Angewandte Chemie International Edition

Cover image for Vol. 46 Issue 17

April 20, 2007

Volume 46, Issue 17

Pages 2955–3155

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Review
    8. Highlight
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Cover Picture: Template-Directed Synthesis of a π-Conjugated Porphyrin Nanoring (Angew. Chem. Int. Ed. 17/2007) (page 2955)

      Markus Hoffmann, Craig J. Wilson, Barbara Odell and Harry L. Anderson

      Article first published online: 12 APR 2007 | DOI: 10.1002/anie.200790067

      A molecular wire is forged into a smooth ring—not by the blacksmith's fire, as shown in the background of the picture—but by the vicelike grip of an octadentate template. H. L. Anderson and co-workers describe in their Communication on page 3122 ff. how a linear porphyrin oligomer can be cyclized to generate a highly symmetric belt-shaped π system (image by M. Hoffmann; background photograph by J. McNerney, Yukon Forge, www.yukonforge.com).

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Review
    8. Highlight
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
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    1. Inside Cover: An Isolable and Monomeric Phosphorus Radical That Is Resonance-Stabilized by the Vanadium(IV/V) Redox Couple (Angew. Chem. Int. Ed. 17/2007) (page 2956)

      Paresh Agarwal, Nicholas A. Piro, Karsten Meyer, Peter Müller and Christopher C. Cummins

      Article first published online: 12 APR 2007 | DOI: 10.1002/anie.200790068

      Bulky redox-active metalloligands stabilize the phosphorus radical [.P{N[DOUBLE BOND]V[N(Np)Ar]3}2] (Np=neopentyl) to the extent that it exists as a monomer even in the solid state. C. C. Cummins and co-workers describe in their Communication on page 3111 ff. the EPR spectrum of the radical (see picture; P orange, N blue, V yellow), which reveals delocalization of the unpaired electron onto both vanadium centers. Radical bond formation at the phosphorus atom leads to diamagnetic products.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Review
    8. Highlight
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
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    1. Graphical Abstract: Angew. Chem. Int. Ed. 17/2007 (pages 2959–2971)

      Article first published online: 12 APR 2007 | DOI: 10.1002/anie.200790069

  4. Corrigenda

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Review
    8. Highlight
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    1. You have free access to this content
      Towards Biological Supramolecular Chemistry: A Variety of Pocket-Templated, Individual Metal Oxide Cluster Nucleations in the Cavity of a Mo/W-Storage Protein (page 2970)

      Jörg Schemberg, Klaus Schneider, Ulrike Demmer, Eberhard Warkentin, Achim Müller and Ulrich Ermler

      Article first published online: 12 APR 2007 | DOI: 10.1002/anie.200790070

    2. You have free access to this content
      Catalytic Asymmetric Acylcyanation of Imines (page 2971)

      Subhas Chandra Pan, Jian Zhou and Benjamin List

      Article first published online: 12 APR 2007 | DOI: 10.1002/anie.200790071

      This article corrects:

      Catalytic Asymmetric Acylcyanation of Imines1

      Vol. 46, Issue 4, 612–614, Article first published online: 12 DEC 2006

    3. You have free access to this content
      Antibacterial Aminoglycosides with a Modified Mode of Binding to the Ribosomal-RNA Decoding Site (page 2971)

      Boris François, Janek Szychowski, Susanta Sekhar Adhikari, Kandasamy Pachamuthu, Eric E. Swayze, Richard H. Griffey, Michael T. Migawa, Eric Westhof and Stephen Hanessian

      Article first published online: 12 APR 2007 | DOI: 10.1002/anie.200790074

      This article corrects:

      Antibacterial Aminoglycosides with a Modified Mode of Binding to the Ribosomal-RNA Decoding Site1

      Vol. 43, Issue 48, 6735–6738, Article first published online: 9 DEC 2004

  5. News

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Review
    8. Highlight
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
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    1. The Click Reaction in the Luminescent Probing of Metal Ions, and Its Implications on Biolabeling Techniques (pages 2980–2982)

      Otto S. Wolfbeis

      Article first published online: 6 MAR 2007 | DOI: 10.1002/anie.200604897

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      Copper concentrations at a click: The copper(I)-catalyzed Huisgen cycloaddition (the “click reaction”) enables micromolar concentrations of physiologically active Cu+ ions to be sensed through photonic energy transfer (ET, see scheme), and offers great potential in terms of labeling methods.

  8. Correspondence

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Review
    8. Highlight
    9. Correspondence
    10. Minireview
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    1. Réplique: A New Concept for Bonding in Carbodiphosphoranes? (pages 2984–2985)

      Hubert Schmidbaur

      Article first published online: 1 MAR 2007 | DOI: 10.1002/anie.200700139

      The conclusions drawn from results of recent theoretical and experimental investigations on the chemistry of carbodiphosphoranes are reconsidered in light of the state-of-the-art reached after extensive investigations that were carried out a few decades ago.

    2. Reply to Réplique: A New Concept for Bonding in Carbodiphosphoranes? (pages 2986–2987)

      Gernot Frenking, Bernhard Neumüller, Wolfgang Petz, Ralf Tonner and Florian Öxler

      Article first published online: 1 MAR 2007 | DOI: 10.1002/anie.200700327

      Neither is the synthesis of a molecule a mere technical conformation of a theoretical prediction, nor is a quantum chemical investigation a mere supplement to experimental work—the two sides rather complement each other. The theoretical study in question has shown that more compounds of the general formula EL2 with donor–acceptor bonds may exist which await synthesis.

  9. Minireview

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
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    8. Highlight
    9. Correspondence
    10. Minireview
    11. Review
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    1. N-Heterocyclic Carbenes as Organocatalysts (pages 2988–3000)

      Nicolas Marion, Silvia Díez-González and Steven P. Nolan

      Article first published online: 9 MAR 2007 | DOI: 10.1002/anie.200603380

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      Gifted NHCs: The scope of N-heterocyclic carbenes (NHCs) as organocatalysts has been broadened tremendously in the last few years (see picture). The numerous novel reactions catalyzed by NHCs, as well as their mechanistic implications, are reviewed.

  10. Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Review
    8. Highlight
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
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    1. Lithium Diisopropylamide: Solution Kinetics and Implications for Organic Synthesis (pages 3002–3017)

      David B. Collum, Anne J. McNeil and Antonio Ramirez

      Article first published online: 23 MAR 2007 | DOI: 10.1002/anie.200603038

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      Lessons learned: Lithium diisopropylamide metalates organic substrates through a variety of mechanisms. Although the mechanistic complexity can be daunting, this Review attempts to distill mechanistic studies down to a collection of simple maxims, with particular attention paid to the influence of solvation and aggregation on reactivity.

  11. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Book Review
    8. Highlight
    9. Correspondence
    10. Minireview
    11. Review
    12. Communications
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    1. Alkoxy Derivatives of Dodecaborate: Discrete Nanomolecular Ions with Tunable Pseudometallic Properties (pages 3018–3022)

      Mark W. Lee, Omar K. Farha, M. Frederick Hawthorne and Corwin H. Hansch

      Article first published online: 27 MAR 2007 | DOI: 10.1002/anie.200605126

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      Twelve of one, a dozen of the other: Synthetic pseudometallic molecules were prepared by fully substituting the [B12H12]2− ion with 12 alkoxy groups. Reversible redox reactions reveal substituent-dependent potentials varying over 1.2 V (see picture) which were characterized and correlated using Hammett and QSAR linear free-energy relationships.

    2. Synthesis and Characterization of (Z)-[N3NFO]+ and (E)-[N3NFO]+ (pages 3023–3027)

      William W. Wilson, Ralf Haiges, Jerry A. Boatz and Karl O. Christe

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200700130

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      A new stable polynitrogen ion: The second known example of a stable nitrogen fluoride oxide ion, [N3NFO]+, was prepared as its [SbF6] salt and characterized by multinuclear NMR and vibrational spectroscopy and electronic-structure calculations. The cation is planar and exists as two stereoisomers (see picture; N blue, O red, F dark blue).

    3. On the Stereodivergent Behavior Observed in the Staudinger Reaction between Methoxyketene and (E)-N-Benzylidenearyl Amines (pages 3028–3032)

      Bimal K. Banik, Begoña Lecea, Ana Arrieta, Abel de Cózar and Fernando P. Cossío

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200605231

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      The answer is out there: Detailed calculations on the Staudinger reaction between methoxyketene and imines derived from aromatic amines show that the stereochemistry of the reaction is determined by an isomerization barrier that does not belong to the cycloaddition stages (see picture).

    4. Triangle-Shaped Polycyclic Aromatic Hydrocarbons (pages 3033–3036)

      Xinliang Feng, Jishan Wu, Min Ai, Wojciech Pisula, Linjie Zhi, Jürgen P. Rabe and Klaus Müllen

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200605224

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      Triangles and zigzags: Large triangle-shaped C3-symmetrical polycyclic aromatic hydrocarbons with multiple zigzag peripheries were synthesized. The molecules display mesophase stability over a wide temperature range as a result of helical packing. Moreover, a 2D honeycomb pattern was observed for one of the larger structures (see picture).

    5. Self-Assembly of Bidentate Ligands for Combinatorial Homogeneous Catalysis: Methanol-Stable Platforms Analogous to the Adenine–Thymine Base Pair (pages 3037–3039)

      Christoph Waloch, Jörg Wieland, Manfred Keller and Bernhard Breit

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200605202

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      Complementary partners: A combinatorial library of self-assembled ligand systems has been designed by analogy to the A–T base pair. When these ligand systems are applied in the rhodium-catalyzed hydroformylation of 1-octene (see scheme), high regioselectivities (rs) are obtained, even in the protic solvent methanol.

    6. Self-Assembled Supramolecular Bidentate Ligands for Aqueous Organometallic Catalysis (pages 3040–3042)

      Cécile Machut, Julien Patrigeon, Sébastien Tilloy, Hervé Bricout, Frédéric Hapiot and Eric Monflier

      Article first published online: 16 MAR 2007 | DOI: 10.1002/anie.200605166

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      Sugar snap P: An N,P heterobidentate supramolecular ligand was synthesized in water by mixing a monoamino-β-cyclodextrin with an appropriate phosphane. The resultant assembly was used with a platinum(II) salt in aqueous medium to catalyze the hydrogenation of an allylic alcohol (see picture).

    7. Double Insertion of Isocyanides into Dihydropyridines: Direct Access to Substituted Benzimidazolium Salts (pages 3043–3046)

      Carme Masdeu, Elena Gómez, Nana Aba O. Williams and Rodolfo Lavilla

      Article first published online: 13 MAR 2007 | DOI: 10.1002/anie.200605070

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      Double agent: The insertion of two isocyanide molecules into the dihydropyridine ring in the presence of iodine results in the formation of a benzimidazole core (see scheme). Four bonds are generated (bold lines) in a highly efficient and atom-economical manner. Access to a range of benzimidazolium derivatives is possible through a cascade reaction.

    8. Enesulfonamides as Nucleophiles in Catalytic Asymmetric Reactions (pages 3047–3050)

      Ryosuke Matsubara, Takashi Doko, Ryosuke Uetake and Shū Kobayashi

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200605054

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      A biased copper-coin toss: Highly diastereo- and enantioselective copper-catalyzed addition reactions of enesulfonamides to α-keto aldehydes and azodicarboxylates have been developed. Low loadings of the chiral copper catalyst efficiently promoted the reaction (see scheme). The product sulfonylimines could be reduced diastereoselectively to the biologically important chiral sulfonamide compounds.

    9. Self-Assembled Peptide Nanoarrays: An Approach to Studying Protein–Protein Interactions (pages 3051–3054)

      Berea A. R. Williams, Kyle Lund, Yan Liu, Hao Yan and John C. Chaput

      Article first published online: 16 MAR 2007 | DOI: 10.1002/anie.200603919

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      On show: High-density peptide arrays capable of displaying many different amino acid sequences at well-defined and addressable locations on the same DNA nanostructure have been produced. The strategy used relies on the genetic information encoded in the nucleic acid portion of a DNA-tagged peptide to position the amino acid sequence at a predetermined location on the array.

    10. 1-Alkyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octanes: Unconventional Class of Mesomorphic Columnar Compounds (pages 3055–3058)

      Masaki Shimizu, Masanori Nata, Kenji Mochida, Tamejiro Hiyama, Seiji Ujiie, Masafumi Yoshio and Takashi Kato

      Article first published online: 15 MAR 2007 | DOI: 10.1002/anie.200604170

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      Phasing up to matters: Hexagonal columnar mesophases have been formed by polysilacage compounds based on 1-alkyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octanes that contain neither aromatic rings nor long alkyl chains. These mesophases have been characterized by polarizing optical photomicroscopy (see picture), differential scanning calorimetry, and diffraction studies.

    11. Translation of Mutarotation into Induced Circular Dichroism Signals through Helix Inversion of Host Polymers (pages 3059–3061)

      Minoru Waki, Hajime Abe and Masahiko Inouye

      Article first published online: 13 MAR 2007 | DOI: 10.1002/anie.200604176

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      About turn: The preferred helical sense of the complex formed between glucose and the meta-ethynylpyridine polymer in aqueous methanol is inverted by mutarotation (see picture). The strong circular dichroism effects induced by pure α- and β-D-glucose weakened with time because the diastereomer excess decreased through mutarotation. The transition curve of the ellipticity closely reflected that of the anomer ratio.

    12. Bioceramic Macrocapsules for Cell Immunoisolation (pages 3062–3065)

      Shaomin Liu, Lihong Liu, Zhi Ping Xu, Aimin Yu, Gao Qing Lu and Joao C. Diniz da Costa

      Article first published online: 16 MAR 2007 | DOI: 10.1002/anie.200604682

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      A bone to pick: Tailor-made zirconia macrocapsules are biocompatible and friendly to MC3T3-E1 cells and can facilitate osteoblast cell differentiation. Cells encapsulated within such capsular chambers are viable and grow well by absorbing the nutrients permeated through the capsule micropores from the outside environment. These capsules are promising as immunoisolation medical templates for bone-tissue engineering.

    13. Dynamic Hydrogels: Translating a Protein Conformational Change into Macroscopic Motion (pages 3066–3069)

      William L. Murphy, W. Shannon Dillmore, Justin Modica and Milan Mrksich

      Article first published online: 15 MAR 2007 | DOI: 10.1002/anie.200604808

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      Natural inspiration: A bioinspired functional material in the form of a hydrogel created by cross-linking an engineered version of calmodulin, a protein which undergoes a conformational change in response to ligand binding (see schematic representation), with a four-armed poly(ethylene glycol) molecule terminated with acrylate groups decreased in volume by 20 % when treated with the ligand trifluoperazine. Multiple cycles of gel swelling and shrinkage were possible.

    14. Molecular Recognition Drives Oligonucleotide Binding to Nucleolipid Self-Assemblies (pages 3070–3073)

      Martina Banchelli, Debora Berti and Piero Baglioni

      Article first published online: 15 MAR 2007 | DOI: 10.1002/anie.200604826

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      Ordered interactions: Selective supramolecular association of oligonucleotides with like-charged amphiphilic self-assemblies in aqueous solution, in the absence of divalent cations, is reported. A structural model of the nucleolipoplex, the ordered mesophase formed upon interaction of DNA (red) with anionic nucleolipid assemblies (green), is shown. The hexagonal arrangement is templated by the complementary polynucleotide.

    15. Highly Efficient and Versatile Synthesis of Proteoglycan Core Structures from 1,6-Anhydro-β-lactose as a Key Starting Material (pages 3074–3079)

      Ken Shimawaki, Yoshinori Fujisawa, Fumihiro Sato, Naoki Fujitani, Masaki Kurogochi, Hiroko Hoshi, Hiroshi Hinou and Shin-Ichiro Nishimura

      Article first published online: 15 MAR 2007 | DOI: 10.1002/anie.200604909

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      Versatile building blocks in the form of novel derivatives of 1,6-anhydro-β-lactose have been used for the rapid and highly efficient synthesis of various proteoglycan core structures (see example). The resulting oligosaccharide–tetrapeptide conjugates can be used to investigate the mechanism of biosynthesis of glycosaminoglycans in human cartilage cells. Bn=benzyl.

    16. Variable C2-Symmetric Analogues of N-Hydroxyphthalimide as Enantioselective Catalysts for Aerobic Oxidation: Kinetic Resolution of Oxazolidines (pages 3080–3083)

      Malek Nechab, Dhondi Naveen Kumar, Christian Philouze, Cathy Einhorn and Jacques Einhorn

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200603780

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      Fast and selective: The aerobic oxidative ring opening of oxazolidine 1 in the presence of a catalytic amount of the chiral N-hydroxyphthalimide analogue 2 was accompanied by efficient kinetic resolution of the oxazolidine. Thus, 50.5 % conversion was attained within 2 h, and the remaining 1 had an ee value of 89 %. The corresponding stereoselectivity factor, s=krel(fast/slow), is very high at around 40.

    17. An Unexpected Pathway in the Cage Opening and Aggregation of P4 (pages 3084–3086)

      Wesley Ting Kwok Chan, Felipe García, Alexander D. Hopkins, Lucy C. Martin, Mary McPartlin and Dominic S. Wright

      Article first published online: 2 MAR 2007 | DOI: 10.1002/anie.200604267

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      Graceful degradation: The reaction of the [(Me3Si)3Si] ion with white phosphorus results in a new phosphorus-based dianion (see scheme; R=Si(SiMe3)3), apparently arising from the unexpected aggregation of two [RP4] units into a P7 nortricyclic core with an exo anionic P atom. The formation of this dianion sheds new light on the mechanism(s) of P4 degradation by nucleophiles and the ability of silyl substituents to direct product formation.

    18. Manual Assembly of Microcrystal Monolayers on Substrates (pages 3087–3090)

      Jin Seok Lee, Jae Hyun Kim, Young Ju Lee, Nak Cheon Jeong and Kyung Byung Yoon

      Article first published online: 2 MAR 2007 | DOI: 10.1002/anie.200604367

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      Do-it-yourself: Monolayers of molecules and nanoparticles should be prepared on substrates only by self-assembly, but monolayers of microparticles can be produced by both self-assembly and direct manual attachment as if they are tiles (see picture). The quality of the monolayers is better when they are assembled by hand than by self-assembly.

    19. Xerogel-Encapsulated W110A Secondary Alcohol Dehydrogenase from Thermoanaerobacter ethanolicus Performs Asymmetric Reduction of Hydrophobic Ketones in Organic Solvents (pages 3091–3094)

      Musa M. Musa, Karla I. Ziegelmann-Fjeld, Claire Vieille, J. Gregory Zeikus and Robert S. Phillips

      Article first published online: 16 MAR 2007 | DOI: 10.1002/anie.200604615

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      To gel well: The asymmetric reduction of hydrophobic ketones by xerogel-immobilized W110A secondary alcohol dehydrogenase from Thermoanaerobacter ethanolicus (TeSADH) in organic solvents affords their S-configured alcohols in yields comparable with those achieved by using the free enzyme, and, in some cases, with higher enantioselectivities. R=phenyl-ring-containing substituent.

    20. Addition of Terminal Alkynes to a Molecular Titanium–Zinc Nitride (pages 3095–3098)

      Jorge J. Carbó, Avelino Martín, Miguel Mena, Adrián Pérez-Redondo, Josep-M. Poblet and Carlos Yélamos

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200604677

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      Cubic cages: The alkynylimido clusters 2 ([Ti]=Ti(η5-C5Me5); R=SiMe3, Ph) are formed upon reaction of 1 with terminal alkynes. Density functional calculations show that the process involves a two-electron reduction of the Ti3 fragment. A concerted C[BOND]H activation, which leads to an alkynyl titanium complex, is followed by alkynyl migration to the apical nitrido ligand (see picture).

    21. In Situ Formation of Protein–Polymer Conjugates through Reversible Addition Fragmentation Chain Transfer Polymerization (pages 3099–3103)

      Jingquan Liu, Volga Bulmus, David L. Herlambang, Christopher Barner-Kowollik, Martina H. Stenzel and Thomas P. Davis

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200604922

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      A good place for rafting: Bovine serum albumin (BSA) was site-specifically modified with a reversible addition fragmentation chain transfer (RAFT) agent and used in γ-radiation-initiated polymerization of oligo(ethylene glycol) acrylate. Well-defined polymer chains were formed at the RAFT agent conjugation site of BSA leading to the generation of BSA–polymer conjugates in situ.

    22. Enantioselective Total Synthesis of the Osteoclastogenesis Inhibitor (+)-Symbioimine (pages 3104–3106)

      Justin Kim and Regan J. Thomson

      Article first published online: 15 MAR 2007 | DOI: 10.1002/anie.200605160

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      No bones about it: The first enantioselective total synthesis of the osteoclastogenesis inhibitor (+)-symbioimine (1) has been achieved. The synthesis features a convergent enol silane addition to a dimethyl acetal and a key, possibly biomimetic, intramolecular Diels–Alder reaction promoted by a dihydropyridinium ion to build four of the five requisite stereocenters in one step.

    23. A Highly Enantioselective Intramolecular Michael Reaction Catalyzed by N-Heterocyclic Carbenes (pages 3107–3110)

      Eric M. Phillips, Manabu Wadamoto, Audrey Chan and Karl A. Scheidt

      Article first published online: 15 MAR 2007 | DOI: 10.1002/anie.200605235

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      Metal-less Michael: A highly diastereo- and enantioselective intramolecular Michael addition of α,β-unsaturated aldehydes to enones catalyzed by an N-heterocyclic carbene (NHC) has been developed. The reaction is tolerant of alkyl and aromatic substituents, as well as saturated and unsaturated tethers between the enal and conjugate acceptor (see scheme).

    24. An Isolable and Monomeric Phosphorus Radical That Is Resonance-Stabilized by the Vanadium(IV/V) Redox Couple (pages 3111–3114)

      Paresh Agarwal, Nicholas A. Piro, Karsten Meyer, Peter Müller and Christopher C. Cummins

      Article first published online: 12 MAR 2007 | DOI: 10.1002/anie.200700059

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      Aiding and abetting a wanted radical: The neutral phosphorus radical [.P{NV[N(Np)Ar]3}2] (Np=neopentyl, Ar=3,5-Me2C6H3) exists as a monomer in the solid state and is resonance-stabilized by two nitridovanadium trisanilide metalloligands through the VIV/VV redox couple (see EPR trace and calculated SOMO of [.P{NV[N(Me)Ph]3}2]). The compound undergoes radical reactions at its phosphorus center to form diamagnetic compounds.

    25. Evolving a Thermostable DNA Polymerase That Amplifies from Highly Damaged Templates (pages 3115–3117)

      Christian Gloeckner, Katharina B. M. Sauter and Andreas Marx

      Article first published online: 15 MAR 2007 | DOI: 10.1002/anie.200603987

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      The foreign lesion: DNAs with damage generated, for example, by UV light are not good targets for standard replicative DNA polymerases. A DNA polymerase has been derived by directed evolution that faithfully amplifies light-damaged DNA. Interestingly, a single mutation is sufficient for this property (see picture).

    26. Synthesis of Stable Isothiazole Carbenes (pages 3118–3121)

      Janine Wolf, Winfried Böhlmann, Matthias Findeisen, Thomas Gelbrich, Hans-Jörg Hofmann and Bärbel Schulze

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200604305

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      Through deprotonation of isothiazolium salts, stable substituted singlet carbenes of isothiazol-3-ylidenes (see scheme) could be synthesized for the first time. The carbenes, which were characterized by solid-state and solution NMR spectroscopy, undergo typical carbene reactions, such as dimerization and insertion into polarized X[BOND]H bonds, and might be important for a number of further reactions.

    27. Template-Directed Synthesis of a π-Conjugated Porphyrin Nanoring (pages 3122–3125)

      Markus Hoffmann, Craig J. Wilson, Barbara Odell and Harry L. Anderson

      Article first published online: 23 FEB 2007 | DOI: 10.1002/anie.200604601

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      Round the bend: Bending a molecular wire round an eight-spoked template leads to the formation of a highly symmetric belt-shaped π system (green in picture). Addition of a large excess of pyridine releases the corresponding cyclic octamer from the template.

    28. Alkyl Migration and an Unusual Tetramethylaluminate Coordination Mode: Unexpected Reactivity of Organolanthanide Imino–Amido–Pyridine Complexes (pages 3126–3130)

      Melanie Zimmermann, Karl W. Törnroos and Reiner Anwander

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200604729

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      Remove-Al: Organolanthanide complexes with anionic ligands derived from bis(imino)pyridine give insight into organoaluminum-mediated alkylation of the ligand backbone and self-complexation. In addition, they provide structural evidence of the elusive η1 coordination mode in {Ln(μ-Me)AlMe3} (see picture).

    29. Stereo- and Regiochemical Divergence in the Substitution of a Lithiated Alk-1-en-3-yn-2-yl Carbamate: Synthesis of Highly Enantioenriched Vinylallenes or Alk-3-en-5-yn-1-ols (pages 3131–3134)

      Roland Bou Chedid, Michael Brümmer, Birgit Wibbeling, Roland Fröhlich and Dieter Hoppe

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200604978

      Thumbnail image of graphical abstract

      Alternative outcomes. The regio- and stereoselectivity of the hydroxyalkylation of a lithiated alk-1-en-3-yn-2-yl carbamate such as (S)-1 can be controlled simply for the synthesis of highly enantioenriched vinylallenes 2. Alternatively, lithium–titanium exchange proceeds with inversion of configuration, and addition of carbonyl electrophiles produces enantioenriched homoaldol products such as (S,Z)-3 (see scheme, Cb=carbamoyl).

    30. An Efficient Bimetallic Rhodium Catalyst for the Direct Arylation of Unactivated Arenes (pages 3135–3138)

      Sebastian Proch and Rhett Kempe

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200604988

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      Together we stand: A novel N,P-ligand-stabilized bimetallic rhodium complex 1 accomplishes an efficient nondirected arylation of unactivated arenes. Aryl halides with several functional groups (FG) undergo these direct coupling reactions. The key to the catalytic efficiency is the bimetallic nature of the catalyst.

    31. Iridium-Catalyzed Synthesis of Primary Allylic Amines from Allylic Alcohols: Sulfamic Acid as Ammonia Equivalent (pages 3139–3143)

      Christian Defieber, Martin A. Ariger, Patricia Moriel and Erick M. Carreira

      Article first published online: 12 MAR 2007 | DOI: 10.1002/anie.200700159

      Thumbnail image of graphical abstract

      Two for the price of one: Sulfamic acid serves not only as a nitrogen source but also as an in situ activator of hydroxy groups in the first direct iridium-catalyzed synthesis of primary allylic amines from allylic alcohols (see scheme; cod=cycloocta-1,5-diene). The reaction is catalyzed by a commercially available iridium complex and a phosphoramidite-based bidentate phosphorus–olefin ligand.

    32. Na29Zn24Sn32: A Zintl Phase Containing a Novel Type of {Sn14} Enneahedra and Heteroatomic {Zn8Sn4} Icosahedra (pages 3144–3148)

      Sung-Jin Kim, Stephan D. Hoffman and Thomas F. Fässler

      Article first published online: 13 MAR 2007 | DOI: 10.1002/anie.200604356

      Thumbnail image of graphical abstract

      A new type of polyhedron: An {Sn14} enneahedron, which can be derived from a trigonal bipyramid by truncating the three equatorial vertices, occurs in linear chains in Na29Zn24Sn32 (see picture; Sn blue). A pseudorotation of the {Sn14} enneahedron allows the number of covalent interactions within the complex three-dimensional atom arrangement to be adjusted, so that an electron-precise Zintl phase is attained.

    33. Self-Assembly of Metal–Virus Nanodumbbells (pages 3149–3151)

      Sinan Balci, Kei Noda, Alexander M. Bittner, Anan Kadri, Christina Wege, Holger Jeske and Klaus Kern

      Article first published online: 20 MAR 2007 | DOI: 10.1002/anie.200604558

      Thumbnail image of graphical abstract

      Golden viruses: The rodlike tobacco mosaic virus and citrate-covered gold nanoparticles of 6-nm diameter self-assemble into a metal-virus nanodumbbell. The gold nanoparticles selectively bind to the ends of the rods, and can be enlarged by electroless deposition to yield gold-virus-gold dumbbells (see picture).

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      Preview: Angew. Chem. Int. Ed. 18/2007 (page 3155)

      Article first published online: 12 APR 2007 | DOI: 10.1002/anie.200790073

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