Angewandte Chemie International Edition

Cover image for Vol. 47 Issue 2

December 28, 2007

Volume 47, Issue 2

Pages 219–417

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Highlights
    8. Minireview
    9. Review
    10. Communications
    11. Preview
    1. Cover Picture: A Supramolecular Catalyst for Regioselective Hydroformylation of Unsaturated Carboxylic Acids (Angew. Chem. Int. Ed. 2/2008) (page 219)

      Tomáš Šmejkal and Bernhard Breit

      Version of Record online: 19 DEC 2007 | DOI: 10.1002/anie.200790258

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      The Venus Flytrap … …waits patiently for unsuspecting prey. Once it recognizes an insect in the trap, the jaws close and soon the plant digests its meal. In their Communication on page 311 ff., T. Šmejkal and B. Breit describe the development of a novel catalytic system which combines supramolecular recognition of the substrate and transition-metal catalysis. This catalyst can effect challenging transformations such as the regioselective hydroformylation of an internal alkene.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Highlights
    8. Minireview
    9. Review
    10. Communications
    11. Preview
    1. Inside Cover: Shining New Light on an Old Problem: Retooling MALDI Mass Spectrometry for Organotransition-Metal Catalysis (Angew. Chem. Int. Ed. 2/2008) (page 220)

      Melanie D. Eelman, Johanna M. Blacquiere, Maeve M. Moriarty and Deryn E. Fogg

      Version of Record online: 19 DEC 2007 | DOI: 10.1002/anie.200790259

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      Inert-atmosphere MALDI-MS is a powerful new tool for identifying organometallic compounds. As described by D. E. Fogg and co-workers in the Communication on page 303 ff., sample decomposition is minimized by interfacing the spectrometer to a glovebox and ionizing by charge transfer. Neutral compounds, such as the Grubbs-class catalyst shown, are observed as radical cations. The metal isotope patterns expand the utility and scope of this methodology in transition-metal chemistry.

  3. Graphical Abstract

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

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Highlights
    8. Minireview
    9. Review
    10. Communications
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    1. B[BOND]N versus C[BOND]C: How Similar Are They? (pages 242–244)

      Zhiqiang Liu and Todd B. Marder

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/anie.200703535

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      One of these bonds is not like the others: Cyclic π systems in which B[BOND]N units replace their isoelectronic C[BOND]C counterparts have intrigued chemists and materials scientists for decades. The recent report of Piers et al. on the synthesis, crystal structure, and optical properties of 10a-aza-10b-borapyrenes (see picture) represents a major breakthrough in this field.

    2. Reactivity of Chromium Complexes under Spin Control (pages 245–247)

      Randolf D. Köhn

      Version of Record online: 15 NOV 2007 | DOI: 10.1002/anie.200703827

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      Spin blocking: Facile reductive C–H elimination is a key step in chromium-catalyzed selective trimerization of olefins. The direct conversion (see scheme) is prevented by the change in spin states. This Highlight also describes the latest advances in the mechanistic understanding of the catalytic trimerization with a focus on spin states.

    3. Kinetic Resolution and Desymmetrization by Stereoselective Silylation of Alcohols (pages 248–250)

      Sebastian Rendler and Martin Oestreich

      Version of Record online: 6 NOV 2007 | DOI: 10.1002/anie.200704210

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      Watch out asymmetric acylation! Non-enzymatic kinetic resolution and desymmetrization by the asymmetric acylation of alcohols has found its rival in the related silylation of alcohols. The scheme shows the two-point binding of the substrate in catalyst- (left) and reagent-controlled stereoselective silylation (right).

  7. Minireview

    1. Top of page
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    4. Graphical Abstract
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    6. Book Review
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    8. Minireview
    9. Review
    10. Communications
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    1. Hydrogen Activation by Unsaturated Mixed-Metal Cluster Complexes: New Directions (pages 252–257)

      Richard D. Adams and Burjor Captain

      Version of Record online: 6 NOV 2007 | DOI: 10.1002/anie.200702407

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      Recent studies of unsaturated mixed-metal cluster complexes containing platinum and bulky phosphine ligands for hydrogen activation are reviewed (see picture; Pt blue, Rh green, P yellow, O red, C light brown, H gray). A summary of some related studies on bimetallic cooperativity and trimetallic nanoparticles for catalytic hydrogenation is also included.

  8. Review

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Highlights
    8. Minireview
    9. Review
    10. Communications
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    1. Metal-Catalyzed Enantioselective Allylation in Asymmetric Synthesis (pages 258–297)

      Zhan Lu and Shengming Ma

      Version of Record online: 29 OCT 2007 | DOI: 10.1002/anie.200605113

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      Chiral carbon centers can be constructed in a highly stereoselective manner by the reaction of allylic substrates containing a leaving group with a range of nucleophiles in the presence of metal compexes and chiral ligands.

  9. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Highlights
    8. Minireview
    9. Review
    10. Communications
    11. Preview
    1. The Structure of the Plutonium Oxide Nanocluster [Pu38O56Cl54(H2O)8]14− (pages 298–302)

      L. Soderholm, Philip M. Almond, S. Skanthakumar, Richard E. Wilson and Peter C. Burns

      Version of Record online: 10 DEC 2007 | DOI: 10.1002/anie.200704420

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      Oxide inside: The structure of a plutonium(IV) oxide nanoparticle (see picture; Pu green, O red and blue, Cl yellow) has been determined by single-crystal diffraction in the solid state and verified in aqueous solution by high-energy X-ray scattering. The nanoparticles are composed of 38 Pu ions arranged in an oxide lattice with a structure slightly distorted from the fluorite phase seen in PuO2. An absorption spectrum of the Pu clusters in solution is consistent with the classic Pu-polymer optical response.

    2. Shining New Light on an Old Problem: Retooling MALDI Mass Spectrometry for Organotransition-Metal Catalysis (pages 303–306)

      Melanie D. Eelman, Johanna M. Blacquiere, Maeve M. Moriarty and Deryn E. Fogg

      Version of Record online: 28 NOV 2007 | DOI: 10.1002/anie.200704489

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      Getting the air out: A bottleneck in transition-metal chemistry is the laborious process of identifying organometallic molecules. Anaerobic, charge-transfer MALDI-MS is a powerful new tool for observation of these reactive, often fragile species. Examples are drawn from catalysts relevant to olefin metathesis, hydrogenation, polymerization, and cyclopropanation. IMes=N,N′-bis(mesityl)imidazol-2-ylidene.

    3. Gold(0) Porphyrins on Gold Nanoparticles (pages 307–310)

      Masayuki Kanehara, Hirokazu Takahashi and Toshiharu Teranishi

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/anie.200703943

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      Bound through S–Au bonds, multidentate macrocyclic porphyrin thioester derivatives densely protect Au nanoparticles in a face-coordination fashion (see picture) to form quite stable Au0 porphyrins. The spectroscopic Soret-band intensity can be tuned by the distance between the porphyrin ring and the Au surface.

    4. A Supramolecular Catalyst for Regioselective Hydroformylation of Unsaturated Carboxylic Acids (pages 311–315)

      Tomáš Šmejkal and Bernhard Breit

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/anie.200703192

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      The quest to capture the catalytic power of enzymes is one of the great challenges of modern chemistry. A novel system inspired by the principles of enzymatic catalysis combines recognition of the substrate and transition-metal catalysis (see scheme; Do=donor, FG=functional group) and mimics enzyme properties—high efficiency, substrate selectivity, and reaction-site selectivity.

    5. Quantum Dot Bioconjugation during Core–Shell Synthesis (pages 316–319)

      Qiangbin Wang, Yan Liu, Yonggang Ke and Hao Yan

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/anie.200703648

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      One small step: A facile and robust one-step method for creating stable, water-soluble quantum dot (QD)–biomolecule conjugates is described. DNA molecules can be readily attached to QDs during core–shell synthesis (see picture of DNA functionalization of a CdSe@ZnS core–shell QD).

    6. Stimuli-Responsive Reversible Transport of Nanoparticles Across Water/Oil Interfaces (pages 320–323)

      Erik W. Edwards, Munish Chanana, Dayang Wang and Helmuth Möhwald

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/anie.200702597

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      To cap it all: With the aid of stimuli-responsive polymer capping, gold nanoparticles (Au-NPs) can be highly colloidally stable in both aqueous and organic media. They spontaneously and reversibly cross water/oil interfaces in both directions upon formation of a biphasic salty water–oil system (see picture).

    7. Structure of the Protein BPTI Derived with NOESY in Supercooled Water: Validation and Refinement of Solution Structures (pages 324–326)

      Yang Shen and Thomas Szyperski

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/anie.200702842

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      Fidelity without frostbite: Refinement of an NMR solution structure of 6-kDa protein BPTI determined at 36 °C (see picture, red) with NOE distance constraints measured in supercooled water at −15 °C increased precision of backbone and core side-chain coordinates about twofold (blue). In contrast to cryogenic X-ray crystallography (−150 °C), supercooling to about −15 °C hardly affects the conformation of flexibly disordered surface side chains.

    8. Highly Efficient and Thermally Stable Organic Sensitizers for Solvent-Free Dye-Sensitized Solar Cells (pages 327–330)

      Hyunbong Choi, Chul Baik, Sang Ook Kang, Jaejung Ko, Moon-Sung Kang, Md. K. Nazeeruddin and Michael Grätzel

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200703852

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      A sense for sensitizers: Devices based on JK-46 (see structure) and a volatile electrolyte yielded an extremely high overall conversion efficiency of 8.6 % under AM 1.5 sunlight. Solar cells fabricated employing the JK-46 sensitizer and a solvent-free ionic-liquid electrolyte gave an efficiency of over 7 % and demonstrated excellent stability under light soaking at 60 °C for 1000 h.

      Corrected by:

      Corrigendum: Highly Efficient and Thermally Stable Organic Sensitizers for Solvent-Free Dye-Sensitized Solar Cells

      Vol. 48, Issue 10, 1712, Version of Record online: 17 FEB 2009

    9. Capture and Release of Protein by a Reversible DNA-Induced Sol–Gel Transition System (pages 331–333)

      Bryan Wei, Immensee Cheng, Kathy Q. Luo and Yongli Mi

      Version of Record online: 21 NOV 2007 | DOI: 10.1002/anie.200704143

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      Cross-links holding on, then letting go: Polyacrylamide main chains were branched with DNA strands, which could be gelatinized by DNA base pairing with a thrombin-bound cross-linking strand (see scheme). A complementary DNA strand can form a duplex with the cross-linking strand to dissolve the hydrogel and release the thrombin.

    10. Ga–Al Mixed-Oxide-Supported Gold Nanoparticles with Enhanced Activity for Aerobic Alcohol Oxidation (pages 334–337)

      Fang-Zheng Su, Yong-Mei Liu, Lu-Cun Wang, Yong Cao, He-Yong He and Kang-Nian Fan

      Version of Record online: 20 NOV 2007 | DOI: 10.1002/anie.200704370

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      Toward greener organic synthesis: A high activity for the aerobic oxidation of alcohols is achieved under base-free and ambient conditions by using gold catalysts supported on mesostructured γ-Ga2O3/Al2O3 solid solutions (see picture). The enhanced activity is attributed to the extraordinary alcohol-dehydrogenation activity of gallia-based mixed oxides.

    11. Interplay between Hydrogen Bonding and Macromolecular Architecture Leading to Unusual Phase Behavior in Thermosensitive Microgels (pages 338–341)

      Martina Keerl, Vytautas Smirnovas, Roland Winter and Walter Richtering

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/anie.200703728

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      In a depressed state: The intra- and intermolecular hydrogen-bonding pattern of microgels comprising N-isopropylacrylamide (NIPAM) and N,N-diethylacrylamide (DEAAM) can be determined by FTIR spectroscopy. In contrast to core–shell systems (see picture, right), an increase in intramolecular hydrogen bonding in copolymer microgels (left) favors polymer–polymer interactions and leads to a marked depression of the phase-transition temperature.

    12. Mechanistic Insight into the Diastereoselective Rhodium-Catalyzed Pauson–Khand Reaction: Role of Coordination Number in Stereocontrol (pages 342–345)

      Huijun Wang, James R. Sawyer, P. Andrew Evans and Mu-Hyun Baik

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/anie.200702822

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      How much CO? Theoretical analysis of the origin of diastereocontrol in the rhodium-catalyzed Pauson–Khand reaction (see scheme) provides two mechanistic scenarios in which optimum selectivity can be attributed to a five- rather than a four-coordinate organorhodium complex. The relative population of these complexes is related to carbon monoxide concentration, a finding which is in contrast to phosphine-containing rhodium(I) complexes.

    13. Platinum-Catalyzed Formation of Cyclic-Ketone-Fused Indoles from N-(2-Alkynylphenyl)lactams (pages 346–349)

      Guotao Li, Xiaogen Huang and Liming Zhang

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/anie.200702931

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      An oxygen atmosphere aids the efficient formation of highly substituted ring-fused indoles by the versatile title reaction through an initial cyclization followed by the sequential migration of two groups. The cycloisomerization can be viewed as a net intramolecular insertion of one end of the alkyne into the lactam amide bond with concurrent migration of the substituent at the alkyne terminus (see scheme; n=0–2; R=alkyl, alkenyl, aryl, H; R′=OMe, Br, CO2Et).

    14. One-Pot Multicomponent Synthesis of Indoles from 2-Iodobenzoic Acid (pages 350–352)

      Olivier Leogane and Hélène Lebel

      Version of Record online: 23 NOV 2007 | DOI: 10.1002/anie.200703671

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      A synergism: The multicomponent assembly of an alkyne, a nucleophile, and a carboxylic acid gave indole derivatives in good yield and high regioselectivity by a one-pot Curtius rearrangement/palladium-catalyzed indolization process (see scheme). A synergistic effect was observed; the by-product of the first reaction served as a reagent for the second step. The first synthesis of indole N-carboxamide derivatives by heteroannulation is also described.

      Corrected by:

      Corrigendum: One-Pot Multicomponent Synthesis of Indoles from 2-Iodobenzoic Acid

      Vol. 47, Issue 16, 2907, Version of Record online: 1 APR 2008

    15. A Core/Shell Catalyst Produces a Spatially Confined Effect and Shape Selectivity in a Consecutive Reaction (pages 353–356)

      Jun Bao, Jingjiang He, Yi Zhang, Yoshiharu Yoneyama and Noritatsu Tsubaki

      Version of Record online: 15 NOV 2007 | DOI: 10.1002/anie.200703335

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      A well-wrapped catalyst: Coating an H-beta zeolite membrane onto the surface of a preshaped Co/Al2O3 pellet leads to a novel core/shell catalyst with a confined reaction environment which shows excellent selectivity for the synthesis of isoparaffins from syngas (see picture; FT=Fischer–Tropsch). Long-chain hydrocarbon formation is totally suppressed by the zeolite membrane. This kind of membrane catalyst could be extended to various other consecutive reactions by modifying the shell membrane and the core catalyst.

    16. Fluorine-Directed Diastereoselective Iodocyclizations (pages 357–360)

      Matthew Tredwell, Jennifer A. R. Luft, Marie Schuler, Kenny Tenza, Kendall N. Houk and Véronique Gouverneur

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200703465

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      An inside job: β-Fluorinated lactones and tetrahydrofurans are synthesized by iodocyclization of various allylic fluorides. The fluorine substituent acts as a highly efficient syn-stereodirecting group for the ring closure. The experimental results combined with theoretical studies provide evidence in support of an “inside fluoro effect” to account for the sense and level of stereocontrol of these reactions.

    17. Unusual B4N2C2 Ligand in a Ruthenium Pseudo-Triple-Decker Sandwich Complex Displaying Three Reversible Electron-Transfer Steps (pages 361–364)

      Hanh V. Ly, Heikki M. Tuononen, Masood Parvez and Roland Roesler

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200703556

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      Open, sesame: The reaction of a heterobicyclic pentalenediyl-like Me2Ph4B4N2C2 dianion with [{(C5Me5)RuCl}4] cleaves the N[BOND]N bond of the ligand and affords a pseudo-triple-decker sandwich complex containing a B4N2C2 middle deck (see picture). This eight-membered ring features nearly linear B-N-B moieties and brings the ruthenium centers unusually close. Cyclic voltammetry indicates efficient electron delocalization over the framework.

    18. Converting Free-Standing Porous Silicon into Related Porous Membranes (pages 365–367)

      Yajun Yang, Guowen Meng, Xianyun Liu and Lide Zhang

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/anie.200703698

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      Like a chip off the old block: Compound porous membranes SixAy, such as Si3N4, SiC, and Zn2SiO4, have been synthesized by in situ conversion of porous silicon (PS) films (see picture). The resultant membranes inherit the morphology and microstructure of the mother PS films and have potential applications in filters, catalytic supports, and sensing materials.

    19. Elucidation of an Overpotential-Limited Branching Phenomenon Observed During the Electrocrystallization of Cuprous Oxide (pages 368–372)

      Matthew J. Siegfried and Kyoung-Shin Choi

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200702432

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      Molecular bonsai: Depending on the reaction conditions, the growth of copper(I) oxide crystals proceeds by an overpotential-limited or a conventional diffusion-limited dendritic branching mechanism (see picture). Faceting and branching are critically effected by the pH value and overpotential.

    20. 3D Aperiodic Hierarchical Porous Graphitic Carbon Material for High-Rate Electrochemical Capacitive Energy Storage (pages 373–376)

      Da-Wei Wang, Feng Li, Min Liu, Gao Qing Lu and Hui-Ming Cheng

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/anie.200702721

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      Electrochemical capacitors: A hierarchical porous graphitic carbon material, composed of macroporous ion-buffering microreservoirs, ion-transporting channels, and localized graphitic wall structures, is presented (see images; top: 3D skeleton, bottom: carbon platelet). The properties of this new material combine to overcome the electrode kinetic problems normally found in electrochemical capacitors, thus resulting in an excellent high-rate energy-storage performance.

      Corrected by:

      Corrigendum: 3D Aperiodic Hierarchical Porous Graphitic Carbon Material for High-Rate Electrochemical Capacitive Energy Storage

      Vol. 48, Issue 9, 1525, Version of Record online: 10 FEB 2009

    21. Self-Assembly in Systems of Subcomponents: Simple Rules, Subtle Consequences (pages 377–380)

      Rupam J. Sarma and Jonathan R. Nitschke

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200703877

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      All together now: Five subcomponents (see scheme) come together cleanly with CuI to form simultaneously all four product structures shown. Simply by changing the stoichiometry, any given subset of product structures is accessible. To explain the observed selectivity, it is necessary to consider the stability not only of individual products, but of the system as a whole.

    22. Direct Detection and Mapping of Sites of Base Modification in DNA Fragments by Tandem Mass Spectrometry (pages 381–384)

      Goutam Chowdhury and F. Peter Guengerich

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/anie.200703942

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      Map reading: Alkylation of a 15-base-pair double-stranded oligonucleotide modified with the carcinogen (±)-anti-benzo[a]pyrene diol epoxide (see picture) or N-hydroxy-4-aminobiphenyl is mapped by liquid chromatograhy–tandem mass spectrometry and collision-induced dissociation (CID). The method does not require prior DNA cleavage or hydrolysis.

    23. Nickel/BPh3-Catalyzed Alkynylcyanation of Alkynes and 1,2-Dienes: An Efficient Route to Highly Functionalized Conjugated Enynes (pages 385–387)

      Yoshiaki Nakao, Yasuhiro Hirata, Masaaki Tanaka and Tamejiro Hiyama

      Version of Record online: 15 NOV 2007 | DOI: 10.1002/anie.200704095

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      Adding across: A C(sp)[BOND]C(sp) bond of alkynyl cyanides is activated by nickel/Lewis acid catalysis derived from [Ni(cod)2] and BPh3, and the alkynylcyanation reaction of alkynes and 1,2-dienes is achieved by the binary catalysis for the first time to give a range of functionalized conjugated enyne molecules with defined stereo- and regioselectivities.

    24. Catalytic Enantioselective Passerini Three-Component Reaction (pages 388–391)

      Shi-Xin Wang, Mei-Xiang Wang, De-Xian Wang and Jieping Zhu

      Version of Record online: 15 NOV 2007 | DOI: 10.1002/anie.200704315

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      Make it enantioselective: The [(salen)AlIIICl] complex 1 catalyzes the title reaction of an aldehyde, a carboxylic acid, and an isocyanide to afford α-acyloxyamides 2 with good to excellent enantioselectivity. A variety of nonchelating substrates can be used to generate the versatile chiral products. R1=alkyl; R2=alkyl, alkenyl, aryl; R3=alkyl, aryl.

    25. Highly Enantioselective Hydrophosphonylation of Aldehydes Catalyzed by Tridentate Schiff Base Aluminum(III) Complexes (pages 392–394)

      Xin Zhou, Xiaohua Liu, Xu Yang, Deju Shang, Junguo Xin and Xiaoming Feng

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/anie.200704116

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      Active in dimeric form: A tridentate Schiff base aluminum(III) complex has been applied in the asymmetric hydrophosphonylation of various aldehydes, giving the corresponding products in good yields with good to excellent ee values (up to 97 %). The strong positive nonlinear effect, along with high-resolution MS analyses, indicates that the reaction is performed in the presence of a dimeric aluminum species. Ad=adamantyl.

    26. IR Spectrum of the Ethyl Cation: Evidence for the Nonclassical Structure (pages 395–397)

      Horia-Sorin Andrei, Nicola Solcà and Otto Dopfer

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/anie.200704163

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      Argon tagging allowed the IR spectrum of the ethyl cation C2H5+ to be inferred by resonant IR photodissociation spectroscopy of weakly bound C2H5+⋅Ar complexes (see picture). The experimental spectrum closely resembles the theoretical spectra of 1 and 1⋅Ar but shows large deviations from the spectrum predicted for 2, and thus it provides the first direct spectroscopic evidence for the nonclassical structure 1 of protonated ethene.

    27. Catalytic Enantioselective 1,6-Conjugate Addition of Grignard Reagents to Linear Dienoates (pages 398–401)

      Tim den Hartog, Syuzanna R. Harutyunyan, Daniel Font, Adriaan J. Minnaard and Ben L. Feringa

      Version of Record online: 28 NOV 2007 | DOI: 10.1002/anie.200703702

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      Dual function of catalyst: Both regio- and enantioselectivity are dictated by Cu catalysis using the reversed josiphos ligand. This allows enantioselective 1,6-addition of Grignard reagents to acyclic α,β,γ,δ-unsaturated esters monosubstituted at the β and δ positions (see scheme).

    28. Rational Design of a Double-Walled Tetrahedron Containing Two Different C3-Symmetric Ligands (pages 402–405)

      Iris M. Oppel (née Müller) and Kirsten Föcker

      Version of Record online: 13 NOV 2007 | DOI: 10.1002/anie.200703789

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      Two is better than one: The predictability of supramolecular coordination compounds relies on an exact match between the ligands used and the steric demand of the metal center. However, the use of two different C3-symmetric ligands results in a double-walled tetrahedron (see picture; inside: red, outside: blue; orange Zn2+, yellow methanolate, green MeOH or H2O) that does not contain a perfectly matched ligand–metal pair.

    29. Selective Activity-Based Probes for Cysteine Cathepsins (pages 406–409)

      Anja Watzke, Gregor Kosec, Maik Kindermann, Volker Jeske, Hans-Peter Nestler, Vito Turk, Boris Turk and K. Ulrich Wendt

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/anie.200702811

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      By “reverse design”: The core structures of protease inhibitors, whose selectivity has been optimized by extensive medicinal chemistry, have been redesigned into selective protease substrates by replacing the reactive electrophilic group (e.g. nitrile) with a cleavable peptide bond. Attachment of appropriate reporter groups yields cell-permeable activity-based probes for the cellular imaging of selected cysteine cathepsins.

    30. The Multidentate Ligand (MeOMe2Si)3Si: Unusual Coordination Modes in Alkali Metal Silanides (pages 410–413)

      Clemens Krempner, Malcolm H. Chisholm and Judith Gallucci

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/anie.200703575

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      Chain gang: Introducing methoxy groups into (Me3Si)4Si and treatment with alkali metal alkoxides leads to hitherto unknown zwitterionic alkali metal silanides [(MeOMe2Si)3SiM] with a bicyclooctane (Li, Na) or heterocubane (K) structure. The lithium and sodium compounds form infinite chains in the solid state (see picture: green Li, blue Si, red O, gray C) and dissociate in THF solutions into zwitterionic monomers.

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      Preview: Angew. Chem. Int. Ed. 3/2008 (page 417)

      Version of Record online: 19 DEC 2007 | DOI: 10.1002/anie.200790262

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