Angewandte Chemie International Edition

Cover image for Vol. 50 Issue 11

March 7, 2011

Volume 50, Issue 11

Pages 2407–2648

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Cover Picture: Graphene Nanoribbons by Chemists: Nanometer-Sized, Soluble, and Defect-Free (Angew. Chem. Int. Ed. 11/2011) (page 2407)

      Dipl.-Chem. Lukas Dössel, Dipl.-Chem. Lileta Gherghel, Dr. Xinliang Feng and Prof. Dr. Klaus Müllen

      Article first published online: 20 JAN 2011 | DOI: 10.1002/anie.201007922

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      Ironing with iron(III) chloride: A bottom-up organic synthesis in solution to synthesize defect-free graphene ribbons that cannot be obtained by top-down methods such as lithography or unzipping of carbon nanotubes is described by K. Müllen and co-workers in their Communication on page 2540 ff. Three-dimensional polyphenylene precursors with a unique kinked backbone enable full planarization into a rigid ribbon in a single reaction step. This cyclodehydrogenation is achieved by an intramolecular Scholl reaction with FeCl3.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Inside Cover: Three-Dimensional Chemical Patterns for Cellular Self-Organization (Angew. Chem. Int. Ed. 11/2011) (page 2408)

      Dr. Yevgeniy V. Kalinin, Jatinder S. Randhawa and Prof. David H. Gracias

      Article first published online: 15 FEB 2011 | DOI: 10.1002/anie.201100533

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      Three-dimensional chemical scaffolds are achieved by the diffusion of chemicals through precisely patterned polyhedral containers. In their Communication on page 2549 ff., D. H Gracias et al. describe strategies to control the chemical release and consequently demonstrate chemotactic self-assembly of living cells (E. coli) to express green fluorescent protein in helical patterns. (Graphics: M. Rietveld and A. Zarafshar.)

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Graphical Abstract: Angew. Chem. Int. Ed. 11/2011 (pages 2411–2423)

      Article first published online: 2 MAR 2011 | DOI: 10.1002/anie.201190018

  4. News

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Zhaomin Hou (page 2430)

      Article first published online: 22 FEB 2011 | DOI: 10.1002/anie.201007334

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      “When I wake up I do some simple stretching exercises for a little while before having breakfast. A good work day begins with a ‘good morning’ …” This and more about Zhaomin Hou can be found on page 2430.

  6. Obituary

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Dudley Williams (pages 2431–2432)

      Prof. Jeremy K. M. Sanders

      Article first published online: 10 FEB 2011 | DOI: 10.1002/anie.201100049

  7. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. C[BOND]H Activation. Topics in Current Chemistry, Volume 292. Edited by Jin-Quan Yu and Zhangjie Shi. (page 2433)

      Rubén Martín Romo

      Article first published online: 2 FEB 2011 | DOI: 10.1002/anie.201008057

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      Springer, 2010. 380 pp., hardcover, € 245.03.—ISBN 978-3642123559

  8. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. [2+2+2] Cycloaddition

      Metal-Free Cyclotrimerization for the De Novo Synthesis of Pyridines (pages 2434–2435)

      Karolin Kral and Dr. Marko Hapke

      Article first published online: 1 MAR 2011 | DOI: 10.1002/anie.201007647

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      Two routes, one destination: The metal-free, uncatalyzed [2+2+2] cycloaddition of cyanodiynes can proceed through two different reaction cascades, both yielding pyridines as products (see scheme). The unactivated cyano group can act either as an enophile in Alder–ene or as a dienophile in hetero-Diels–Alder reactions—both of which are rather uncommon for this well-known functional group.

    2. Porphyrinoids

      How Should Aromaticity Be Described in Porphyrinoids? (pages 2436–2438)

      Prof. Dr. Martin Bröring

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201007442

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      Porphyrins really are the [18]annulenes of nature”—This is the title of a report dealing with a new macrocycle (see structure; gray C, white H, blue N), which can be considered as either a porphyrin or an [18]annulene. The spectroscopic data prove the aromatic and porphyrinoid character of the new compound, and support the simple concept of a (4n+2)π main conjugation pathway as a key criterion for porphyrinoid Hückel aromaticity.

    3. Chlorophyll

      A New Factor in Life’s Quest for Energy (pages 2439–2441)

      Prof. Dr. Bernhard Kräutler

      Article first published online: 22 FEB 2011 | DOI: 10.1002/anie.201007339

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      A bacterium sees red: Chlorophyll f (Chl f), a tetrapyrrole displaying unprecedented red-shifted absorption bands, was discovered in cyanobacteria and its structure was deduced by spectroscopic means. The new chromophore of Chl f is likely a result of biological adaptation and biochemical optimization in bacteria in their struggle for survival. It is a sign of life's constant demand for energy obtained from sunlight through photosynthesis.

  9. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Enzyme Inhibitors

      From Conventional to Unusual Enzyme Inhibitor Scaffolds: The Quest for Target Specificity (pages 2442–2448)

      Prof. Dr. Eric Meggers

      Article first published online: 15 FEB 2011 | DOI: 10.1002/anie.201005673

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      Creativity in demand: Enzyme inhibitor scaffolds ranging from typical small organic molecules to inorganic clusters and even to polymers demonstrate that the whole repertoire of organic, inorganic, and macromolecular chemistry can be used to meet the challenge of specific molecular recognition in complex biological systems.

  10. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Directed Reactions

      Removable Directing Groups in Organic Synthesis and Catalysis (pages 2450–2494)

      Dr. Géraldine Rousseau and Prof. Dr. Bernhard Breit

      Article first published online: 1 MAR 2011 | DOI: 10.1002/anie.201006139

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      Controlling the outcome: Directing groups have been widely used in recent years to control chemical reactions. In cases when the existing functional group within a substrate is unsuited to achieve an efficient intramolecular reagent/catalyst delivery, the specific introduction of an appropriately designed removable reagent-directing group can be used to address this problem (see scheme).

      Corrected by:

      Corrigendum: Corrigendum: Removable Directing Groups in Organic Synthesis and Catalysis

      Vol. 50, Issue 22, 5007, Article first published online: 16 MAY 2011

  11. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Biosensors

      Single-Molecule Detection of Proteins Using Aptamer-Functionalized Molecular Electronic Devices (pages 2496–2502)

      Song Liu, Xinyue Zhang, Wangxi Luo, Zhenxing Wang, Prof. Xuefeng Guo, Dr. Michael L. Steigerwald and Prof. Xiaohong Fang

      Article first published online: 21 FEB 2011 | DOI: 10.1002/anie.201006469

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      Filling in the gap: Label-free, real-time electrical detection of proteins is achieved with high selectivity and real single-molecule sensitivity by using aptamer-functionalized molecular electronic devices with single-walled carbon nanotubes as point contacts.

    2. Mass Spectrometry

      Synchronized Inductive Desorption Electrospray Ionization Mass Spectrometry (pages 2503–2506)

      Guangming Huang, Guangtao Li, Jason Ducan, Zheng Ouyang and Prof.  R. Graham Cooks

      Article first published online: 18 FEB 2011 | DOI: 10.1002/anie.201007819

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      Well-orchestrated: A new mass spectrometry protocol (see picture) synchronizes microdroplet creation, nebulizing gas pulsing, and DAPI interface opening. A number of advances result: 100-fold improved detection limit, simultaneous positive and negative ion spectra, and decreased spray volumes in desorption electrospray ionization (DESI).

    3. Catenanes

      Chloride Anion Templated Synthesis and Crystal Structure of a Handcuff Catenane (pages 2507–2510)

      Nicholas H. Evans, Dr. Christopher J. Serpell and Prof. Paul D. Beer

      Article first published online: 14 FEB 2011 | DOI: 10.1002/anie.201007741

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      Chloride, you're nicked! A novel handcuff catenane was prepared by anion templation and π–π stacking interactions. In addition, the first crystal structure determination of such a catenane is reported (see picture).

    4. Natural Product Synthesis

      Synthesis and Biological Evaluation of ABCD Ring Fragments of the Kibdelones (pages 2511–2515)

      David L. Sloman, Branko Mitasev, Stephen S. Scully, Dr. John A. Beutler and Prof. John A. Porco Jr.

      Article first published online: 18 FEB 2011 | DOI: 10.1002/anie.201007613

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      Arylation goes platinum: The synthesis of the ABCD ring fragments of the kibdelones has been achieved through a novel PtIV-catalyzed arylation of a quinone monoketal followed by photocyclization (see scheme). Biological evaluation in the NCI 60-cell screen revealed that the kibdelone ABCD ring analogues were about 2000 times less active than kibdelones B and C, suggesting that the tetrahydroxanthone structure of the kibdelones is crucial for cytotoxicity.

    5. Supramolecular Chemistry

      Self-Assembled Polymeric Supramolecular Frameworks (pages 2516–2520)

      Dr. Nikolay Houbenov, Johannes S. Haataja, Dr. Hermis Iatrou, Prof. Nikos Hadjichristidis, Prof. Janne Ruokolainen, Dr. Charl F. J. Faul and Prof. Olli Ikkala

      Article first published online: 14 FEB 2011 | DOI: 10.1002/anie.201007185

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      Within the framework: Ionic complexation of diblock copolypeptide poly(γ-benzyl-L-glutamate)-block-poly(L-lysine) (PBLG-b-PLL) with 2′-deoxyguanosine 5′-monophosphate (dGMP, gray) generates a polymeric supramolecular framework solid with self-assembled cages based on two orthogonal shape-persistent motifs: PBLG α helices (blue) and PLL β sheets (red), which in turn are held together by shape-persistent hydrogen-bonded G-ribbons.

    6. Polyoxometalates

      A Double-Tailed Fluorescent Surfactant with a Hexavanadate Cluster as the Head Group (pages 2521–2525)

      Panchao Yin, Pingfan Wu, Dr. Zicheng Xiao, Dong Li, Emily Bitterlich, Dr. Jin Zhang, Peng Cheng, Prof. Dmitri V. Vezenov, Prof. Tianbo Liu and Prof. Yongge Wei

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201006144

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      Blue rinse: A hybrid surfactant that comprises a hexavanadate cluster and two C18 alkyl chains shows unexpected blue luminescence (see picture). The luminescence arises from the interaction between the counterions and the hexavanadate clusters, and varies with the type of counterions. This behavior was confirmed by studying the self-assembly of the hybrids with various counterions in different solvents.

    7. Solid Electrolytes

      LiZnSO4F Made in an Ionic Liquid: A Ceramic Electrolyte Composite for Solid-State Lithium Batteries (pages 2526–2531)

      Dr. Prabeer Barpanda, Dr. Jean-Noël Chotard, Dr. Charles Delacourt, Marine Reynaud, Dr. Yaroslav Filinchuk, Prof. Michel Armand, Dr. Michael Deschamps and Prof. Jean-Marie Tarascon

      Article first published online: 18 JAN 2011 | DOI: 10.1002/anie.201006331

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      Wrapped in IL: Solid electrolytes are key for safer lithium batteries. The novel LiZnSO4F fluorosulfate prepared by an ionic-liquid-assisted synthesis delivers high ionic conductivity at room temperature (see picture). The lithium-containing ionic-liquid layer tailors the ionic conductivity of inorganic composites by a surface effect. This finding can be useful in designing solid electrolytes with high ionic conductivity.

    8. Amyloid β Peptides

      Rapid Formation of a Preoligomeric Peptide–Metal–Peptide Complex Following Copper(II) Binding to Amyloid β Peptides (pages 2532–2535)

      Jeppe T. Pedersen, Prof. Kaare Teilum, MD DSc Niels H. H. Heegaard, Prof. Jesper Østergaard, Prof. Hans-Werner Adolph and Prof. Lars Hemmingsen

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201006335

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      CuIIconnects peptides: The mechanism of binding of CuII to amyloid β peptides (Aβ) implicated in Alzheimer's disease was elucidated by stopped-flow spectroscopy, NMR relaxation, and simulation of the kinetics on the millisecond timescale. Two monomeric Cu–Aβ species and a dimeric Aβ–Cu–Aβ species were identified (see picture). Aberrant aggregation apparently occurs from the monomeric species.

    9. 3D Covalent Arrays

      Three-Dimensional Covalent Co-Assembly between Inorganic Supertetrahedral Clusters and Imidazolates (pages 2536–2539)

      Tao Wu, Ripsime Khazhakyan, Le Wang, Prof. Xianhui Bu, Dr. Shou-Tian Zheng, Victoria Chau and Prof. Pingyun Feng

      Article first published online: 23 FEB 2011 | DOI: 10.1002/anie.201006531

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      An unlikely marriage between chalcogenide clusters and imidazolates leads to a family of 3D covalent arrays of supertetrahedral chalcogenide clusters and imidazolate ligands (see picture). These are the first examples of supertetrahedral clusters being assembled with anionic ligands.

    10. Nanoribbon Synthesis

      Graphene Nanoribbons by Chemists: Nanometer-Sized, Soluble, and Defect-Free (pages 2540–2543)

      Dipl.-Chem. Lukas Dössel, Dipl.-Chem. Lileta Gherghel, Dr. Xinliang Feng and Prof. Dr. Klaus Müllen

      Article first published online: 12 JAN 2011 | DOI: 10.1002/anie.201006593

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      Closing the zipper: A method for the bottom-up organic synthesis of defect-free graphene nanoribbons in solution has been developed. Polyphenylene precursors with a unique kinked backbone enabled full cyclodehydrogenation in a single reaction step by an intramolecular Scholl reaction with FeCl3 (see scheme).

    11. Diazo Cross-Coupling

      Rhodium(II)-Catalyzed Cross-Coupling of Diazo Compounds (pages 2544–2548)

      Jørn H. Hansen, Brendan T. Parr, Dr. Philip Pelphrey, Dr. Quihui Jin, Dr. Jochen Autschbach and Prof. Huw M. L. Davies

      Article first published online: 14 FEB 2011 | DOI: 10.1002/anie.201004923

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      Nothing left to chance: A convenient protocol for selective cross-coupling of diazo compounds for the convergent synthesis of alkenes was developed (see scheme; EDG=aryl, heteroaryl, vinyl; R=O-alkyl, aryl). The selectivity control elements were identified by ReactIR and DFT calculations and provide a framework for the design of viable diazo coupling reactions.

    12. 3D Chemical Scaffolds

      Three-Dimensional Chemical Patterns for Cellular Self-Organization (pages 2549–2553)

      Dr. Yevgeniy V. Kalinin, Jatinder S. Randhawa and Prof. David H. Gracias

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201007107

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      Falling into line: A method for the precise generation of durable 3D chemical patterns within stationary media was used to direct the chemotactic self-organization of living cells. A container with carefully positioned slits, through which a chemoattractant (yellow) can diffuse, controls the self-organization of Escherichia coli cells (green ellipsoids) expressing green fluorescent protein into a helical pattern (see fluorescence images).

    13. DNA Recognition

      Specific Blocking of CREB/DNA Binding by Cyclometalated Platinum(II) Complexes (pages 2554–2558)

      Ping Wang, Dr. Chung-Hang Leung, Dr. Dik-Lung Ma, Dr. Raymond Wai-Yin Sun, Dr. Siu-Cheong Yan, Dr. Qing-Shou Chen and Prof. Dr. Chi-Ming Che

      Article first published online: 18 FEB 2011 | DOI: 10.1002/anie.201006887

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      In the groove: The unique major-groove-binding properties of a PtII complex can be used to block the interaction between the transcription factor CREB and DNA (see picture). Variation of the ligands around the PtII center changes the DNA binding mode and results in specific gene regulators with superior potency and selectivity.

    14. Fluorinated Sulfonates

      From Difluoromethyl 2-Pyridyl Sulfone to Difluorinated Sulfonates: A Protocol for Nucleophilic Difluoro(sulfonato)methylation (pages 2559–2563)

      Prof. Dr. G. K. Surya Prakash, Dr. Chuanfa Ni, Fang Wang, Prof. Dr. Jinbo Hu and Prof. Dr. George A. Olah

      Article first published online: 18 FEB 2011 | DOI: 10.1002/anie.201007594

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      An efficient method for the synthesis of alkyl α,α-difluorosulfonates has been developed. The selection of the 2-pyridyl group as the aryl substitute on the sulfone is critically important for the success of this transformation (see scheme). The synthetic application of fluorinated sulfones is extended and a unique solution is provided for a long-standing challenge in nucleophilic difluoro(sulfonato)methylation reactions.

    15. Deuterium Isotope Effects

      On the Origin of Conformational Kinetic Isotope Effects (pages 2564–2567)

      Prof. Daniel J. O'Leary, Prof. Paul R. Rablen and Prof. Matthew P. Meyer

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201007322

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      Neatly dissected: The computed conformational kinetic isotope effects (KIEs) for biphenyls 1 and 2 (X=D or H) are in good agreement with experimental values and have been partitioned according to the Bigeleisen–Mayer and ΔHS approaches. In [D8]-1 the KIE is dominated by a normal entropic contribution which overshadows an enthalpic contribution determined by Hvib and not HZPE. The inverse isotope effect in [D6]-2 is governed by an enthalpic zero-point energy term (HZPE) working against a normal entropic contribution.

    16. Magnetic Superhalogens

      Manganese-Based Magnetic Superhalogens (pages 2568–2572)

      Miao Miao Wu, Haopeng Wang, Yeon Jae Ko, Prof. Qian Wang, Prof. Qiang Sun, Prof. Boggavarapu Kiran, Prof. Anil K. Kandalam, Prof. Kit H. Bowen and Prof. Puru Jena

      Article first published online: 10 FEB 2011 | DOI: 10.1002/anie.201007205

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      Magnetic superoxidizers: A series of magnetic superhalogens formed of (MnxCl2x+1) units has been discovered (see picture; Mn violet, Cl green). The series was characterized by photoelectron spectroscopy, mass spectrometry, and theoretical studies.

    17. Asymmetric Catalysis

      Catalytic Asymmetric Addition of Alkyl Enol Ethers to 1,2-Dicarbonyl Compounds: Highly Enantioselective Synthesis of Substituted 3-Alkyl-3-Hydroxyoxindoles (pages 2573–2577)

      Ke Zheng, Chengkai Yin, Dr. Xiaohua Liu, Dr. Lili Lin and Prof. Dr. Xiaoming Feng

      Article first published online: 14 FEB 2011 | DOI: 10.1002/anie.201007145

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      A familiar ring: An efficient catalytic asymmetric hetero-ene reaction of 1,2-dicarbonyl compounds (including isatins, α-ketoesters, and glyoxal derivatives) is described. The catalyst system derived from 1 can be used for a broad substrate scope and the corresponding products were obtained in good yield and excellent enantioselectivity. M.S.=molecular sieves.

    18. CO2 Activation

      Highly Regio- and Stereoselective Three-Component Nickel-Catalyzed syn-Hydrocarboxylation of Alkynes with Diethyl Zinc and Carbon Dioxide (pages 2578–2582)

      Suhua Li, Weiming Yuan and Prof. Dr. Shengming Ma

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201007128

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      Hydrocarboxylation of alkynes: The first example of nickel-catalyzed hydrozincation of alkynes that form stereodefined hydrocarboxylation products is presented (see scheme; cod=cycloocta-1,5-diene). This catalytic system is efficient for the activation of CO2 and the three-component reaction produces products that could be converted into important oxindole or γ-butyrolactam derivatives.

    19. Gold Catalysis

      Gold(I)-Catalyzed Cycloisomerization of 1,6-Diynes: Synthesis of 2,3-Disubstituted 3-Pyrroline Derivatives (pages 2583–2587)

      Di-Han Zhang, Liang-Feng Yao, Yin Wei and Prof. Min Shi

      Article first published online: 15 FEB 2011 | DOI: 10.1002/anie.201006969

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      A novel synthetic protocol for the preparation of the title compounds has been developed from a gold-catalyzed cycloisomerization of 1,6-diynes containing propargylic ester and arene–yne units. The corresponding nitrogen-containing five-membered heterocyclic compounds have been obtained in moderate to good yields (see scheme; DCE=1,2-dichloroethane, Tf=triflate). A plausible reaction mechanism has been proposed on the basis of deuterium labeling experiments.

    20. Fluoromethylation

      Nucleophilic Fluoromethylation of Aldehydes with Fluorobis(phenylsulfonyl)methane: The Importance of Strong Li–O Coordination and Fluorine Substitution for C[BOND]C Bond Formation (pages 2588–2592)

      Xiao Shen, Laijun Zhang, Yanchuan Zhao, Lingui Zhu, Guangyu Li and Prof. Dr. Jinbo Hu

      Article first published online: 15 FEB 2011 | DOI: 10.1002/anie.201006931

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      The tighter, the better! Fluorobis(phenylsulfonyl)methane reacts readily with aldehydes to give addition products in excellent yields (see scheme; LiHMDS=lithium hexamethyldisilazide), which is in sharp contrast to previous findings. Both strong Li–O coordination at low temperature and fluorine substitution play important roles in successful C[BOND]C bond formation.

    21. Asymmetric Synthesis

      A Catalytic Asymmetric Chlorocyclization of Unsaturated Amides (pages 2593–2596)

      Arvind Jaganathan, Atefeh Garzan, Dr.  Daniel C. Whitehead, Dr.  Richard J. Staples and Prof.  Babak Borhan

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201006910

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      The asymmetric chlorocyclization of unsaturated amides catalyzed by (DHQD)2PHAL yields oxazoline and dihydrooxazine derivatives (see scheme). The reaction is operationally simple and employs 1–2 mol % of the commercially available (DHQD)2PHAL (hydroquinidine 1,4-phthalazinediyl diether) catalyst. Different substitution patterns of the olefin as well as aromatic and aliphatic olefin substituents are well tolerated. DCDPH=N,N-dichloro-5,5-diphenylhydantoin.

    22. Drug Delivery

      Biodegradable Nanoparticles Composed Entirely of Safe Materials that Rapidly Penetrate Human Mucus (pages 2597–2600)

      Ming Yang, Dr. Samuel K. Lai, Ying-Ying Wang, Weixi Zhong, Christina Happe, Michael Zhang, Dr. Jie Fu and Prof. Dr. Justin Hanes

      Article first published online: 18 FEB 2011 | DOI: 10.1002/anie.201006849

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      Slipping through: Pluronic molecules adsorb onto nanoparticle surfaces through their polypropylene oxide (PPO) segments with the flanking polyethylene glycol (PEG) segments forming a dense muco-inert brush (see picture; top). While uncoated particles are immobilized in mucus through adhesive interactions with mucus mesh elements, coated particles diffuse rapidly through spaces in the mucus mesh (bottom).

    23. Polymer-Encased Nanoparticles

      Stabilization of Virus-like Particles with Poly(2-oxazoline)s (pages 2601–2605)

      Dr. Florian Manzenrieder, Dr. Robert Luxenhofer, Dr. Marco Retzlaff, Prof. Rainer Jordan and Prof. M. G. Finn

      Article first published online: 20 JAN 2011 | DOI: 10.1002/anie.201006134

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      Wrap it up! Highly efficient copper-catalyzed click chemistry can cover virus-like particles with functionalized poly(2-oxazoline) chains without interparticle aggregation. The resulting core–shell structures are significantly more temperature-stable than the native protein particles.

    24. Antitumor Agents

      Selective Treatment of Hypoxic Tumor Cells In Vivo: Phosphate Pre-Prodrugs of Nitro Analogues of the Duocarmycins (pages 2606–2609)

      Dr. Moana Tercel, Graham J. Atwell, Dr. Shangjin Yang, Dr. Amir Ashoorzadeh, Dr. Ralph J. Stevenson, K. Jane Botting, Dr. Yongchuan Gu, Sunali Y. Mehta, Prof. William A. Denny, Prof. William R. Wilson and Dr. Frederik B. Pruijn

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201004456

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      Hitting the hypoxic target: Combining a nitro prodrug with a water-soluble phosphate converts duocarmycin analogues from highly toxic DNA-alkylating agents to highly selective antitumor compounds. These prodrugs (see scheme) have outstanding activity against hypoxic tumor cells in vivo, cells which are usually considered the most resistant to conventional therapy.

    25. Synthetic Methods

      Rapid Total Syntheses Utilizing “Supersilyl” Chemistry (pages 2610–2612)

      Dr. Brian J. Albert, Dr. Yousuke Yamaoka and Prof. Dr. Hisashi Yamamoto

      Article first published online: 8 FEB 2011 | DOI: 10.1002/anie.201007210

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      In short order: The shortest total syntheses of natural product EBC-23 (see scheme, PMB=para-methoxybenzyl, TMS=trimethylsilyl) and a polymethoxy-1-alkene to date have been accomplished in just ten total steps each from commercially available chemicals. The syntheses took advantage of highly diastereoselective supersilyl-directed cascade polyaldol reactions.

    26. Catalytic Fluorination

      Palladium-Catalyzed Allylic Fluorination (pages 2613–2617)

      Charlotte Hollingworth, Dr. Amaruka Hazari, Matthew N. Hopkinson, Dr. Matthew Tredwell, Elena Benedetto, Dr. Mickael Huiban, Prof. Antony D. Gee, Dr. John M. Brown and Prof. Véronique Gouverneur

      Article first published online: 8 FEB 2011 | DOI: 10.1002/anie.201007307

      Thumbnail image of graphical abstract

      Mild and rapid: The title reaction is presented and its applicability to 18F radiolabeling is demonstrated (see scheme; TBAF=tetra-n-butylammonium fluoride, THF=tetrahydrofuran, dba=dibenzylideneacetone). The use of p-nitrobenzoate as the leaving group is significant to the success of this catalytic organometallic fluorination process. A range of allylic fluorides were synthesized by this method.

    27. Natural Product Synthesis

      Total Synthesis of Aspergillide A and B Based on the Transannular Oxy-Michael Reaction (pages 2618–2620)

      Makoto Kanematsu, Dr. Masahiro Yoshida and Prof. Dr. Kozo Shishido

      Article first published online: 15 FEB 2011 | DOI: 10.1002/anie.201007327

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      Keys to the kingdom: A highly efficient and diastereoselective transannular oxy-Michael reaction for the construction of the syn- and anti-tetrahydropyran units from a common 14-membered macrolactone is the key step for the total synthesis of aspergillide A and B (see scheme; CM=cross-metathesis, HWE=Horner–Wadsworth–Emmons, TBS=tert-butyldimethylsilyl).

    28. Imaging Agents

      Heteroditopic Binding of Magnetic Resonance Contrast Agents for Increased Relaxivity (pages 2621–2624)

      Dr. Zhaoda Zhang, Dr. Andrew F. Kolodziej, Matthew T. Greenfield and Prof. Peter Caravan

      Article first published online: 8 FEB 2011 | DOI: 10.1002/anie.201007689

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      Kept within bounds: For peptide-targeted contrast agents, internal motion limits the relaxivity gain. A focused library approach identified an N-terminal thymine peptide nucleic acid (PNA) that reaches an additional binding pocket on the protein fibrin. The heteroditopic binding rigidifies the molecule upon binding, resulting in increased protein-bound relaxivity (see picture).

    29. Microbial Electron Transfer

      In Situ Spectroelectrochemical Investigation of Electrocatalytic Microbial Biofilms by Surface-Enhanced Resonance Raman Spectroscopy (pages 2625–2627)

      Dr. Diego Millo, Dr. Falk Harnisch, Sunil A. Patil, Hoang K. Ly, Prof. Dr. Uwe Schröder and Prof. Dr. Peter Hildebrandt

      Article first published online: 17 FEB 2011 | DOI: 10.1002/anie.201006046

      Thumbnail image of graphical abstract

      A mixed-culture-derived microbial biofilm, grown on silver electrodes, was studied in vivo with surface-enhanced resonance Raman scattering (SERRS) in combination with cyclic voltammetry. This experimental approach provides unprecedented structural information about the outer membrane cytochromes involved in the direct electron transfer across the bacterium–electrode interface.

    30. Cluster Compounds

      Tetrahedral Gold(I) Clusters with Carba-closo-dodecaboranylethynido Ligands: [{12-(R3PAu)2C[TRIPLE BOND]C-closo-1-CB11H11}2] (pages 2628–2631)

      Alexander Himmelspach, Priv.-Doz. Dr. Maik Finze and Dr. Stephan Raub

      Article first published online: 15 FEB 2011 | DOI: 10.1002/anie.201007239

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      On golden bond: In both the solid state and in solution, the neutral dinuclear gold(I) complexes [12-(R3PAu)2C[TRIPLE BOND]C-closo-1-CB11H11] (R=Me, Et) dimerize to tetranuclear gold(I) clusters held together by aurophilic interactions. For the Et3P complex, the dimer and the monomer exist in equilibrium in solution at 25 °C. In contrast, even at 75 °C only dimers (AuI4 clusters), are observed for the Me3P complex (see structure: C black, B brown, P pink, Au yellow).

    31. Biocatalysis

      SEIRA Spectroscopy of the Electrochemical Activation of an Immobilized [NiFe] Hydrogenase under Turnover and Non-Turnover Conditions (pages 2632–2634)

      Dr. Diego Millo, Prof. Dr. Peter Hildebrandt, Dr. Maria-Eirini Pandelia, Prof. Dr. Wolfgang Lubitz and Dr. Ingo Zebger

      Article first published online: 10 FEB 2011 | DOI: 10.1002/anie.201006646

      Thumbnail image of graphical abstract

      Effective and unaffected: An [NiFe] hydrogenase was immobilized on Au electrodes. Surface-enhanced infrared absorption (SEIRA) spectroscopy monitored structural changes of the active site as a function of the applied potential. The redox titration of the enzyme gave a formal potential (E1/2) similar to that obtained for the enzyme in solution, demonstrating that the structure of the active site is not affected by the immobilization.

    32. Heterogeneous Catalysis

      Activation of Oxygen on MgO: O2.− Radical Ion Formation on Thin, Metal-Supported MgO(001) Films (pages 2635–2638)

      Anastasia Gonchar, Prof. Dr. Thomas Risse, Prof. Dr. Hans-Joachim Freund, Dr. Livia Giordano, Dr. Cristiana Di Valentin and Prof. Dr. Gianfranco Pacchioni

      Article first published online: 11 FEB 2011 | DOI: 10.1002/anie.201005729

      Thumbnail image of graphical abstract

      Distortion is the key: In situ EPR spectroscopy provides the first experimental confirmation that the adsorption of O2 molecules on a stoichiometric ultrathin MgO(001) film on Mo(001) leads to the spontaneous formation of O2.− radicals. The results show that polaronic distortion of the MgO lattice (see picture; Mg yellow, O blue) stabilizes the radical, and this distortion is only possible in very thin films.

    33. Noble Metalates

      Synthesis and Characterization of the Dicopper(II)-Containing 22-Palladate(II)[CuII2PdII22PV12O60(OH)8]20− (pages 2639–2642)

      Maria Barsukova-Stuckart, Dr. Natalya V. Izarova, Prof. Geoffrey B. Jameson, Vasanth Ramachandran, Zhenxing Wang, Dr. Johan van Tol, Prof. Naresh S. Dalal, Rosa Ngo Biboum, Dr. Bineta Keita, Prof. Louis Nadjo and Prof. Ulrich Kortz

      Article first published online: 10 FEB 2011 | DOI: 10.1002/anie.201006734

      Thumbnail image of graphical abstract

      A couple of coppers: Two CuII ions exhibit highly distorted cubic coordination and unexpectedly large magnetic exchange coupling in a discrete dicopper(II)-containing 22-palladate(II). The compound is isolated as the hydrated sodium salt Na20[CuII2PdII22PV12O60(OH)8]⋅58 H2O (1) in which the polyanion (see structure: Cu turquoise, Pd blue, O red balls, {PO4} purple tetrahedra) is the largest noble metalate reported to date.

    34. Structure Elucidation

      Residual Dipolar Couplings as a Powerful Tool for Constitutional Analysis: The Unexpected Formation of Tricyclic Compounds (pages 2643–2645)

      Dr. Grit Kummerlöwe, Dr. Benedikt Crone, Manuel Kretschmer, Prof. Dr. Stefan F. Kirsch and Prof. Dr. Burkhard Luy

      Article first published online: 18 FEB 2011 | DOI: 10.1002/anie.201007305

      Thumbnail image of graphical abstract

      Analyze this! Residual dipolar couplings (RDCs) can be used to determine the constitution of a small molecule when traditional methods for structure elucidation fail. In a case study, a highly congested, tricyclic compound resulting from the electrophilic cyclization of an azide-containing 1,5-enyne was investigated.

  12. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
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    14. Back Cover
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      Preview: Angew. Chem. Int. Ed. 12/2011 (page 2647)

      Article first published online: 2 MAR 2011 | DOI: 10.1002/anie.201190019

  13. Back Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Obituary
    8. Book Review
    9. Highlights
    10. Minireview
    11. Review
    12. Communications
    13. Preview
    14. Back Cover
    1. Back Cover: Residual Dipolar Couplings as a Powerful Tool for Constitutional Analysis: The Unexpected Formation of Tricyclic Compounds (Angew. Chem. Int. Ed. 11/2011) (page 2648)

      Dr. Grit Kummerlöwe, Dr. Benedikt Crone, Manuel Kretschmer, Prof. Dr. Stefan F. Kirsch and Prof. Dr. Burkhard Luy

      Article first published online: 21 FEB 2011 | DOI: 10.1002/anie.201101025

      Thumbnail image of graphical abstract

      Puzzle solved:Residual dipolar couplings (RDCs) can be a powerful method to determine the constitution of molecules when traditional methods for structure elucidation fail. In their Communication on page 2643 ff., B. Luy, S. F. Kirsch, and co-workers demonstrate this method with products obtained by treating an azide-containing 1,5-enyne in the presence of electrophilic iodine sources: whereas standard analytical methods only left an unsolved structural jigsaw puzzle, the use of RDCs allowed the molecules to be identified. The authors thank R. Oehme for his support with the back-cover design.

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