Angewandte Chemie International Edition

Cover image for Vol. 47 Issue 22

May 19, 2008

Volume 47, Issue 22

Pages 4029–4237

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: Amine Grafting on Coordinatively Unsaturated Metal Centers of MOFs: Consequences for Catalysis and Metal Encapsulation (Angew. Chem. Int. Ed. 22/2008) (page 4029)

      Young Kyu Hwang, Do-Young Hong, Jong-San Chang, Sung Hwa Jhung, You-Kyong Seo, Jinheung Kim, Alexandre Vimont, Marco Daturi, Christian Serre and Gérard Férey

      Article first published online: 9 MAY 2008 | DOI: 10.1002/anie.200890100

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      Site-selective functionalization … of coordinatively unsaturated sites in MIL-101, Cr3(F,OH)(H2O)2O[(O2C)-C6H4-(CO2)]3n H2O (n≈25), is described by J.-S. Chang, G. Férey et al. in their Communication on page 4144 ff. After dehydration of MIL-101, grafting with amine molecules followed by noble-metal encapsulation leads to metal–organic frameworks having high catalytic activity in the Knoevenagel condensation and the Heck coupling reaction.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS) (Angew. Chem. Int. Ed. 22/2008) (page 4030)

      Joseph M. Mabry, Ashwani Vij, Scott T. Iacono and Brent D. Viers

      Article first published online: 9 MAY 2008 | DOI: 10.1002/anie.200890101

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      The lotus leaf obtains its superhydrophobic properties from the presence of both microscopic and nanoscopic roughness on the leaf surface. A fluorinated polyhedral oligomeric silsesquioxane (FD-POSS) forms a molecular package with similar nanoscopic surface roughness. J. M. Mabry, A. Vij et al. report in their Communication on page 4137 ff. on what is probably the most hydrophobic crystalline compound known. Leaf photographs: William Thielicke and Yves Rubin.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Graphical Abstract: Angew. Chem. Int. Ed. 22/2008 (pages 4033–4044)

      Article first published online: 9 MAY 2008 | DOI: 10.1002/anie.200890102

  4. Corrigendum

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

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Implications of a Carboxylate-Bound C-Cluster Structure of Carbon Monoxide Dehydrogenase (pages 4054–4056)

      Paul A. Lindahl

      Article first published online: 11 APR 2008 | DOI: 10.1002/anie.200800223

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      Seeing the C: Nickel-containing carbon monoxide dehydrogenases reversibly oxidize CO to CO2 at a {[Fe3S4]:[Ni Fea]} active site known as the C-cluster. Recently reported structures of the enzyme by Jeoung and Dobbek, including those of CO2-bound and OH-bound intermediates, shed new light on the enzyme's catalytic mechanism. This Highlight describes these developments and their implications.

    2. Carbodicarbenes: Divalent Carbon(0) Compounds (pages 4057–4061)

      Oliver Kaufhold and F. Ekkehardt Hahn

      Article first published online: 25 APR 2008 | DOI: 10.1002/anie.200800846

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      Polarization of C[DOUBLE BOND]C bonds is the trick! A “push–push” polarization of the double bonds stabilized the nonlinear allene 1 a (∢C[BOND]C[BOND]C 134.8(2)°), which can be described as carbodicarbene 1 b. A similar behavior has been observed for 1,3-dimethyl-2-methyleneimidazoline, which can be seen as an olefin 2 a or an ylide 2 b. Both compounds 1 and 2 act as interesting electron-rich η1 ligands for transition metals.

  8. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Amyloids: Not Only Pathological Agents but Also Ordered Nanomaterials (pages 4062–4069)

      Izhack Cherny and Ehud Gazit

      Article first published online: 15 APR 2008 | DOI: 10.1002/anie.200703133

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      Domestication of amyloids: Amyloid structures, some beneficial, some detrimental, exist in nature. Now that these protein assemblies have been characterized and the amyloidogenic motifs identified, these types of structures will soon be utilized in a range of nanotechnological applications.

  9. Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
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    1. Organic Semiconductors for Solution-Processable Field-Effect Transistors (OFETs) (pages 4070–4098)

      Sybille Allard, Michael Forster, Benjamin Souharce, Heiko Thiem and Ullrich Scherf

      Article first published online: 20 MAR 2008 | DOI: 10.1002/anie.200701920

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      Part of the solution: Solution-processable organic semiconductor materials will take on a pivotal role in printed components of organic electronics (see photo; copyright Evonik). This Review gives an overview of the favored strategies for the solubilization of organic semiconductors and their synthetic conversion. Low molecular weight and oligomeric semiconductor materials as well as semiconductor polymers are discussed.

  10. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Review
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Structural Effects of Solvents on the Breathing of Metal–Organic Frameworks: An In Situ Diffraction Study (pages 4100–4105)

      Franck Millange, Christian Serre, Nathalie Guillou, Gérard Férey and Richard I. Walton

      Article first published online: 18 APR 2008 | DOI: 10.1002/anie.200705607

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      Breathing space: Time-resolved diffraction studies of the breathing of metal–organic frameworks in the presence of liquids reveal rapid exchange of one guest molecule by another. In some cases this occurs by direct exchange (as shown for water by pyridine), in others with the transient appearance of crystalline intermediates corresponding to partially expanded forms.

    2. U-Shaped Conformation of Alkyl Chains Bound to a Synthetic Host (pages 4106–4109)

      Young Ho Ko, Hyunuk Kim, Youngkook Kim and Kimoon Kim

      Article first published online: 29 APR 2008 | DOI: 10.1002/anie.200800581

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      Taking it in turn: Despite the high internal strain, the long aliphatic chains of alkyltrimethylammonium ions buried deeply inside the cucurbit[8]uril (CB[8]) cavity adopt a U-shaped conformation (see X-ray structure), which is stabilized by electrostatic and van der Waals interactions with the carbonyl-laced portal and hydrophobic cavity of CB[8]. This conformation is similar to that of fatty acids bound to fatty acid binding proteins.

    3. Binding of Aminoglycoside Antibiotics to the Duplex Form of the HIV-1 Genomic RNA Dimerization Initiation Site (pages 4110–4113)

      Séverine Freisz, Kathrin Lang, Ronald Micura, Philippe Dumas and Eric Ennifar

      Article first published online: 25 APR 2008 | DOI: 10.1002/anie.200800726

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      Targeting HIV RNA: High-resolution X-ray structures of the HIV-1 genomic RNA dimerization initiation site (DIS) extended duplex bound to several aminoglycoside antibiotics have been obtained (see ribostamycin complex as an example). They show the feasibility of targeting viral RNA with small drugs, and open up the possibility of structure-based rational drug design aimed against viral replication.

    4. Quantitative Evaluation of Anion–π Interactions in Solution (pages 4114–4118)

      Guzmán Gil-Ramírez, Eduardo C. Escudero-Adán, Jordi Benet-Buchholz and Pablo Ballester

      Article first published online: 21 APR 2008 | DOI: 10.1002/anie.200800636

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      Anions included: A series of meso-tetraaryl calix[4]pyrrole receptors have been used as a model system to quantify chloride–π interactions in solution (see picture; green balls are chloride ions). The free energy values are generally indicative of a repulsive interaction; their magnitude depends on the substituent on the aromatic ring.

    5. Sensitive NMR Sensors Detect Antibodies to Influenza (pages 4119–4121)

      Isaac Koh, Rui Hong, Ralph Weissleder and Lee Josephson

      Article first published online: 21 APR 2008 | DOI: 10.1002/anie.200800069

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      Catching the flu: Magnetic particle aggregation has been used to provide a highly sensitive, NMR-based sensor for detecting antibodies to an influenza virus. To achieve high sensitivity, a homogeneous magnetic field (H) was employed to enhance antibody-based cross-linking between particles suspended in solution (see scheme; ΔT2: change in the transverse relaxation time).

    6. Enantioselective Activation of Aldehydes by Chiral Phosphoric Acid Catalysts in an Aza-ene-type Reaction between Glyoxylate and Enecarbamate (pages 4122–4125)

      Masahiro Terada, Kazuyo Soga and Norie Momiyama

      Article first published online: 17 APR 2008 | DOI: 10.1002/anie.200800232

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      Double interaction does it: Highly enantio- and diastereoselective aza-ene-type reaction of glyoxylate with an enecarbamate is accomplished by using a binol-derived phosphoric acid catalyst (see scheme). DFT computational analysis revealed that two hydrogen bonds formed between the catalyst and the aldehyde are critical for the high enantioselectivity.

    7. The Origin of Nonmagnetic Kramers Doublets in the Ground State of Dysprosium Triangles: Evidence for a Toroidal Magnetic Moment (pages 4126–4129)

      Liviu F. Chibotaru, Liviu Ungur and Alessandro Soncini

      Article first published online: 21 APR 2008 | DOI: 10.1002/anie.200800283

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      Triangular donuts: High-level ab initio calculations reveal a toroidal arrangement of local magnetizations at dysprosium sites in the ground state of triangular dysprosium complexes (see picture), an arrangement that explains their unusual magnetic properties.

    8. A Coordinatively Linked Yb Metal–Organic Framework Demonstrates High Thermal Stability and Uncommon Gas-Adsorption Selectivity (pages 4130–4133)

      Shengqian Ma, Xi-Sen Wang, Daqiang Yuan and Hong-Cai Zhou

      Article first published online: 24 APR 2008 | DOI: 10.1002/anie.200800312

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      Narrow pores for high selectivity: The ytterbium metal–organic framework PCN-17, which contains coordinatively (through SO42− ions) linked, doubly interpenetrated (8,3)-nets (see picture), is stable up to 480 °C and exhibits selective adsorption of H2 and O2 over N2 and CO.

    9. A Polar Radical Pair Pathway To Assemble the Pyrimidinone Core of the HIV Integrase Inhibitor Raltegravir Potassium (pages 4134–4136)

      Philip J. Pye, Yong-Li Zhong, Gavin O. Jones, Robert A. Reamer, Kendall N. Houk and David Askin

      Article first published online: 24 APR 2008 | DOI: 10.1002/anie.200703681

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      Break up to make up: Combined experimental and computational studies provide evidence that the key step in the synthesis of a novel anti-HIV drug involves an unprecedented stepwise radical pair rearrangement mechanism in which radical fragments are held together by strong electrostatic forces (see scheme); this is favored over alternative mechanisms involving concerted pericyclic rearrangement.

    10. Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS) (pages 4137–4140)

      Joseph M. Mabry, Ashwani Vij, Scott T. Iacono and Brent D. Viers

      Article first published online: 24 APR 2008 | DOI: 10.1002/anie.200705355

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      Water-repellent: Fluorinated polyhedral oligomeric silsesquioxanes (POSS) are produced by facile, single-step, base-catalyzed condensation of trialkoxy silanes. The octameric fluorinated polyhedra are soluble, thermally stable, and hydrophobic, exhibiting static water contact angles up to 154°. The fluorodecyl POSS is believed to be the most hydrophobic crystalline solid known.

    11. Structural and Spectroscopic Characterization of an Unprecedented Cationic Transition-Metal η1-Silane Complex (pages 4141–4143)

      Jian Yang, Peter S. White, Cynthia K. Schauer and Maurice Brookhart

      Article first published online: 24 APR 2008 | DOI: 10.1002/anie.200705359

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      No room for side-on: In the complex shown, Et3SiH is bound to the cationic IrIII center in an unprecedented end-on fashion through the Si[BOND]H bond with no appreciable metal–silicon interaction (white H, green Si, pink Ir, red O, orange P, gray C). The long Ir⋅⋅⋅Si distance of 3.346(1) Å is 0.97 Å greater than the sum of the covalent radii of Ir and Si. DFT studies indicate that the tBu substituents on the bidentate phosphorus ligand dictate the coordination mode of the silane.

    12. Amine Grafting on Coordinatively Unsaturated Metal Centers of MOFs: Consequences for Catalysis and Metal Encapsulation (pages 4144–4148)

      Young Kyu Hwang, Do-Young Hong, Jong-San Chang, Sung Hwa Jhung, You-Kyong Seo, Jinheung Kim, Alexandre Vimont, Marco Daturi, Christian Serre and Gérard Férey

      Article first published online: 24 APR 2008 | DOI: 10.1002/anie.200705998

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      The coordinatively unsaturated sites in MIL-101, Cr3(F,OH)(H2O)2O[(O2C)-C6H4-(CO2)]3n H2O (n≈25), having zeotypic giant pores can be selectively functionalized in a way differing from that of mesoporous silica. Metal–organic frameworks, grafted with ethylenediamine or diethylenetriamine on the unsaturated CrIII sites of MIL-101, exhibit remarkably high activities in the Knoevenagel condensation relative to that of the mesophase.

    13. Wavelength-Dependent Photochromic Inorganic–Organic Hybrid Based on a 3D Iodoplumbate Open-Framework Material (pages 4149–4152)

      Zhang-Jing Zhang, Sheng-Chang Xiang, Guo-Cong Guo, Gang Xu, Ming-Sheng Wang, Jian-Ping Zou, Sheng-Ping Guo and Jing-Shun Huang

      Article first published online: 22 APR 2008 | DOI: 10.1002/anie.200800603

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      Plumb pudding: A 3D iodoplumbate inorganic–organic hybrid built from purely octahedral units, obtained through in situ solvothermal synthesis, belongs to a new structural subclass of organically templated inorganic open-framework materials. It exhibits the properties of its 1D incomplete-cubane-chain building block and shows ordered and periodic quantum-wire behavior, as well as a wavelength-dependent photochromic response.

    14. Converting Sequences of Aromatic Amino Acid Monomers into Functional Three-Dimensional Structures: Second-Generation Helical Capsules (pages 4153–4156)

      Chunyan Bao, Brice Kauffmann, Quan Gan, Kolupula Srinivas, Hua Jiang and Ivan Huc

      Article first published online: 28 APR 2008 | DOI: 10.1002/anie.200800625

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      New codes for sequence–structure–function relationships can be elaborated in aromatic oligoamide foldamers upon varying main-chain components. Each monomer carries its own structural and functional features and enables oligomeric sequences to be designed to encapsulate specific guests.

    15. Cinchona Alkaloid Catalyzed Enantioselective Fluorination of Allyl Silanes, Silyl Enol Ethers, and Oxindoles (pages 4157–4161)

      Takehisa Ishimaru, Norio Shibata, Takao Horikawa, Naomi Yasuda, Shuichi Nakamura, Takeshi Toru and Motoo Shiro

      Article first published online: 21 APR 2008 | DOI: 10.1002/anie.200800717

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      Catalytic variant: Allyl silanes and silyl enol ethers 1 are good substrates for the catalytic highly enantioselective fluorodesilylation using a combination of a bis-cinchona alkaloid, N-fluorobenzenesulfonimide (NFSI), and base (see scheme). Pharmaceutically attractive 3-aryl-3-fluorooxindoles such as 3 can also be synthesized with high enantioselectivity.

    16. A Rational Approach towards the Nucleophilic Substitutions of Alcohols “on Water” (pages 4162–4166)

      Pier Giorgio Cozzi and Luca Zoli

      Article first published online: 25 APR 2008 | DOI: 10.1002/anie.200800622

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      Walking on water: Which alcohols react with nucleophiles on the surface of water? The correlations introduced by Mayr et al., in which electrophiles are characterized by the parameter E, gives practical indications about the reactivity of alcohols with nucleophiles in pure water. Stable carbocations generated from the alcohols and characterized by E<−2.5 readily react with nucleophiles in pure water at 80 °C, without added Brønsted or Lewis acids.

    17. Synthesis of Diastereomers of Complestatin and Chloropeptin I: Substrate-Dependent Atropstereoselectivity of the Intramolecular Suzuki–Miyaura Reaction (pages 4167–4172)

      Yanxing Jia, Michèle Bois-Choussy and Jieping Zhu

      Article first published online: 11 APR 2008 | DOI: 10.1002/anie.200800599

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      See the effect of C: Atropisomers as well as CC2 epimers of complestatin and chloropeptin I (see picture) are readily synthesized through an intramolecular SNAr reaction and the Suzuki–Miyaura reaction. The absolute configuration of amino acid C (red) was found to determine the atropselectivity of the aryl–aryl (blue) bond-forming reaction.

    18. Sc3N@C80-Ferrocene Electron-Donor/Acceptor Conjugates as Promising Materials for Photovoltaic Applications (pages 4173–4176)

      Julio R. Pinzón, Marta E. Plonska-Brzezinska, Claudia M. Cardona, Andreas J. Athans, S. Shankara Gayathri, Dirk M. Guldi, M. Ángeles Herranz, Nazario Martín, Tomas Torres and Luis Echegoyen

      Article first published online: 22 APR 2008 | DOI: 10.1002/anie.200800473

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      Intriguing materials for photovoltaics: The first trimetallic nitride endohedral metallofullerene covalently connected to a donor group is efficiently synthesized in a 1,3-dipolar cycloaddition reaction. Exclusive formation of the [5,6]-regioisomer in the isolated N-methyl-2-ferrocenyl-Ih-Sc3N@C80-fulleropyrrolidine is confirmed by NMR spectroscopy and electrochemistry (see picture).

    19. A Highly Stereoselective Hydrogen-Bond-Mediated Michael–Michael Cascade Process through Dynamic Kinetic Resolution (pages 4177–4179)

      Jian Wang, Hexin Xie, Hao Li, Liansuo Zu and Wei Wang

      Article first published online: 17 APR 2008 | DOI: 10.1002/anie.200800381

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      Oh Mickey, you're so fine: The title reaction, which is efficiently catalyzed by a cinchona alkaloid thioure affords direct access to thiochromanes in high efficiency. The reaction features a new activation mode of organocatalytic dynamic kinetic resolution involving a Michael–retro-Michael–Michael–Michael cascade.

    20. Simultaneous Copper(I)-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) and Living Radical Polymerization (pages 4180–4183)

      Jin Geng, Josefina Lindqvist, Giuseppe Mantovani and David M. Haddleton

      Article first published online: 15 APR 2008 | DOI: 10.1002/anie.200800179

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      All in one: CuBr/iminopyridine systems can catalyze simultaneously both copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC, “click”) and living radical polymerization (LRP) processes (see scheme). The relative rate of the two processes can be tailored by a judicious choice of the reaction conditions (solvent, temperature, [CuBr]0) leading to the development of a potentially very efficient synthetic route to well-defined functional polymers.

    21. Diastereoselective Tetrahydropyrone Synthesis through Transition-Metal-Free Oxidative Carbon–Hydrogen Bond Activation (pages 4184–4187)

      Wangyang Tu, Lei Liu and Paul E. Floreancig

      Article first published online: 21 APR 2008 | DOI: 10.1002/anie.200706002

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      C[BOND]C bonds from C[BOND]H bonds: Tethering nucleophilic groups to benzylic and allylic ethers allows cyclization reactions by DDQ-mediated oxidative carbon–hydrogen bond activation (see scheme; DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone). The method is operationally simple, proceeds with a wide range of ether groups, is tolerant of functional groups, and is highly stereoselective.

    22. Amphoteric Amino Aldehydes Enable Rapid Assembly of Unprotected Amino Alcohols (pages 4188–4191)

      Ryan Hili and Andrei K. Yudin

      Article first published online: 25 APR 2008 | DOI: 10.1002/anie.200705776

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      Apples and oranges: The term “amphoteric” is derived from the Greek “amphoteros”, which literally means “both of two”. Amphoteric amino aldehydes are counterintuitive molecules in that they contain both electrophilic and nucleophilic centers. These small but powerful reagents can be used for the streamlined construction of complex amino alcohol scaffolds (see scheme). Their premature self-destruction is prevented on kinetic grounds.

    23. Nanoribbons Self-Assembled from Triblock Peptide Polymers and Coordination Polymers (pages 4192–4195)

      Yun Yan, Aernout A. Martens, Nicolaas A. M. Besseling, Frits A. de Wolf, Arie de Keizer, Markus Drechsler and Martien A. Cohen Stuart

      Article first published online: 21 APR 2008 | DOI: 10.1002/anie.200705242

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      Concerted effects: Triblock peptide copolymers, organic multidentate ligands, and Zn2+ ions associate spontaneously into well-defined nanoribbons when dissolved at proper ratios in water at moderate pH values. These nanofibers are stabilized by an extraordinary concerted effect of distinct noncovalent interactions: metal–ligand complexation, hydrogen bonding, hydrophobic interaction, and polyelectrolyte complexation between coordination polymers and the charged blocks of the peptide copolymers.

    24. Catalytic Enantioselective Aldol-type Reaction of β-Ketosters with Acetals (pages 4196–4199)

      Natsuko Umebayashi, Yoshitaka Hamashima, Daisuke Hashizume and Mikiko Sodeoka

      Article first published online: 25 APR 2008 | DOI: 10.1002/anie.200705344

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      Two activations, one catalyst: By using cationic Pd and Pt complexes, a catalytic enantioselective aldol-type reaction of β-ketoesters with acetals has been developed (see scheme). The formation of metal enolates occurs under acidic conditions to allow the use of acetals as electrophiles to give the desired aldol products in high diastereoseletivity and enantioselectivity.

    25. A General Strategy for Construction of Both 2,6-cis- and 2,6-trans-Disubstituted Tetrahydropyrans: Substrate-Controlled Asymmetric Total Synthesis of (+)-Scanlonenyne (pages 4200–4203)

      Hyunjoo Lee, Kwan Woo Kim, Janghyun Park, Hyoungsu Kim, Sanghee Kim, Deukjoon Kim, Xiangqian Hu, Weitao Yang and Jiyong Hong

      Article first published online: 25 APR 2008 | DOI: 10.1002/anie.200705663

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      A synthetic three-ring circus: The asymmetric total synthesis of (+)-scanlonenyne includes a sequential epimerization and intramolecular hetero-Michael addition for the construction of pyrano-γ-lactones (see scheme; DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene), a highly efficient one-carbon homologation/bromination strategy, and a Weinreb ketone synthesis/cross-metathesis protocol for the elaboration of a sensitive side chain.

    26. Surfactant-Free Synthesis of SnO2@PMMA and TiO2@PMMA Core–Shell Nanobeads Designed for Peptide/Protein Enrichment and MALDI-TOF MS Analysis (pages 4204–4207)

      Huan-Ming Xiong, Xiao-Yan Guan, Ling-Hua Jin, Wen-Wen Shen, Hao-Jie Lu and Yong-Yao Xia

      Article first published online: 25 APR 2008 | DOI: 10.1002/anie.200705942

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      Extremely low concentrations of peptides and proteins can be enriched from complex solutions by SnO2@PMMA and TiO2@PMMA core–shell nanobeads with controlled size and composition (see picture for schematic synthesis), and their MALDI-TOF MS signal intensities and signal-to-noise ratios are also significantly improved. These effects are ascribed to the physical properties and structure of the nanobeads. PMMA=poly(methyl methacrylate).

    27. Is Deuterium Always Smaller than Protium? (pages 4208–4210)

      Jack D. Dunitz and Richard M. Ibberson

      Article first published online: 15 APR 2008 | DOI: 10.1002/anie.200800063

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      A question of size: At low temperatures the molecular volume in crystalline deuterated benzene is smaller than in the hydrogen isotopologue; above 170 K, however, the reverse is true (see graph).

    28. A Metallacryptand-Based Manganese(II)–Cobalt(II) Ferrimagnet with a Three-Dimensional Honeycomb Open-Framework Architecture (pages 4211–4216)

      Emilio Pardo, Danielle Cangussu, Marie-Claire Dul, Rodrigue Lescouëzec, Patrick Herson, Yves Journaux, Emerson F. Pedroso, Cynthia L. M. Pereira, M. Carmen Muñoz, Rafael Ruiz-García, Joan Cano, Pedro Amorós, Miguel Julve and Francesc Lloret

      Article first published online: 11 APR 2008 | DOI: 10.1002/anie.200800208

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      Building a three-dimensional magnet: The manganese(II)-mediated self-assembly of a ferromagnetically coupled dicobalt(II) metallacryptand provides the first example of an oxamato-bridged heterobimetallic ferrimagnet with a three-dimensional honeycomb open-framework structure hosting linear arrays of water-bridged lithium(I) guests (see picture; mpba=1,3-phenylenebis(oxamato)).

    29. An Expedient Strategy for the Synthesis of Tryptamines and Other Heterocycles (pages 4217–4220)

      K. C. Nicolaou, Arkady Krasovskiy, Vincent É. Trépanier and David Y.-K. Chen

      Article first published online: 11 APR 2008 | DOI: 10.1002/anie.200800404

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      Making many from one: N-Boc-protected anilines are converted into an array of useful N-heterocycles and tryptamines through an expedient, cascade-based synthetic sequence involving ortho metalation and subsequent coupling with N-Boc-pyrrolidin-3-one (see scheme).

    30. Total Synthesis of (+)-Fawcettidine (pages 4221–4223)

      Jennifer A. Kozak and Gregory R. Dake

      Article first published online: 22 APR 2008 | DOI: 10.1002/anie.200800522

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      Alkaloids alchemy: A synthesis of the Lycopodium alkaloid (+)-fawcettidine (see structure) has been developed which requires 16 steps from (R)-(+)-pulegone as the chiral starting material. Key steps include a platinum(II)-catalyzed annulation reaction of a functionalized enamide and a one-pot Ramberg–Bäcklund process.

    31. Straightforward Access to Protected syn α-Amino-β-hydroxy Acid Derivatives (pages 4224–4227)

      Jignesh Patel, Guillaume Clavé, Pierre-Yves Renard and Xavier Franck

      Article first published online: 24 APR 2008 | DOI: 10.1002/anie.200800860

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      Titanium stability: syn α-Amino-β-hydroxy acid derivatives were prepared in excellent diastereoselectivities by an aldol reaction with chiral N-(azidoacetyl)thiazolidin-2-thione derivatives (see scheme; NMP=N-methylpyrrolidinone). Titanium enolates of these derivatives are stable and provide a new and efficient method to access chiral amino acids.

    32. Catalytic Amide-Mediated Methyl Transfer from Silanes to Alkenes in Fujiwara–Moritani Oxidative Coupling (pages 4228–4230)

      Waqar Rauf and John M. Brown

      Article first published online: 22 APR 2008 | DOI: 10.1002/anie.200800815

      Thumbnail image of graphical abstract

      Intramolecular assistance: Carbon-bound trimethylsilyl groups are activated intramolecularly by a carbonyl group and can participate in Heck reactions under oxidative conditions. Good stereoselectivities are obtained for a range of di- and trisubstituted alkenes (see example).

    33. Expanding the [1,2]-Aryl Migration to the Synthesis of Substituted Indoles (pages 4231–4233)

      Tao Pei, Cheng-yi Chen, Peter G. Dormer and Ian W. Davies

      Article first published online: 29 APR 2008 | DOI: 10.1002/anie.200705804

      Thumbnail image of graphical abstract

      Closing in on the product: A range of 2- and 2,3-substituted indoles 2 have been synthesized in moderate to excellent yields by the addition of carbon nucleophiles (organometallic reagents, RM) to readily accessible 1-(2-aminophenyl)-2-chloroethanones of type 1 under mild conditions (see scheme). A mechanism has been proposed that involves a unique [1,2]-aryl migration of intermediate 3.

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      Preview: Angew. Chem. Int. Ed. 23/2008 (page 4237)

      Article first published online: 9 MAY 2008 | DOI: 10.1002/anie.200890105

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