Angewandte Chemie International Edition

Cover image for Vol. 45 Issue 17

April 21, 2006

Volume 45, Issue 17

Pages 2641–2813

    1. Cover Picture: Flattened Cone 2,8,14,20-Tetrakis(L-valinamido)[4]resorcinarene: An Enantioselective Allosteric Receptor in the Gas Phase (Angew. Chem. Int. Ed. 17/2006) (page 2641)

      Bruno Botta, Fabiana Caporuscio, Deborah Subissati, Andrea Tafi, Maurizio Botta, Antonello Filippi and Maurizio Speranza

      Version of Record online: 11 APR 2006 | DOI: 10.1002/anie.200690060

      Protein allosterism is the basis for the molecular control of fundamental processes in living systems, but despite its importance, basic questions on the mechanisms involved remain unanswered. A gas-phase approach to the problem is described by M. Speranza et al. in their Communication on page 2717 ff., in which they report the highly enantioselective, 2-aminobutane-induced loss of D- and L-tryptophan from the achiral hydrophobic rim of a chiral resorcin[4]arene.

    2. Dynamic Combinatorial Chemistry: The Unexpected Choice of Receptors by Guest Molecules (pages 2660–2663)

      Bas de Bruin, Peter Hauwert and Joost N. H. Reek

      Version of Record online: 4 APR 2006 | DOI: 10.1002/anie.200504480

      Thumbnail image of graphical abstract

      Survival of the fittest? Amplification of the best receptor from a dynamic combinatorial library does not always proceed according to survival of the “fittest”. However, it has recently resulted in the discovery of some unexpected receptors for various substrates, as illustrated by the example of a catenane receptor (see picture; green) for the neurotransmitter acetylcholine (red).

    3. Ring-Closing Metathesis as a Basis for the Construction of Aromatic Compounds (pages 2664–2670)

      Timothy J. Donohoe, Allan J. Orr and Matilda Bingham

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200503512

      Thumbnail image of graphical abstract

      Openings from ring closing: Ring-closing metathesis (RCM) is an extremely useful technique for constructing heterocyclic and carbocyclic ring systems, which can be transformed into aromatic derivatives by a variety of different strategies. This Minireview brings together the different approaches reported to date.

    4. Multisegmented One-Dimensional Nanorods Prepared by Hard-Template Synthetic Methods (pages 2672–2692)

      Sarah J. Hurst, Emma Kathryn Payne, Lidong Qin and Chad A. Mirkin

      Version of Record online: 29 MAR 2006 | DOI: 10.1002/anie.200504025

      Thumbnail image of graphical abstract

      Each component does its part: Multisegmented 1D nanostructures can be reliably synthesized within the micro- or nanosized pores of hard templates. When released from these templates (see picture), the individual components of these structures can be used to perform multiple tasks simultaneously. In this way, these single structures provide possibilities for novel applications and new directions in fundamental areas of study.

    5. A Bis(pyridyl)allenylidene Complex of Ruthenium: A “Molecular Clip” That Displays Intense Near-Infrared Absorption upon Coordination to a Ruthenium(II) Center (pages 2694–2698)

      Chun-Yuen Wong, Glenna So Ming Tong, Chi-Ming Che and Nianyong Zhu

      Version of Record online: 4 APR 2006 | DOI: 10.1002/anie.200600139

      Thumbnail image of graphical abstract

      Making the band: A bis(pyridyl)allenylidene–ruthenium complex acts as a metalloligand for the binding of metal ions. The dinuclear complex [(16-TMC)ClRu[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]C(2-py)2Ru(acac)2]+ (16-TMC=1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane) features an intense low-energy metal-to-ligand charge transfer in an excited state delocalized over both Ru ions and the allenylidene bridge (see plot of the LUMO).

    6. Control of Amyloid β-Peptide Protofibril Formation by a Designed Template Assembly (pages 2699–2702)

      Gunnar T. Dolphin, Pascal Dumy and Julian Garcia

      Version of Record online: 23 MAR 2006 | DOI: 10.1002/anie.200600395

      Thumbnail image of graphical abstract

      Insight into amyloids: Four identical segments of the amyloid β-peptide, which is associated with Alzheimer's disease by fibril formation, were successfully attached to a cyclic decapeptide template. The assembly forms soluble protofibrils (see picture) that reveal a cross-β-sheet structure, with fast controllable kinetics and without a lag phase.

    7. DNA Recognition with Large Calixarene Dimers (pages 2703–2706)

      Reza Zadmard and Thomas Schrader

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200502946

      Thumbnail image of graphical abstract

      Feeling groovy: A large dimeric calix[4]arene hexaaniline binds selectively to double-stranded DNA and especially RNA with submicromolar KD values. The picture shows a simulation of the complex between a 12-base-pair B-DNA (green and blue) and an anilinocalixarene dimer (red), which fits snugly into the major groove. Several physical and spectroscopic characteristics strongly indicate insertion into the major groove.

    8. A Fluorescent Indicator To Visualize Activities of the Androgen Receptor Ligands in Single Living Cells (pages 2707–2712)

      Muhammad Awais, Moritoshi Sato, Xianfen Lee and Yoshio Umezawa

      Version of Record online: 23 MAR 2006 | DOI: 10.1002/anie.200503185

      Thumbnail image of graphical abstract

      Seeing the light: An androgen promotes interactions between the androgen-receptor ligand-binding domain (AR LBD) and a coactivator protein. This results in an increase in the fluorescence resonant energy transfer (FRET) from cyan fluorescent protein (CFP) to yellow fluorescent protein (YFP). The indicator distinguishes ligands of different potencies for the AR.

    9. Generating Isotropic Superparamagnetic Interconnectivity for the Two-Dimensional Organization of Nanostructured Building Blocks (pages 2713–2717)

      Hao Ming Chen, Ru-Shi Liu, Hongliang Li and Hua Chun Zeng

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200503632

      Thumbnail image of graphical abstract

      Attractive exteriors: Surface reduction of Co3O4 nanocubes leads to the formation of ordered 2D arrays (see picture), in which the nanocubes are connected through isotropic superparamagnetic interactions. This method provides an efficient means for generating assemblies of nanoparticles, without using organic surfactants or external magnetic fields.

    10. Flattened Cone 2,8,14,20-Tetrakis(L-valinamido)[4]resorcinarene: An Enantioselective Allosteric Receptor in the Gas Phase (pages 2717–2720)

      Bruno Botta, Fabiana Caporuscio, Deborah Subissati, Andrea Tafi, Maurizio Botta, Antonello Filippi and Maurizio Speranza

      Version of Record online: 27 FEB 2006 | DOI: 10.1002/anie.200503987

      Thumbnail image of graphical abstract

      A get-out clause: Displacement of the enantiomers of tryptophan from the achiral hydrophobic rim of a flattened cone resorcinarene derivative is induced by 2-aminobutane (B). The displacement exhibits a marked enantioselectivity which is traced to a conformational coupling between the achiral hydrophobic rim of the resorcinarene host and its chiral hydrophilic rim wherein the 2-aminobutane enantiomers are trapped.

    11. You have free access to this content
      Room-Temperature Nucleophilic Aromatic Fluorination: Experimental and Theoretical Studies (pages 2720–2725)

      Haoran Sun and Stephen G. DiMagno

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200504555

      Thumbnail image of graphical abstract

      Taming the reagent: The use of anhydrous tetrabutylammonium fluoride (TBAFanh) in nucleophilic aromatic substitution reactions, including variants of the selective halogen-exchange and fluorodenitration processes (see scheme), was investigated. It was shown that TBAFanh permits these reactions to be performed under surprisingly mild conditions if it is used in relatively nonpolar media.

    12. Construction of a Ball-and-Spike Protein Supramolecule (pages 2725–2728)

      Kenji Sugimoto, Shuji Kanamaru, Kenji Iwasaki, Fumio Arisaka and Ichiro Yamashita

      Version of Record online: 23 MAR 2006 | DOI: 10.1002/anie.200504018

      Thumbnail image of graphical abstract

      On the ball: Fusion of gp5C (spike) to LisDps (ball) through a flexible linker connecting the respective C and N termini allowed the engineered construction of a ball-and-spike protein supramolecule. The two symmetric protein components self-assemble to form a large protein supramolecule made of artificial components.

    13. A Genetically Encoded Photocaged Tyrosine (pages 2728–2731)

      Alexander Deiters, Dan Groff, Youngha Ryu, Jianming Xie and Peter G. Schultz

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200600264

      Thumbnail image of graphical abstract

      Activating proteins with light: A photocaged tyrosine was genetically encoded in E. coli in response to the amber codon TAG. Substitution of Tyr 503 in the active site of β-galactosidase allowed photoactivation of this enzyme in vitro or directly in bacteria with 360-nm light. This method should allow photoregulation of the activity of a variety of biological processes including transcription, signal transduction, and cellular trafficking.

    14. Total Synthesis of (+)-β-Erythroidine (pages 2731–2734)

      Hironori Fukumoto, Keisuke Takahashi, Jun Ishihara and Susumi Hatakeyama

      Version of Record online: 21 MAR 2006 | DOI: 10.1002/anie.200600210

      Thumbnail image of graphical abstract

      Enyne enyne oh! The first total synthesis of (+)-β-erythroidine, a non-aromatic Erythrina alkaloid, is demonstrated. The key steps involved are Lewis acid promoted cyclization of an epoxy–trichloroacetimidate intermediate and tandem ring-closing metathesis (RCM) of the dienyne (see scheme).

    15. Rh-Catalyzed [4+2] Annulation of 4-Alkynals with Isocyanates and Its Application to the Parallel Kinetic Resolution of Unfunctionalized 4-Alkynals (pages 2734–2737)

      Ken Tanaka, Yuji Hagiwara and Masao Hirano

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200504470

      Thumbnail image of graphical abstract

      Enantioenriched 2-alkylideneglutarimides and cyclopentenones are prepared by parallel kinetic resolution of 3-substituted 4-alkynals with a cationic RhI/(S)-segphos catalyst system. This is an attractive route to the above-mentioned products given the one-step access to 4-alkynals from readily available terminal alkynes.

    16. Oxidative De-aromatization of para-Alkyl Phenols into para-Peroxyquinols and para-Quinols Mediated by Oxone as a Source of Singlet Oxygen (pages 2737–2741)

      M. Carmen Carreño, Marcos González-López and Antonio Urbano

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200504605

      Thumbnail image of graphical abstract

      Easy does it: Easily handled and environmentally safe oxone generates singlet oxygen which effects the simple and selective oxidative de-aromatization of para-alkyl phenols 1 into para-peroxyquinols 2 under very mild conditions with good to excellent yields. A one-pot access to para-quinols 3 from 1 is also possible after treatment of the crude reaction mixture with sodium thiosulfate.

    17. Hydrosilylation of Alkenes with Early Main-Group Metal Catalysts (pages 2741–2745)

      Frank Buch, Julie Brettar and Sjoerd Harder

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200504164

      Thumbnail image of graphical abstract

      Clean conversion of conjugated alkenes with exclusive formation of one regioisomer is achieved by using a new class of hydrosilylation catalysts based on early main-group metals (Ca, Sr, and K). The regioselectivity can be switched to the other isomer through the choice of the metal and solvent polarity.

    18. Polymethacrylates with a Covalently Linked CuII–Cyclen Complex for the In Situ Generation of Nitric Oxide from Nitrosothiols in Blood (pages 2745–2748)

      Sangyeul Hwang, Wansik Cha and Mark. E. Meyerhoff

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200503588

      Thumbnail image of graphical abstract

      In the matrix: A new cross-linked hydrogel polymer, poly(2-hydroxyethyl methacrylate) (pHEMA), containing appended CuII–cyclen sites (cyclen=1,4,7,10-tetraazacyclododecane) was prepared and shown to generate nitric oxide from endogenous S-nitrosothiol species (RSNO) typically found in circulating whole blood.

    19. Substrate Specificity of the Macrolide-Glycosylating Enzyme Pair DesVII/DesVIII: Opportunities, Limitations, and Mechanistic Hypotheses (pages 2748–2753)

      Svetlana A. Borisova, Changsheng Zhang, Haruko Takahashi, Hua Zhang, Alexander W. Wong, Jon S. Thorson and Hung-wen Liu

      Version of Record online: 15 MAR 2006 | DOI: 10.1002/anie.200503195

      Thumbnail image of graphical abstract

      Two's Company: DesVII, a glycosyltransferase involved in the biosynthesis of macrolide antibiotics, is unusual in that it requires an additional protein partner, DesVIII, for its full activity. The level of substrate tolerance of the DesVII/DesVIII pair was explored.

    20. Reactivity-Based One-Pot Synthesis of the Tumor-Associated Antigen N3 Minor Octasaccharide for the Development of a Photocleavable DIOS-MS Sugar Array (pages 2753–2757)

      Jinq-Chyi Lee, Chung-Yi Wu, Junefredo V. Apon, Gary Siuzdak and Chi-Huey Wong

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200504067

      Thumbnail image of graphical abstract

      Sweet and light: Readily available thioglycosides with defined relative reactivity values were used as building blocks in a one-pot strategy to synthesize the tumor-associated carbohydrate antigen N3 minor (1). The target molecule was attached covalently to a porous silicon surface through a photocleavable linker for direct characterization in a mass spectrometer equipped with a laser source.

    21. Short Oxo–Titanium(IV) Bond in Bacterial Transferrin: A Protein Target for Metalloantibiotics (pages 2758–2761)

      Maolin Guo, Ian Harvey, Dominic J. Campopiano and Peter J. Sadler

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200600260

      Thumbnail image of graphical abstract

      A competitive edge? TiIV binding to a bacterial transferrin (ferric-ion-binding protein, FBP; see picture, foreground) is rapid, competes with FeIII binding, and results in a short oxo–TiIV bond (EXAFS studies; see picture, background). Inhibitors of iron uptake by FBP should be active against diseases caused by bacterial pathogens. The results suggest that Ti complexes could provide such inhibition.

    22. Catalysis in Capillaries by Pd Thin Films Using Microwave-Assisted Continuous-Flow Organic Synthesis (MACOS) (pages 2761–2766)

      Gjergji Shore, Sylvie Morin and Michael G. Organ

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200503600

      Thumbnail image of graphical abstract

      Finally … metal in a microwave! Thin films of Pd black deposited onto the inner surface of microcapillaries are efficient for metal-catalyzed transformations under flow conditions including the Suzuki–Miyama and Heck couplings. The reaction mixture is flowed through these miniature capillaries while being microwaved, and conversion times are on the order of seconds.

    23. Rhenium- and Aniline-Catalyzed One-Pot Annulation of Aromatic Ketones and α,β-Unsaturated Esters Initiated by C[BOND]H Bond Activation (pages 2766–2768)

      Yoichiro Kuninobu, Yuta Nishina, Makoto Shouho and Kazuhiko Takai

      Version of Record online: 23 MAR 2006 | DOI: 10.1002/anie.200503627

      Thumbnail image of graphical abstract

      Several reaction steps, including C[BOND]H activation, lead to indene derivatives in good yields in the rhenium-catalyzed reaction of aromatic ketimines and ethyl acrylate. Indene derivatives can also be obtained by the reactions of aromatic ketones with α,β-unsaturated esters in the presence of a catalytic rhenium complex and p-anisidine (see scheme).

    24. You have free access to this content
      Total Syntheses of Hexacyclinol, 5-epi-Hexacyclinol, and Desoxohexacyclinol Unveil an Antimalarial Prodrug Motif (pages 2769–2773)

      James J. La Clair

      Version of Record online: 9 FEB 2006 | DOI: 10.1002/anie.200504033

      Thumbnail image of graphical abstract

      All sewn up: A “three-staged stitch” was used to append the A–C rings of desoxohexacyclinol (1), which was further converted into the related compounds hexacyclinol (2) and 5-epi-hexacyclinol (3). Screening of the late-staged intermediates indicated that precursors to 1 retain potent antimalarial activity. The mechanism of this action is suggested to involve a three-step prodrug-like activation.

      Corrected by:

      Retraction: Retraction: Total Syntheses of Hexacyclinol, 5-epi-Hexacyclinol, and Desoxohexacyclinol Unveil an Antimalarial Prodrug Motif

      Vol. 51, Issue 47, 11661, Version of Record online: 14 NOV 2012

    25. Cyclic Dimethylsiloxanes as Pseudo Crown Ethers: Syntheses and Characterization of Li(Me2SiO)5[Al{OC(CF3)3}4], Li(Me2SiO)6[Al{OC(CF3)3}4], and Li(Me2SiO)6[Al{OC(CF3)2Ph}4] (pages 2773–2777)

      Andreas Decken, Jack Passmore and Xinping Wang

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200504262

      Thumbnail image of graphical abstract

      An unexpected guest: The salts LiD5[AlF], LiD6[AlF], and LiD6[AlPhF] (Dn=(Me2SiO)n; [AlF]=Al{OC(CF3)3}4; [AlPhF]=Al{OC(CF3)2Ph}4) are the first host–guest complexes to be synthesized directly from cyclic dimethylsiloxanes, alkali-metal ions, and weakly coordinating anions. Their experimental and calculated structures imply that the cyclic dimethylsiloxanes act as pseudo crown ethers (see structure of [LiD6]+).

    26. An Organic Photoelectrode Working in the Water Phase: Visible-Light-Induced Dioxygen Evolution by a Perylene Derivative/Cobalt Phthalocyanine Bilayer (pages 2778–2781)

      Toshiyuki Abe, Keiji Nagai, Satoko Kabutomori, Masao Kaneko, Akio Tajiri and Takayoshi Norimatsu

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200504454

      Thumbnail image of graphical abstract

      Two layers are better than one: The organic bilayer composed of 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole (PTCBI, an n-type semiconductor) and cobalt phthalocyanine (CoPc, a p-type semiconductor) was found to act as a novel photoanode that is responsive to visible light under 750 nm to induce efficiently the photoelectrochemical splitting of water to evolve dioxygen.

    27. Highly Active, Productive, and Syndiospecific Yttrium Initiators for the Polymerization of Racemic β-Butyrolactone (pages 2782–2784)

      Abderramane Amgoune, Christophe M. Thomas, Simona Ilinca, Thierry Roisnel and Jean-François Carpentier

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200600058

      Thumbnail image of graphical abstract

      Alternate tacticities: The ring-opening polymerization of rac-β-butyrolactone (rac-BBL) using a six-coordinate yttrium complex bearing a dianionic amine-bis(phenolate) ligand as initiator proceeds readily at room temperature to give the corresponding poly(3-hydroxybutyrate) (PHB) with up to 94 % syndiotacticity and narrow molecular-weight distributions (see scheme).

    28. Highly Enantioselective Conjugate Reduction of β,β-Disubstituted α,β-Unsaturated Nitriles (pages 2785–2787)

      Daehyung Lee, Daesung Kim and Jaesook Yun

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200600184

      Thumbnail image of graphical abstract

      Easy access: The highly enantioselective conjugate reduction of α,β-unsaturated nitriles is achieved by employing bench-top stable copper(II) acetate and josiphos (L) as the ligand in the presence of polymethylhydrosiloxane (PMHS). This protocol provides ready access to valuable chiral β-aryl substituted nitriles in good yields and with excellent enantioselectivities.

    29. A Ligand-Library Approach to the Highly Efficient Rhodium/Phosphoramidite-Catalyzed Asymmetric Arylation of N,N-Dimethylsulfamoyl-Protected Aldimines (pages 2789–2791)

      Richard B. C. Jagt, Patrick Y. Toullec, Danny Geerdink, Johannes G. de Vries, Ben L. Feringa and Adriaan J. Minnaard

      Version of Record online: 23 MAR 2006 | DOI: 10.1002/anie.200504309

      Thumbnail image of graphical abstract

      Small but effective: The title reaction, after microwave-assisted removal of the N,N-dimethylsulfamoyl protecting group, leads to chiral diarylmethyl amines. The use of 1 mol % catalyst and 1.3 equivalents of aryl boronic acid results in excellent yields (up to 98 %) and enantioselectivities (up to 95 % ee) of the isolated products. acac=acetylacetonate; eth=ethylene.

    30. A Nonanuclear Gallium(III) Cluster: An Intermediate in the Formation of Dinuclear Triple-Stranded Helicates? (pages 2792–2794)

      Markus Albrecht, Sabrina Dehn and Roland Fröhlich

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200600123

      Thumbnail image of graphical abstract

      What happens in between? A nonanuclear gallium(III) cluster (see structure: white H, gray C, red O, orange Br, beige Ga) is a potential intermediate in the assembly of a dinuclear helicate. The cluster could be isolated because of conformational restrictions at the ligand which disfavor the formation of the triple-stranded helical complex.

    31. A Hexanuclear Iron(III) Carboxylate with an [Fe63-O)32-OH)]11+ Core as an Efficient Catalyst for Cycloalkane Oxidation (pages 2794–2798)

      Günter Trettenhahn, Michael Nagl, Norbert Neuwirth, Vladimir B. Arion, Walther Jary, Peter Pöchlauer and Walther Schmid

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200504406

      Thumbnail image of graphical abstract

      Six of one: A hexanuclear iron p-nitrobenzoate compound (see structure; green Fe, red O, blue N, gray C), a novel type of iron cluster was prepared and characterized. The complex has an [Fe63-O)32-OH)]11+ core and shows a remarkable catalytic activity in the oxidation of cyclohexane.

    32. Cleavage of the N2 Triple Bond by the Ti Dimer: A Route to Molecular Materials for Dinitrogen Activation? (pages 2799–2802)

      Hans-Jörg Himmel, Olaf Hübner, Wim Klopper and Laurent Manceron

      Version of Record online: 21 MAR 2006 | DOI: 10.1002/anie.200503709

      Thumbnail image of graphical abstract

      The Ti dimer is fairly weakly bound, but highly reactive, and completely cleaves the strong N2 triple bond in just one step without activation energy (see scheme; Ti red, N blue). In contrast, a Ti atom in its ground electronic state does not react with N2.

    33. Structural and Spectroscopic Characterization of Active Sites in a Family of Light-Emitting Sodium Lanthanide Tetrafluorides (pages 2802–2806)

      Annina Aebischer, Marc Hostettler, Jürg Hauser, Karl Krämer, Thomas Weber, Hans Ulrich Güdel and Hans-Beat Bürgi

      Version of Record online: 20 MAR 2006 | DOI: 10.1002/anie.200503966

      Thumbnail image of graphical abstract

      Illuminating disorder: Many highly efficient light emitters are members of the family β-NaLnF4 (Ln=Y, La–Lu). Diffuse X-ray scattering is combined with single-crystal absorption spectroscopy at cryogenic temperatures to unambiguously identify and characterize two crystallographically inequivalent spectroscopic sites (A and B). The high light yield is correlated with the existence and nature of these sites.

    34. You have free access to this content

SEARCH

SEARCH BY CITATION