using quantum chemical calculations and X-ray crystallography (see scheme).

      Corrected by:

      Corrigendum: Snapshots of the Al[BOND]Al σ-Bond Formation Starting from {AlR2} Units: Experimental and Computational Observations

      Vol. 48, Issue 52, 9773, Version of Record online: 15 DEC 2009

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