Angewandte Chemie International Edition

Cover image for Vol. 47 Issue 51

December 8, 2008

Volume 47, Issue 51

Pages 9783–9997

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Obituary
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: Organocatalytic Asymmetric Inverse-Electron-Demand Aza-Diels–Alder Reaction of N-Sulfonyl-1-aza-1,3-butadienes and Aldehydes (Angew. Chem. Int. Ed. 51/2008) (page 9783)

      Bo Han, Jun-Long Li, Chao Ma, Shan-Jun Zhang and Ying-Chun Chen

      Version of Record online: 4 DEC 2008 | DOI: 10.1002/anie.200890263

      Thumbnail image of graphical abstract

      The inverse-electron-demand … aza Diels–Alder reaction of N-sulfonyl-1-aza-1,3-butadienes and aldehydes shown in the cover picture is explored through catalysis by an α,α-diphenylprolinol OTMS ether salt. In their Communication on page 9971 ff., Y.-C. Chen and co-workers show how this simple process affords highly enantioenriched hemiaminal intermediates, which are readily converted into a diversity of chiral piperidine derivatives.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Obituary
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: A Facile Way to Control the Number of Walls in Carbon Nanotubes through the Synthesis of Exposed-Core/Shell Catalyst Nanoparticles (Angew. Chem. Int. Ed. 51/2008) (page 9784)

      Kyung Min Choi, Saji Augustine, Jung Hoon Choi, Ju Ho Lee, Weon Ho Shin, Seong Ho Yang, Jeong Yong Lee and Jeung Ku Kang

      Version of Record online: 4 DEC 2008 | DOI: 10.1002/anie.200890264

      Thumbnail image of graphical abstract

      Simultaneous Control of the number of walls and the diameter of carbon nanotubes is possible by using exposed-core/shell (ECS) catalyst nanoparticles. In their Communication on page 9904 ff. J. K. Kang and co-workers demonstrate that the confined size of this catalyst controls the diameter of the carbon nanotubes while the number of walls is controlled by the inactive area which consists of the iron nitride at the exposed-core region of the catalyst.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Obituary
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. A Chemist's Guide to Valence Bond Theory. By Sason S. Shaik and Philippe C. Hiberty. (page 9802)

      Adelina Nemirowski and Peter R. Schreiner

      Version of Record online: 4 DEC 2008 | DOI: 10.1002/anie.200785589

  6. Obituary

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Obituary
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. Ernest Ludwig Eliel (1921–2008) (page 9803)

      Michael T. Crimmins

      Version of Record online: 4 DEC 2008 | DOI: 10.1002/anie.200805316

  7. Highlight

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

      A Reverse Ozone Hole on Mars (pages 9804–9807)

      Jos Lelieveld

      Version of Record online: 14 NOV 2008 | DOI: 10.1002/anie.200804551

      Thumbnail image of graphical abstract

      The Martian atmosphere accumulates ozone in the winter and destroys it in the summer—exactly opposite the situation on Earth. The large fluctuation in the ozone concentration can only be adequately described if heterogeneous reactions on ice clouds are accounted for in the chemistry–climate model.

  8. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Obituary
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. [2.2]Paracyclophanes

      [2.2]Paracyclophanes in Polymer Chemistry and Materials Science (pages 9808–9812)

      Henning Hopf

      Version of Record online: 7 OCT 2008 | DOI: 10.1002/anie.200800969

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      More than just pretty faces: [2.2]Paracyclophanes are becoming important monomers for the preparation of novel polymers in which the layered structure of the substrate molecules can either be destroyed or retained, allowing intraannular transmission of electronic effects in the polymeric products. The rigid structure of paracyclophanes has also been exploited for molecular scaffolding to create novel extended π systems.

  9. Review

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

      Natural-Product Sugar Biosynthesis and Enzymatic Glycodiversification (pages 9814–9859)

      Christopher J. Thibodeaux, Charles E. Melançon III and Hung-wen Liu

      Version of Record online: 4 DEC 2008 | DOI: 10.1002/anie.200801204

      Thumbnail image of graphical abstract

      A new kind of sweet: To understand the biosynthesis of unusual sugars, the sequence of enzymatic transformations and the fundamental mechanisms of pathway enzymes must be understood. Only then can sugar biosynthetic enzymes and glycosyltransferases be manipulated to engineer the structures of glycosylated natural products to generate new glycoforms with potentially novel activities.

  10. Communications

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

      Reactivity of the 3,4,5-Tridehydropyridinium Cation—An Aromatic σ,σ,σ-Triradical (pages 9860–9865)

      Bartłomiej J. Jankiewicz, Jennifer N. Reece, Nelson R. Vinueza, John J. Nash and Hilkka I. Kenttämaa

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200802714

      Thumbnail image of graphical abstract

      Seeing the sites: Reactivity studies on the σ,σ,σ-triradical 3,4,5-tridehydropyridinium cation by using a Fourier transform ion cyclotron resonance mass spectrometer show that bond formation first occurs at C3 for radical reactions, and at either C3 or C4 for nonradical reactions (see scheme). The isomeric 2,4,6-tridehydropyridinium cation shows different chemical properties because of the lower reactivity of its meta-benzyne group(s) and its greater Brønsted acidity.

    2. Nanoparticle Synthesis

      Synthesis of Gold Nanoparticles for In Situ Conjugation with Structural Carbohydrates (pages 9866–9869)

      Shingo Yokota, Takuya Kitaoka, Martina Opietnik, Thomas Rosenau and Hiroyuki Wariishi

      Version of Record online: 17 NOV 2008 | DOI: 10.1002/anie.200803922

      Thumbnail image of graphical abstract

      Sugaring the pill: Gold nanoparticles (GNPs) were successfully synthesized from tetrachloroauric acid through a novel redox reaction in an aqueous N-methylmorpholine-N-oxide (NMMO) solution, which is a well-known solvent for structural carbohydrates such as cellulose (see picture, TSC=thiosemicarbazone). This unique approach allowed facile, simultaneous GNP synthesis and in situ glycosurface modification in one pot.

    3. Structure Elucidation

      Structure and Dynamics of 13C,15N-Labeled Lipopolysaccharides in a Membrane Mimetic (pages 9870–9874)

      Wei Wang, Hans Jürgen Sass, Ulrich Zähringer and Stephan Grzesiek

      Version of Record online: 25 NOV 2008 | DOI: 10.1002/anie.200803474

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      The natural look of endotoxin: A new approach has been developed to determine the chemical structure, dynamics, and conformation of lipopolysaccharide (endotoxin, see structure) by solution NMR spectroscopy. Using isotope labeling and solubilization by dihexanoylphosphatidylcholine as a mimetic of the bacterial membrane, a general approach makes complex endotoxin molecules amenable to analysis by heteronuclear NMR methods.

    4. Nanoparticle Phase Transfer

      A Temperature-Driven Reversible Phase Transfer of 2-(Diethylamino)ethanethiol-Stabilized CdTe Nanoparticles (pages 9875–9878)

      Bing Qin, Zizhao Zhao, Rui Song, Sachin Shanbhag and Zhiyong Tang

      Version of Record online: 10 NOV 2008 | DOI: 10.1002/anie.200803582

      Thumbnail image of graphical abstract

      The reversible phase transfer of 2-(diethylamino)ethanethiol (DEAET)-stabilized CdTe nanoparticles (NPs) in a mixture of water and toluene is driven solely by temperature (see picture). Theoretical studies reveal that the net hydrophobic force of these NPs decreases at high temperature, thus favoring the transfer of NPs into the aqueous phase.

    5. Chiral Aggregates

      Reversible “Chiral Memory” in Ruthenium Tris(phenanthroline)–Anionic Porphyrin Complexes (pages 9879–9882)

      Rosalba Randazzo, Angela Mammana, Alessandro D'Urso, Rosaria Lauceri and Roberto Purrello

      Version of Record online: 17 NOV 2008 | DOI: 10.1002/anie.200803619

      Thumbnail image of graphical abstract

      Happy memories: J aggregates (J) of the tetraanionic meso-tetrakis(4-sulfonatophenyl)porphine (H2TPPS4) gain chirality by interaction with Δ- or Λ-[Ru] (see picture, [Ru]=[Ru(1,10-phenanthroline)3]2+). After destroying and reforming the aggregates by changing the pH of the solution, the final species “remember” the initially imprinted chirality, even in the presence of an excess of the ruthenium complex with the opposite chirality to that memorized.

      Corrected by:

      Corrigendum: Reversible “Chiral Memory” in Ruthenium Tris(phenanthroline)–Anionic Porphyrin Complexes

      Vol. 48, Issue 8, 1351, Version of Record online: 2 FEB 2009

    6. Intercalative Polymerization

      Fabrication of Two-Dimensional Polymer Arrays: Template Synthesis of Polypyrrole between Redox-Active Coordination Nanoslits (pages 9883–9886)

      Nobuhiro Yanai, Takashi Uemura, Masaaki Ohba, Yu Kadowaki, Mitsuhiko Maesato, Mikihito Takenaka, Shotaro Nishitsuji, Hirokazu Hasegawa and Susumu Kitagawa

      Version of Record online: 5 NOV 2008 | DOI: 10.1002/anie.200803846

      Thumbnail image of graphical abstract

      A redox sandwich: Oxidative and intercalative polymerization of pyrrole was conducted within the nanoslits of a layered open coordination framework containing redox-active sites. The resulting polypyrrole, which can be isolated from the host framework, exists as stacked sheet polymer objects, the orientation and morphology of which are directly related to those of the original coordination-polymer template.

    7. Substitution Reactions

      Isoxazole-Assisted Direct Substitution of the Hydroxy Group in α-Ketols: Introduction of Angular Substituents in a Polycyclic System (pages 9887–9890)

      Hiroshi Takikawa, Katsuyoshi Hikita and Keisuke Suzuki

      Version of Record online: 14 NOV 2008 | DOI: 10.1002/anie.200801577

      Thumbnail image of graphical abstract

      The facile introduction of an angular substituent has become viable for the synthesis of natural products such as 2. Ketol 1 serves to achieve this through the direct substitution of its hydroxy group by a Lewis acid (see scheme). The isoxazole unit facilitates the generation of a cation at the α-position (A).

    8. Polycycles

      Synthesis, Structure, and Photophysical Properties of Highly Substituted 8,8a-Dihydrocyclopenta[a]indenes (pages 9891–9894)

      Yao-Ting Wu, Ming-Yu Kuo, Yu-Ting Chang, Chien-Chueh Shin, Tsun-Cheng Wu, Chia-Cheng Tai, Tzu-Heng Cheng and Wei-Szu Liu

      Version of Record online: 14 NOV 2008 | DOI: 10.1002/anie.200802560

      Thumbnail image of graphical abstract

      A triple round: A palladium-catalyzed cyclotrimerization of 1,2-diarylacetylenes has been developed to synthesize highly substituted 8,8a-dihydrocyclopenta[a]indenes. One such cycloadduct (1) displays unusual aggregation-induced emission with a strong blue fluorescence (see picture). The structures of the products have been confirmed by X-ray crystal analysis.

    9. Organometallic Nanowires

      Semiconducting and Electroluminescent Nanowires Self-Assembled from Organoplatinum(II) Complexes (pages 9895–9899)

      Mai-Yan Yuen, V. A. L. Roy, Wei Lu, Steven C. F. Kui, Glenna So Ming Tong, Man-Ho So, Stephen Sin-Yin Chui, Michele Muccini, J. Q. Ning, S. J. Xu and Chi-Ming Che

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200802981

      Thumbnail image of graphical abstract

      Organometallic nanowires with luminescent and current-modulating properties were self-assembled from cyclometalated/terpyridyl platinum(II) complexes with auxiliary arylisocyanide/arylacetylide ligands and incorporated into a compact organic light-emitting field-effect transistor (see picture) by solution-processable protocols. The nanowires exhibit both electron and hole mobilities of 0.1 cm2 V−1 s−1.

    10. Silica–ZnO Nanotubes

      Bubble-Templated and Flow-Controlled Synthesis of Macroscopic Silica Tubes Supporting Zinc Oxide Nanostructures (pages 9900–9903)

      Jason J. Pagano, Tamás Bánsági Jr. and Oliver Steinbock

      Version of Record online: 10 NOV 2008 | DOI: 10.1002/anie.200803203

      Thumbnail image of graphical abstract

      Macrotubes with nanostructures are formed at rates of cm s−1 when aqueous zinc sulfate is injected into a silicate solution and a gas bubble is pinned to the reaction zone. Straight, long (>10 cm), and hollow structures with diameters of 500 μm can be grown, which upon heating are luminescent, and can photodegrade rhodamine B (RhB). The presence of ZnO on the interior surface is confirmed by electron and X-ray diffraction.

    11. Nanotube Synthesis

      A Facile Way to Control the Number of Walls in Carbon Nanotubes through the Synthesis of Exposed-Core/Shell Catalyst Nanoparticles (pages 9904–9907)

      Kyung Min Choi, Saji Augustine, Jung Hoon Choi, Ju Ho Lee, Weon Ho Shin, Seong Ho Yang, Jeong Yong Lee and Jeung Ku Kang

      Version of Record online: 16 OCT 2008 | DOI: 10.1002/anie.200803311

      Thumbnail image of graphical abstract

      Wall Control: An innovative synthesis of nanotubes with precise control of the number of walls in nanotubes (see picture) makes use of exposed-core/shell structured catalyst nanoparticles, which are fabricated by consecutive plasma and chemical treatment processes after micelle patterning of metal particles.

    12. Polyoxometalates

      A Stable “End-On” Iron(III)–Hydroperoxo Complex in Water Derived from a Multi-Iron(II)-Substituted Polyoxometalate and Molecular Oxygen (pages 9908–9912)

      Delina Barats, Gregory Leitus, Ronit Popovitz-Biro, Linda J. W. Shimon and Ronny Neumann

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200803966

      Thumbnail image of graphical abstract

      Head over EELS: Reaction of O2 with a hexa-iron(II)-substituted polyoxometalate in water yields a polyoxometalate with “end-on” hydroperoxo groups, {FeIII[BOND]O2H}, at the terminal positions. The hydroperoxo moiety, stabilized by hydrogen bonding with water, is unusual for its long O[BOND]O bond and nearly linear Fe-O-O bond angle. Electron energy-loss spectroscopy (EELS) is used to determine the oxidation state of iron.

    13. Asymmetric Catalysis

      Enantioselective Enolate Protonations: Friedel–Crafts Reactions with α-Substituted Acrylates (pages 9913–9915)

      Mukund P. Sibi, Julien Coulomb and Levi M. Stanley

      Version of Record online: 17 NOV 2008 | DOI: 10.1002/anie.200804221

      Thumbnail image of graphical abstract

      Templates rule: A Zn(NTf2)2/1 catalyzed tandem Friedel–Crafts alkylation/enantioselective protonation of pyrroles with isoxazolidinone-derived α-substituted α,β-unsaturated imides, provides high levels of rotamer control and enantioselectivity in the tandem sequence, and affords pyrrole derivatives in good-to-excellent yields (68–98 %) and enantioselectivities (43–98 % ee).

    14. Amphibious Nanocrystals

      Nanocrystal Synthesis in an Amphibious Bath: Spontaneous Generation of Hydrophilic and Hydrophobic Surface Coatings (pages 9916–9921)

      Andrew M. Smith and Shuming Nie

      Version of Record online: 17 NOV 2008 | DOI: 10.1002/anie.200804179

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      Universal solubility: A variety of monodisperse nanocrystals have been synthesized in an “amphibious” reaction bath consisting of an amphiphilic multidentate ligand and low-molecular-weight polyethylene glycols (PEGs). These particles are instantly soluble in nearly all solvents and retain their characteristic optical properties after dispersion (see picture).

    15. Self-Assembly

      Tunable Fluorescent Dendron-Cyclodextrin Nanotubes for Hybridization with Metal Nanoparticles and Their Biosensory Function (pages 9922–9926)

      Chiyoung Park, Moon Sup Im, Sanghwa Lee, Jino Lim and Chulhee Kim

      Version of Record online: 10 NOV 2008 | DOI: 10.1002/anie.200804087

      Thumbnail image of graphical abstract

      Take the tube: A systematic approach was used to construct a series of functional nanotubes by cooperative self-assembly of dendrons and cyclodextrins and their nanotube–nanoparticle hybrids (see picture). The nanotubes are also capable of sensing proteins by inducing specific binding of proteins on the tube surface. The “nanotube toolkit” has a great potential for the construction of functional nanomaterials.

    16. Surface Functionalization

      Heterogeneous Catalysis through Microcontact Printing (pages 9927–9932)

      Jason M. Spruell, Bonnie A. Sheriff, Dorota I. Rozkiewicz, William R. Dichtel, Rosemary D. Rohde, David N. Reinhoudt, J. Fraser Stoddart and James R. Heath

      Version of Record online: 14 NOV 2008 | DOI: 10.1002/anie.200803480

      Thumbnail image of graphical abstract

      Minting a Stamp: The preparation of copper metal-coated elastomeric stamps and their use in catalyzing the Cu-catalyzed azide–alkyne cycloaddition reaction heterogeneously through microcontact printing is described (see scheme). This StampCat process is compared to other conventional surface-functionalization techniques, including traditional microcontact printing and solution–surface-based reactions.

    17. Quintuple Bonds

      Quintuply-Bonded Dichromium(I) Complexes Featuring Metal–Metal Bond Lengths of 1.74 Å (pages 9933–9936)

      Chia-Wei Hsu, Jen-Shiang K. Yu, Chun-Hsu Yen, Gene-Hsiang Lee, Yu Wang and Yi-Chou Tsai

      Version of Record online: 17 NOV 2008 | DOI: 10.1002/anie.200803859

      Thumbnail image of graphical abstract

      Closer than most: A series of four dichromium bis(amidinate) complexes of the type [Cr2{μ-η2-ArNC(R)NAr}2] display an extremely short metal–metal bond of 1.74 Å, independent of the steric hindrance of the ligands. DFT calculations of Cr[BOND]Cr bond lengths agree well with the experimental values and computational analysis of their electronic structures indicates quintuple bonding between the two Cr centers.

    18. Metal–Metal Interactions

      Breaking the 1.80 Å Barrier of the Cr[BOND]Cr Multiple Bond Between CrII Atoms (pages 9937–9940)

      Steven Horvath, Serge I. Gorelsky, Sandro Gambarotta and Ilia Korobkov

      Version of Record online: 10 NOV 2008 | DOI: 10.1002/anie.200804048

      Thumbnail image of graphical abstract

      Short and sweet: By replacing one of the two guanidinate ligands in the monomeric complex [{(Me3Si)2NC(NCy)2}2Cr] with a methyl group, the dimeric complex [{(Me3Si)2NC(NCy)2CrMe}2] (see picture) is generated. This species contains the shortest reported Cr[BOND]Cr quadruple bond. The bonding of the methyl group indicates a Cr–H[BOND]CH2Cr bridging agostic interaction which likely contributes to the short Cr–Cr contact.

    19. C[BOND]H Activation

      C[BOND]H Bond Activation by [{(Diimine)Pd(μ-OH)}2]2+ Dimers: Mechanism-Guided Catalytic Improvement (pages 9941–9943)

      John E. Bercaw, Nilay Hazari, Jay A. Labinger and Paul F. Oblad

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200804455

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      Clearly different: The mechanism of C[BOND]H activation by air- and water-tolerant complexes of the type [{(diimine)Pd(μ-OH)}2]2+ (see scheme; Ar=tBu2C6H3, solv=MeOH or trifluoroethanol) and [(diimine)Pd(OH2)2]2+ has been investigated. Surprisingly, there are significant mechanistic differences in activation by the dimeric Pd complex and the analogous Pt species, with the Pd species found to be considerably more reactive.

    20. Organometallic Chemistry

      An ansa-Heteroborabenzene Divalent Lanthanide Amide through C[BOND]H Bond Cleavage (pages 9944–9947)

      Peng Cui, Yaofeng Chen, Guangyu Li and Wei Xia

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200803581

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      Bridging is the ansa: Both neutral borabenzene and anionic boratabenzene coordinate to a lanthanide ion in an ansa-borabenzene divalent lanthanide amide (see picture). The complex, which was synthesized through an unexpected C[BOND]H bond cleavage, displays notable structural features, and is potentially reactive, as demonstrated by the insertion reaction of a carbodiimide into the metal–nitrogen bond.

    21. Hydrogen Formation

      Cobalt Clathrochelate Complexes as Hydrogen-Producing Catalysts (pages 9948–9950)

      Olivier Pantani, Subhendu Naskar, Régis Guillot, Pierre Millet, Elodie Anxolabéhère-Mallart and Ally Aukauloo

      Version of Record online: 13 NOV 2008 | DOI: 10.1002/anie.200803643

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      Wrapper's delight: Clathrochelate complexes, in which the metal center is wrapped in a close-knit macrobicyclic ligand, are often considered to be deprived of chemical reactivity. Boron-capped cobalt tris(glyoximato) complexes show catalytic activity in the reduction of acids in acetonitrile at potentials as small as −0.5 V versus SCE. Alteration of ligand substituents allows for the tuning of their electrochemical reactivity (see structure: red ball Co, grey C, purple B, blue N, red O, green X).

    22. Microcontact Printing

      Topographically Flat, Chemically Patterned PDMS Stamps Made by Dip-Pen Nanolithography (pages 9951–9954)

      Zijian Zheng, Jae-Won Jang, Gengfeng Zheng and Chad A. Mirkin

      Version of Record online: 14 NOV 2008 | DOI: 10.1002/anie.200803834

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      DPN benefits μCP: The intrinsic drawbacks in conventional microcontact printing, that is, roof collapse and lateral ink diffusion, were addressed by using topographically flat, chemically patterned PDMS stamps made by dip-pen nanolithography. The chemically patterned flat stamps were used for contact printing of various inks including thiols, proteins and hydrophilic dyes. The as-made features can reach sub-100 nm resolution and a very low filling factor (see AFM picture).

    23. Carbon Dioxide Fixation

      Insertion of Carbon Dioxide into Main-Group Complexes: Formation of the [N(CO2)3]3− Ligand (pages 9955–9957)

      Diane A. Dickie, Marie V. Parkes and Richard A. Kemp

      Version of Record online: 20 OCT 2008 | DOI: 10.1002/anie.200804218

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      Under mild conditions CO2 reacts with [Sr{N(PPh2)2}2](THF)3 to oxidatively cleave PPh2 groups, resulting in the new ligand [N(CO2)3]3− in [Sr6{O2CN(PPh2)2}6{N(CO2)3}2] (see core structure; Sr green, O red, N blue, C black). The Sr6 framework chemically fixates twelve equivalents of CO2, half by the formation of two [N(CO2)3]3− ligands and the other half by CO2 insertion to form the unprecedented phosphanyl-substituted carbamate ligand O2CN(PPh2)2.

    24. Synthetic Methods

      Asymmetric Synthesis of α-Alkylated Aldehydes using Terminal Epoxide-Derived Chiral Enamines (pages 9958–9960)

      David M. Hodgson and Naeem S. Kaka

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200804369

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      Effective discrimination: Efficient lithium amide-induced terminal epoxide–enamine transformation provides the first enamines capable of generating α-alkylated aldehydes with high asymmetric induction by intermolecular nucleophilic substitution (see scheme).

    25. Copper–Nitrene Complexes in Catalytic C[BOND]H Amination (pages 9961–9964)

      Yosra M. Badiei, Adriana Dinescu, Xuliang Dai, Robert M. Palomino, Frank W. Heinemann, Thomas R. Cundari and Timothy H. Warren

      Version of Record online: 17 NOV 2008 | DOI: 10.1002/anie.200804304

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      Hydrocarbons activate! Isolable β-diketiminato dicopper–nitrene complexes such as 1 derived from the reaction of [{(Cl2NN)Cu}2(μ-benzene)] and 1-adamantylazide are potent towards nitrene insertion into unactivated sp3-hybridized C[BOND]H bonds. 1 allows stoichiometric and catalytic intermolecular C[BOND]H amination of hydrocarbons to give secondary amines (see scheme). Catalyst loadings as low as 0.05 mol % may be used.

    26. Systems Chemistry

      A Simple Synthetic Replicator Amplifies Itself from a Dynamic Reagent Pool (pages 9965–9970)

      Jan W. Sadownik and Douglas Philp

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200804223

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      The fate of a dynamic combinatorial library is determined by coupling the exchange processes to a synthetic replicator. The replicating template is capable of exploiting and dominating the exchanging pool of reagents in order to amplify its own formation at the expense of other species (see picture) through the non-linear kinetics inherent in minimal replication.

    27. Asymmetric Catalysis

      Organocatalytic Asymmetric Inverse-Electron-Demand Aza-Diels–Alder Reaction of N-Sulfonyl-1-aza-1,3-butadienes and Aldehydes (pages 9971–9974)

      Bo Han, Jun-Long Li, Chao Ma, Shan-Jun Zhang and Ying-Chun Chen

      Version of Record online: 20 OCT 2008 | DOI: 10.1002/anie.200804183

      Thumbnail image of graphical abstract

      Water is crucial for high transformation efficiency in the title reaction catalyzed by the α,α-diphenylprolinol derivative 1. Excellent stereoselectivities were observed for a broad spectrum of substrates (see scheme; TMS=trimethylsilyl, Tos=p-toluenesulfonyl). A diverse range of chiral piperidine derivatives and other valuable compounds can be prepared from the hemiaminal products.

    28. Photocatalysis

      The Nature of Nitrogen-Modified Titanium Dioxide Photocatalysts Active in Visible Light (pages 9975–9978)

      Dariusz Mitoraj and Horst Kisch

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200800304

      Thumbnail image of graphical abstract

      Can you see the light? Calcining a mixture of urea and TiO2 produces amino-tri-s-triazine derivatives covalently attached to TiO2 (see scheme). Therefore, the photocatalytic activity of this material in the visible range does not originate from surface defects or the presence of nitridic, amidic, or oxide species. This dye-sensitized titania efficiently photocatalyzes the oxidation of HCOOH to CO2 and H2O.

    29. Ansa Complexes

      Intramolecular Activation of a Disila[2]molybdenocenophanedihydride: Synthesis and Structure of a [1],[1]Metalloarenophane (pages 9979–9981)

      Holger Braunschweig, Manuela Gross, Krzysztof Radacki and Christian Rothgaengel

      Version of Record online: 14 NOV 2008 | DOI: 10.1002/anie.200803223

      Thumbnail image of graphical abstract

      Breaking bridges: Disila[2]molybdenocenophanedihydride was synthesized by dilithiation of 1,2-bis(cyclopentadienyl)tetramethyldisilane and subsequent reaction with MoCl5 in the presence of NaBH4. The photochemical conversion of the ansa complex leads to a highly unusual, twofold bridged [1],[1]molybdenocenophane (see scheme; C black, H white, Si pink, Mo violet).

    30. Main-Group Chemistry

      Well-Defined Stibonic and Tellurinic Acids (pages 9982–9984)

      Jens Beckmann, Pamela Finke, Malte Hesse and Burkhard Wettig

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200803997

      Thumbnail image of graphical abstract

      Upon going from the 4th to the 5th period a qualitative change in the molecular structures of pnictogenic and chalcogenic acids takes place. Unlike the lighter monomeric Group 15 and 16 congeners, the depicted stibonic and tellurinic acids adopt μ2-oxo-bridged dinuclear structures featuring Sb and Te atoms with trigonal-bipyramidal coordination. DFT calculations on the model compounds give dissociation energies of the dimers.

    31. Asymmetric Catalysis

      Proline-Catalyzed Highly Enantioselective and anti-Selective Mannich Reaction of Unactivated Ketones: Synthesis of Chiral α-Amino Acids (pages 9985–9988)

      Björn T. Hahn, Roland Fröhlich, Klaus Harms and Frank Glorius

      Version of Record online: 12 NOV 2008 | DOI: 10.1002/anie.200803515

      Thumbnail image of graphical abstract

      Universal L-proline: The title reaction complements well-known syn-selective Mannich reactions. The Mannich products can be converted readily into the free amino acids by hydrogenolytic deprotection under mild conditions (see scheme). DMSO=dimethyl sulfoxide; R1=alkyl, OH; R2=alkyl.

    32. Ionization Techniques

      A Universal Ionization Label for the APLI-(TOF)MS Analysis of Small Molecules and Polymers (pages 9989–9992)

      Ralf Schiewek, René Mönnikes, Volker Wulf, Siegmar Gäb, Klaus Josef Brockmann, Thorsten Benter and Oliver Johannes Schmitz

      Version of Record online: 13 NOV 2008 | DOI: 10.1002/anie.200804106

      Thumbnail image of graphical abstract

      APLI application: Small molecules and polymers can be analyzed quantitatively by using atmospheric-pressure laser ionization (APLI) coupled to time-of-flight mass spectrometry. This is realized by a derivatization strategy that facilitates selective ionization of polar and non-polar compounds in complex matrices without hyphenated techniques or stable-isotope-labeled standards.

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