Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 14

April 2, 2012

Volume 51, Issue 14

Pages 3277–3490

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Inside Back Cover
    5. Back Cover
    6. Editorial
    7. Graphical Abstract
    8. News
    9. Author Profile
    10. News
    11. Book Review
    12. Highlights
    13. Review
    14. Communications
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    1. Cover Picture: The Crystal Structure of Human α2-Macroglobulin Reveals a Unique Molecular Cage (Angew. Chem. Int. Ed. 14/2012) (page 3277)

      Dr. Aniebrys Marrero, Dr. Stephane Duquerroy, Dr. Stefano Trapani, Dr. Theodoros Goulas, Tibisay Guevara, Prof. Dr. Gregers R. Andersen, Dr. Jorge Navaza, Prof. Dr. Lars Sottrup-Jensen and Prof. Dr. F. Xavier Gomis-Rüth

      Article first published online: 1 FEB 2012 | DOI: 10.1002/anie.201109104

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      The large central cavity of the human methylamine-induced form of α2-macroglobulin (α2M) can accommodate two medium-sized proteinases, as shown by its crystal structure. In their Communication on page 3340 ff., F. X. Gomis-Rüth et al. show how the 720-KDa α2M traps prey proteinases by a major conformational rearrangement from an open to a closed form, a process reminiscent of the action of a Venus flytrap. Photos of a meal worm in a Venus flytrap courtesy of Beatrice Murch (www.beatricemurchphotography.com).

  2. Inside Cover

    1. Top of page
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    4. Inside Back Cover
    5. Back Cover
    6. Editorial
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    8. News
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    10. News
    11. Book Review
    12. Highlights
    13. Review
    14. Communications
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    1. Inside Cover: C[BOND]C or C[BOND]O Bond Cleavage in a Phenolic Lignin Model Compound: Selectivity Depends on Vanadium Catalyst (Angew. Chem. Int. Ed. 14/2012) (page 3278)

      Dr. Susan K. Hanson, Dr. Ruilian Wu and Dr. Louis A. “Pete” Silks

      Article first published online: 8 FEB 2012 | DOI: 10.1002/anie.201200720

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      Vanadium complexes catalyze C[BOND]C and C[BOND]O bond cleavage reactions in lignin model compounds with air as the oxidant. In their Communication on page 3410 ff., S. K. Hanson, R. Wu, and L. A. Silks report the influence of the ligand framework of the vanadium catalyst on the selectivity of the bond cleavage, thus showing the potential of homogeneous catalysts for controlling selectivity in the aerobic oxidation of lignin. (Picture by Josh Smith, LANL Chemistry Division.)

  3. Inside Back Cover

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    11. Book Review
    12. Highlights
    13. Review
    14. Communications
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    1. Inside Back Cover: Highly Stereoselective Metal-Free Oxyaminations Using Chiral Hypervalent Iodine Reagents (Angew. Chem. Int. Ed. 14/2012) (page 3491)

      Umar Farid and Prof. Dr. Thomas Wirth

      Article first published online: 1 MAR 2012 | DOI: 10.1002/anie.201201230

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      About 30 % of the world's iodine production comes from the Chiba area in Japan, shown in the background of the picture (Map data ©2012 ZENRIN Imagery ©2012 TerraMetrics). Enantiomerically pure hypervalent iodine compounds are the key for metal-free, highly stereoselective oxyaminations of alkenes. In their Communication on page 3462 ff., T. Wirth and U. Farid report the use of the reaction for the facile synthesis of 2-arylprolinols.

  4. Back Cover

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    13. Review
    14. Communications
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    1. Back Cover: Tailoring Silicalite-1 Crystal Morphology with Molecular Modifiers (Angew. Chem. Int. Ed. 14/2012) (page 3492)

      Alexandra I. Lupulescu and Prof. Jeffrey D. Rimer

      Article first published online: 8 FEB 2012 | DOI: 10.1002/anie.201200550

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      Bio-inspired crystal engineering of nanoporous zeolites is described by A. I. Lupulescu and J. D. Rimer in their Communication on page 3345 ff. Molecular analogues of silica proteins in unicellular organisms are effective growth modifiers that exhibit molecular recognition for binding to zeolite surfaces to alter the kinetics of crystallization, tune the architecture of exterior surfaces, and selectively tailor crystal habit with precise 3D control.

  5. Editorial

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    14. Communications
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  6. Graphical Abstract

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    12. Highlights
    13. Review
    14. Communications
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  7. News

    1. Top of page
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  8. Author Profile

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    1. François Diederich (pages 3302–3304)

      Article first published online: 1 MAR 2012 | DOI: 10.1002/anie.201200546

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      “My favorite food is Japanese cuisine. The most important thing I learned from my parents is a love for dedicated and reliable craftsmanship …” This and more about François Diederich can be found on page 3302.

  9. News

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  10. Book Review

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    1. Chemistry in the Kitchen Garden. By James R. Hanson. (page 3307)

      Charles Sell

      Article first published online: 1 MAR 2012 | DOI: 10.1002/anie.201200214

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      RSC Publishing, Cambridge, 2011. 300 pp., hardcover, £ 24.99.—ISBN 978-1849733236

  11. Highlights

    1. Top of page
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    1. Hydrogenases

      New Iron–Sulfur Clusters Help Hydrogenases Tolerate Oxygen (pages 3308–3310)

      Katarzyna Grubel and Prof. Patrick L. Holland

      Article first published online: 9 FEB 2012 | DOI: 10.1002/anie.201108761

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      One S less: Recent crystallographic studies have revealed a new, oxygen-tolerant kind of iron–sulfide cluster [4Fe-3S], which contains only three rather than four sulfur atoms in its cage (see picture; yellow=S, red=Fe, blue=N, green=cysteine). It is proposed that the cluster's ability to transfer multiple electrons increases the oxygen tolerance by enabling the enzyme to reduce O2 rapidly, converting the dioxygen into harmless water before it can damage the protein.

    2. Nanomaterials

      Bimetallic Nanoparticles: Kinetic Control Matters (pages 3311–3313)

      Xiaowang Liu and Prof. Xiaogang Liu

      Article first published online: 14 FEB 2012 | DOI: 10.1002/anie.201108661

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      Morphologies à la carte: A kinetic control strategy has been utilized to fabricate bimetallic nanoparticles. Using cubic Pd nanocrystals as seeds and a syringe pump that enables precise control over precursor injection rate, it is possible to synthesize Pd–Ag bimetallic nanoparticles with tailored shapes (see picture: dimers, eccentric hybrid bars, and core–shell structures) and tunable localized surface plasmon resonances.

  12. Review

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    14. Communications
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    1. Cross-Coupling Catalysts

      The Development of Bulky Palladium NHC Complexes for the Most-Challenging Cross-Coupling Reactions (pages 3314–3332)

      Dr. Cory Valente, Dr. Selçuk Çalimsiz, Ka Hou Hoi, Dr. Debasis Mallik, Mahmoud Sayah and Prof. Michael G. Organ

      Article first published online: 27 JAN 2012 | DOI: 10.1002/anie.201106131

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      Adding fizz to catalysis: The Pd-PEPPSI series of catalysts (see scheme) is very active for the Suzuki–Miyaura, Negishi, Stille–Migita, aryl amination, and aryl sulfination reactions. The high reactivities of Pd-PEPPSI-IPr and Pd-PEPPSI-IPent catalysts with N-heterocyclic carbene (NHC) ligands are compared with other state-of-the-art catalysts. Pd-PEPPSI-IPent is shown to be one of the most active and general catalysts for cross-coupling reactions.

  13. Communications

    1. Top of page
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    1. Small-Ring Systems

      Experimental Observation of the 16-Electron Molecules SPN, SNP, and Cyclic PSN (pages 3334–3339)

      Dr. Xiaoqing Zeng, Dr. Helmut Beckers, Prof. Dr. Helge Willner and Prof. Dr. Joseph S. Francisco

      Article first published online: 20 JAN 2012 | DOI: 10.1002/anie.201108636

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      16-Electron triatomic ring: Novel thiazylidynephosphane (SNP) was produced by either flash vacuum pyrolysis (ca. 1000 °C) or laser photolysis (193 nm) of SP(N3)3. Its photointerconversion to cyclic thiazaphosphirine (cyc-PSN) and thiophosphoryl nitride (SPN) was found in Ar matrix at 16 K. Cyc-PSN is the first experimentally observed 16-electron cyclic triatomic molecule.

    2. Molecular Biology

      The Crystal Structure of Human α2-Macroglobulin Reveals a Unique Molecular Cage (pages 3340–3344)

      Dr. Aniebrys Marrero, Dr. Stephane Duquerroy, Dr. Stefano Trapani, Dr. Theodoros Goulas, Tibisay Guevara, Prof. Dr. Gregers R. Andersen, Dr. Jorge Navaza, Prof. Dr. Lars Sottrup-Jensen and Prof. Dr. F. Xavier Gomis-Rüth

      Article first published online: 31 JAN 2012 | DOI: 10.1002/anie.201108015

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      I'm your Venus: The crystal structure of the human methylamine-induced form of α2-macroglobulin (α2M) shows its large central cavity can accommodate two medium-sized proteinases (see structure, front part clipped off to better show central cavity). Twelve major entrances provide access for small substrates to the cavity and the still-active trapped “prey”. The structure unveils the molecular basis of the unique “venus flytrap” mechanism of α2M.

    3. Zeolite Crystallization

      Tailoring Silicalite-1 Crystal Morphology with Molecular Modifiers (pages 3345–3349)

      Alexandra I. Lupulescu and Prof. Jeffrey D. Rimer

      Article first published online: 17 JAN 2012 | DOI: 10.1002/anie.201107725

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      Modified point of view: A bio-inspired approach was used to tailor silicalite-1 crystallization. Growth modifiers (ZGMs) with molecular recognition for binding to specific crystal faces produced drastic changes in zeolite crystal morphology. This facile approach offers an efficient method for tuning zeolite properties.

    4. Bioluminescence

      A Selenium Analogue of Firefly D-Luciferin with Red-Shifted Bioluminescence Emission (pages 3350–3353)

      Dr. Nicholas R. Conley, Dr. Anca Dragulescu-Andrasi, Prof. Jianghong Rao and Prof. W. E. Moerner

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201105653

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      A selenium analogue of amino-D-luciferin, aminoseleno-D-luciferin, is synthesized and shown to be a competent substrate for the firefly luciferase enzyme. It has a red-shifted bioluminescence emission maximum at 600 nm (see scheme) and is suitable for bioluminescence imaging studies in living subjects.

    5. Bio-organometallic Chemistry

      [(Cp-R)M(CO)3] (M=Re or 99mTc) Arylsulfonamide, Arylsulfamide, and Arylsulfamate Conjugates for Selective Targeting of Human Carbonic Anhydrase IX (pages 3354–3357)

      Daniel Can, Priv.-Doz. Dr. Bernhard Spingler, Dr. Paul Schmutz, Dr. Filipa Mendes, Dr. Paula Raposinho, Dr. Célia Fernandes, Fabrizio Carta, Alessio Innocenti, Prof. Dr. Isabel Santos, Prof. Dr. Claudiu T. Supuran and Prof. Dr. Roger Alberto

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201107333

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      Enhanced receptor selectivity: Carbonic anhydrase inhibitors are relevant for both cancer diagnosis and therapy. Combining non-radioactive Re compounds with their radioactive 99mTc homologs enables the use of identical molecules for therapy and imaging (theragnostic). The syntheses and in vitro evaluation of [(Cp-R)M(CO)3] (Cp=cyclopentadienyl, M=Re, 99mTc) with R being a highly potent carbonic-anhydrase-targeting vector is reported (see picture).

    6. Protein Quantification

      Europium-Labeled Activity-Based Probe through Click Chemistry: Absolute Serine Protease Quantification Using 153Eu Isotope Dilution ICP/MS (pages 3358–3363)

      Dr. Xiaowen Yan, Yacui Luo, Zhubao Zhang, Zhaoxin Li, Dr. Qiang Luo, Prof. Limin Yang, Dr. Bo Zhang, Dr. Haifeng Chen, Dr. Peiming Bai and Prof. Dr. Qiuquan Wang

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201108277

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      Click and analyze: The titled probe was synthesized by conjugating a sulfonyl fluoride and azido unit using click chemistry to give SF-Eu, which can react specifically with serine (Ser) in the active site of serine protease (SP). Combination of the method with 153Eu-isotope dilution ICP/MS enables absolute protein quantification of active SPs in biological samples using only one 153Eu(NO3)3 isotopic standard.

    7. Photocatalysis

      An Amine-Functionalized Titanium Metal–Organic Framework Photocatalyst with Visible-Light-Induced Activity for CO2 Reduction (pages 3364–3367)

      Yanghe Fu, Dengrong Sun, Yongjuan Chen, Renkun Huang, Dr. Zhengxin Ding, Prof. Dr. Xianzhi Fu and Prof. Dr. Zhaohui Li

      Article first published online: 22 FEB 2012 | DOI: 10.1002/anie.201108357

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      Let your light shine: The photocatalytic reduction of carbon dioxide to the formate anion under visible light irradiation is for the first time realized over a photoactive Ti-containing metal–organic framework, NH2-MIL-125(Ti), which is fabricated by a facile substitution of ligands in the UV-responsive MIL-125(Ti) material (see scheme; TEOA=triethanolamine).

    8. Arynes

      Catalytic Generation of Arynes and Trapping by Nucleophilic Addition and Iodination (pages 3368–3372)

      Prof. Dr. Toshiyuki Hamura, Yu Chuda, Yuya Nakatsuji and Prof. Dr. Keisuke Suzuki

      Article first published online: 22 FEB 2012 | DOI: 10.1002/anie.201108415

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      A fair exchange: In the title reaction, alkynyllithium serves as an initiator for benzyne generation through an iodine–lithium exchange (see scheme; Tf=trifluoromethanesulfonyl). When performed in the presence of stoichiometric amounts of a nucleophile, the generated benzyne undergoes attack by lithio nucleophiles to generate aryllithium, which is then iodinated by iodoalkyne to give the iodoarenes 1.

    9. Polyoxometalates

      Assembly of Molecular “Layered” Heteropolyoxometalate Architectures (pages 3373–3376)

      Jing Gao, Dr. Jun Yan, Sebastian Beeg, Dr. De-Liang Long and Prof. Leroy Cronin

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108428

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      Neoclassical architecture: A new family of heteropolyoxometalates with “pagoda”-shaped building blocks [TenW6n+3O21n+12](6+2n)− (n=1, 2, 3) was discovered by adding {TeW6O21} layers on a classic {TeW9O33} fragment. Linking of the units allowed the generation of nanostructured clusters whose gross conformation is cation controlled. Studies of the redox behaviors of the multi-layered clusters indicate that the TeIV template is redox-active.

    10. Fullerenes

      Rock-Salt-Type Crystal of Thermally Contracted C60 with Encapsulated Lithium Cation (pages 3377–3381)

      Dr. Shinobu Aoyagi, Yuki Sado, Dr. Eiji Nishibori, Prof. Hiroshi Sawa, Dr. Hiroshi Okada, Prof. Hiromi Tobita, Dr. Yasuhiko Kasama, Dr. Ryo Kitaura and Prof. Hisanori Shinohara

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108551

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      Rock solid: Fullerene-encapsulated Li+ (Li+@C60) is an alkaline cation owing to the spherical shape and positive charge. Li+@C60 crystallizes as a rock-salt-type crystal in the presence of PF6. The orientations of C60 (green; see picture) and PF6 (orange) are perfectly ordered below 370 K, and Li+ (purple) hops within the cage. At temperatures below 100 K two Li+ units are localized at two polar positions within each C60.

    11. DNA Nanostructures

      DNA-Directed Three-Dimensional Protein Organization (pages 3382–3385)

      Chuan Zhang, Cheng Tian, Fei Guo, Zheng Liu, Prof. Wen Jiang and Prof. Chengde Mao

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108710

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      All bound together: Self-assembled symmetric DNA polyhedra were used to organize proteins in 3D space. Biotin moieties were incorporated into the self-assembled symmetric DNA polyhedra. Upon incubation with streptavidin (STV) protein, an STV protein became bound to each polyhedral face, thus resulting in well-structured DNA polyhedra/STV complexes (see picture, TET=tetrahedron). This strategy was also applied to different 3D DNA nanostructures and different proteins.

    12. Sugar Derivatives

      Glycomics for Drug Discovery: Metabolic Perturbation in Androgen-Independent Prostate Cancer Cells Induced by Unnatural Hexosamine Mimics (pages 3386–3390)

      Prof. Shin-Ichiro Nishimura, Dr. Megumi Hato, Satoshi Hyugaji, Dr. Fei Feng and Dr. Maho Amano

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201108742

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      Inhibited: N-acetylglucosamine (GlcNAc) derivatives with a fluorine atom at the C4 position (24) were synthesized, and their ability to inhibit cancer-cell growth was investigated. The administration of these 4F-GlcNAc derivatives to cells led to the unnatural sugar nucleotide 1. Furthermore, N-glycan profiles of cells were determined by using a glycoblotting-based enrichment analysis, which is suitable for high-throughput screenings for drug discovery.

    13. Luminescent Liquids

      Solvent-Free Luminescent Organic Liquids (pages 3391–3395)

      Dr. Sukumaran Santhosh Babu, Dr. Junko Aimi, Dr. Hiroaki Ozawa, Dr. Naoto Shirahata, Dr. Akinori Saeki, Prof. Shu Seki, Prof. Ayyappanpillai Ajayaghosh, Prof. Dr. Helmuth Möhwald and Dr. Takashi Nakanishi

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108853

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      Illuminating! Isolation of a π-core by covalently attached flexible hydrocarbon chains has been employed to synthesize blue-emitting oligo(p-phenylenevinylene) (OPV) liquids with tunable viscosity and optical properties. A solvent-free, stable, white-light emitting ink/paint, which can be applied onto various surfaces and even onto LEDs, was made by blending of liquid OPVs with emissive solid dopants.

    14. Ripostatin B (1)

      Access to Skipped Polyene Macrolides through Ring-Closing Metathesis: Total Synthesis of the RNA Polymerase Inhibitor Ripostatin B (pages 3396–3400)

      Philipp Winter, Dr. Wolf Hiller and Prof. Mathias Christmann

      Article first published online: 15 FEB 2012 | DOI: 10.1002/anie.201108692

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      Rip-Roaring! A convergent total synthesis of antibiotic ripostatin B was developed. A key step in the synthesis is a metathesis reaction allowing for a ring closure to the labile doubly skipped triene macrolide.

    15. Ripostatin B (2)

      Total Synthesis of RNA-Polymerase Inhibitor Ripostatin B and 15-Deoxyripostatin A (pages 3401–3404)

      Wufeng Tang and Dr. Evgeny V. Prusov

      Article first published online: 29 FEB 2012 | DOI: 10.1002/anie.201108749

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      Keep me skipped: A highly convergent total synthesis of ripostatin B, an inhibitor of the bacterial RNA polymerase, is described. The key steps to construct and avoid isomerization of the skipped triene are a double Stille cross-coupling reaction and a ring-closing metathesis. Furthermore, 15-deoxyripostatin A, a stable and conformationally locked analogue of ripostatin A (see scheme, 15-OH group red), was prepared and tested in vivo.

    16. Ripostatin B (3)

      Total Synthesis of the Bacterial RNA Polymerase Inhibitor Ripostatin B (pages 3405–3409)

      MSc Florian Glaus and Prof. Dr. Karl-Heinz Altmann

      Article first published online: 29 FEB 2012 | DOI: 10.1002/anie.201200871

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      A modular and highly stereoselective synthesis of the title compound was developed. Key steps in the assembly of the carbon framework of ripostatin B (1; see scheme) were a stereoselective Paterson aldol reaction and a high-yielding ring-closing metathesis mediated by Grubbs first generation catalyst. The C15 hydroxy group was established through Tishchenko–Evans reduction in excellent yield and selectivity.

    17. Oxidative Cleavage

      C[BOND]C or C[BOND]O Bond Cleavage in a Phenolic Lignin Model Compound: Selectivity Depends on Vanadium Catalyst (pages 3410–3413)

      Dr. Susan K. Hanson, Dr. Ruilian Wu and Dr. Louis A. “Pete” Silks

      Article first published online: 20 JAN 2012 | DOI: 10.1002/anie.201107020

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      The aerobic oxidation of a phenolic lignin model compound with a vanadium catalyst results in the oxidative cleavage of the C[BOND]C bond between the aryl ring and the adjacent hydroxy-substituted carbon atom (see scheme). Labeling experiments indicate key mechanistic differences to a previously reported related C[BOND]O bond cleavage reaction. The selectivity in C[BOND]C versus C[BOND]O bond cleavage depends on the choice of the vanadium catalyst.

    18. Fluorination

      Carbon(sp3)[BOND]Fluorine Bond-Forming Reductive Elimination from Palladium(IV) Complexes (pages 3414–3417)

      Joy M. Racowski, J. Brannon Gary and Prof. Dr. Melanie S. Sanford

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201107816

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      PdIV–fluoride complexes, some of which are remarkably insensitive to water, have been synthesized and used in the title reaction, which proceeds with high selectivity to give the product of the C(sp3)[BOND]F coupling (see scheme, TfO=trifluoromethanesulfonate). Preliminary mechanistic studies implicate a pathway involving dissociation of pyridine followed by direct C[BOND]F coupling at the Pd center.

    19. Solid-State Chemistry

      Chemical Bonding and Atomic Structure in Y2O3:ZrO2-SrTiO3 Layered Heterostructures (pages 3418–3422)

      Dr. Matthew S. Dyer, Dr. George R. Darling, Dr. John B. Claridge and Prof. Matthew J. Rosseinsky

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108068

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      Repeating boundaries: The buried interfaces in artificial heterostructures produced by sequential deposition of nanosized units are critical to their properties. With density functional theory it was shown that in Y2O3:ZrO2 (YSZ) and SrTiO3 (STO) heterostructures reconstruction of the interfaces between the component units is required to access the most favorable structure (see picture).

    20. Inhibitors

      Discovery of Macrocyclic Peptides Armed with a Mechanism-Based Warhead: Isoform-Selective Inhibition of Human Deacetylase SIRT2 (pages 3423–3427)

      Jumpei Morimoto, Dr. Yuuki Hayashi and Prof. Hiroaki Suga

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108118

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      Designed to inhibit: By using the random nonstandard peptide integrated discovery (RaPID) system, highly potent isoform-selective inhibitors can be identified from a library of nonstandard macrocyclic peptides (see picture). These inhibitors, which contain a mechanism-based warhead residue, are active against the human deacetylase SIRT2, with IC50 values in the low nanomolar region.

    21. Enzymes

      The Last Step of Kanamycin Biosynthesis: Unique Deamination Reaction Catalyzed by the α-Ketoglutarate-Dependent Nonheme Iron Dioxygenase KanJ and the NADPH-Dependent Reductase KanK (pages 3428–3431)

      Hilda Sucipto, Prof. Dr. Fumitaka Kudo and Prof. Dr. Tadashi Eguchi

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108122

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      Mystery solved: Using heterologous expression, the activities of two enzymes exclusively belonging to the kanamycin biosynthetic pathway have been identified in vitro. A distinctive reaction mechanism (see scheme) to produce kanamycin is proposed and the previously unknown catalytic deamination activity of KanJ dioxygenase is uncovered.

    22. Photochromism

      A Room-Temperature X-ray-Induced Photochromic Material for X-ray Detection (pages 3432–3435)

      Ming-Sheng Wang, Chen Yang, Guan-E. Wang, Gang Xu, Xiang-Ying Lv, Zhong-Ning Xu, Rong-Guang Lin, Li-Zhen Cai and Prof. Dr. Guo-Cong Guo

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108220

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      A color change: X-ray-induced photochromic species are rare and can be used for detection of X-rays. A highly robust X-ray-sensitive material with the discrete structure of a metal–organic complex has been found to show both soft and hard X-ray-induced photochromism at room temperature (see picture). A new ligand-to-ligand electron-transfer mechanism was proposed to elucidate this photochromic phenomenon.

    23. Total Synthesis

      Total Synthesis of (−)-Dendrobine (pages 3436–3439)

      Lukas M. Kreis and Prof. Dr. Erick M. Carreira

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201108564

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      Cascading to alkaloids: An 18-step total synthesis of (−)-dendrobine is based on a reaction cascade with a key amine group (see scheme, Bn=benzyl). The amine is the initiator of the cascade and provides an efficient method for installing the stereocenters at C11 and C3. The overall transformation occurs stereoselectively only when the conversion is carried out without the isolation of intermediates.

    24. Heterogeneous Catalysis

      Selective Hydrogenation of α,β-Unsaturated Aldehydes Catalyzed by Amine-Capped Platinum-Cobalt Nanocrystals (pages 3440–3443)

      Binghui Wu, Huaqi Huang, Dr. Jing Yang, Prof. Nanfeng Zheng and Prof. Gang Fu

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108593

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      More Greasy, More Selective: Amine-capped Pt3Co nanocatalysts were synthesized and used for the hydrogenation of cinnamaldehyde (CAL). Capping the catalysts with amines that contain long carbon chains results in an ordered surface “array” (see scheme), in which high selectivity towards C[DOUBLE BOND]O hydrogenation can be achieved because the C[DOUBLE BOND]C bond in CAL does not interact with the surface. The longer the carbon chains in the amine, the higher the selectivity.

    25. Hydrides of Lanthanides

      A Double Addition of Ln[BOND]H to a Carbon–Carbon Triple Bond and Competitive Oxidation of Ytterbium(II) and Hydrido Centers (pages 3444–3447)

      Ivan V. Basalov, Dr. Dmitry M. Lyubov, Dr. Georgy K. Fukin, Dr. Andrei S. Shavyrin and Prof. Dr. Alexander A. Trifonov

      Article first published online: 28 FEB 2012 | DOI: 10.1002/anie.201108662

      Thumbnail image of graphical abstract

      Addition of two Ln[BOND]H bonds of an YbII hydrido complex supported by bulky amidinate ligand to a C[TRIPLE BOND]C bond lead to the formation of 1,2-dianionic bibenzyl fragment (see picture). Both YbII and hydrido centers are oxidized under the reaction conditions. The resulting YbII6-arene interaction is surprisingly robust: the arene cannot be replaced from the metal coordination sphere when treated with Lewis bases.

    26. Hydroxylation

      An Iron(III)–Monoamidate Complex Catalyst for Selective Hydroxylation of Alkane C[BOND]H Bonds with Hydrogen Peroxide (pages 3448–3452)

      Prof. Yutaka Hitomi, Kengo Arakawa, Dr. Takuzo Funabiki and Prof. Masahito Kodera

      Article first published online: 29 FEB 2012 | DOI: 10.1002/anie.201108933

      Thumbnail image of graphical abstract

      Selective oxidation: The success of the title reaction (see scheme) is caused by the strong electron donation from the amidate moiety of the dpaq ligand to the iron center (dpaq=2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate). This process facilitates the O[BOND]O bond heterolysis of the intermediate FeIIIOOH species to generate a selective oxidant without forming highly reactive hydroxyl radicals.

    27. Synthetic Methods

      Copper-Catalyzed C[BOND]H Oxidation/Cross-Coupling of α-Amino Carbonyl Compounds (pages 3453–3457)

      Ji-Cheng Wu, Ren-Jie Song, Zhi-Qiang Wang, Xiao-Cheng Huang, Ye-Xiang Xie and Prof. Dr. Jin-Heng Li

      Article first published online: 29 FEB 2012 | DOI: 10.1002/anie.201109027

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      Keeping options open: The new and mild title reaction involving indoles selectively furnishes 1 and 2 with the aid of tert-butyl hydroperoxide (TBHP). The method represents the first example of a copper-catalyzed α arylation of α-amino carbonyl substrates leading to α-aryl α-imino and α-aryl α-oxo carbonyl compounds using a C[BOND]H oxidation strategy.

    28. Radialene Chemistry

      Synthesis and Properties of 4,5,6-Triphospha[3]radialene (pages 3458–3461)

      Dr. Hideaki Miyake, Prof. Dr. Takahiro Sasamori and Prof. Dr. Norihiro Tokitoh

      Article first published online: 22 FEB 2012 | DOI: 10.1002/anie.201200374

      Thumbnail image of graphical abstract

      [3]Radialenes: 4,5,6-Tris(2,4,6-tri-tert-butylphenyl)phospha[3]radialene has been synthesized (see picture). The compound can be easily handled in air under ambient conditions, despite the [3]radialene moiety containing P[DOUBLE BOND]C bonds, and exhibits red-shifted absorption as well as high electron-accepting ability. The unique electronic properties are brought about by the synergistic effect of the [3]radialene framework and the phosphorus substitution.

    29. Stereoselective Synthesis

      Highly Stereoselective Metal-Free Oxyaminations Using Chiral Hypervalent Iodine Reagents (pages 3462–3465)

      Umar Farid and Prof. Dr. Thomas Wirth

      Article first published online: 25 JAN 2012 | DOI: 10.1002/anie.201107703

      Thumbnail image of graphical abstract

      The ring and I: Hypervalent iodine compounds avoid the issues of toxicity or complicated ligands of many transition-metal-based systems. A highly enantioselective oxyamination of alkenes with N-sulfonyl ureas employing chiral, lactic acid-based hypervalent iodine reagents gives a facile synthesis of enantiomerically pure 2-arylproline derivatives (see scheme) for the first time.

    30. Linking DNA

      Synthesis of DNA Interstrand Cross-Links Using a Photocaged Nucleobase (pages 3466–3469)

      Sarah Hentschel, Dr. Jawad Alzeer, Dr. Todor Angelov, Prof. Dr. Orlando D. Schärer and Prof. Dr. Nathan W. Luedtke

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201108018

      Thumbnail image of graphical abstract

      The missing linking: BCNU is a chemotherapy drug that generates an ethylene bridge between N1 of deoxyguanosine and N3 of deoxycytidine. No synthesis of a DNA containing this moiety has been reported until now. A new strategy uses a photocaged nucleobase that, when released, generates a highly reactive intermediate which cross-links the opposing DNA strand in a manner analogous to BCNU (see scheme, NBOC=ortho-nitrobenzyloxycarbonyl).

    31. Enantioselective Allylic Amination

      Direct, Enantioselective Iridium-Catalyzed Allylic Amination of Racemic Allylic Alcohols (pages 3470–3473)

      Dr. Marc Lafrance, Markus Roggen and Prof. Dr. Erick M. Carreira

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201108287

      Thumbnail image of graphical abstract

      The direct route: Iridium-catalyzed direct conversion of branched allylic alcohols into enantioenriched branched primary allylic amines is highly regio- and enantioselective (see scheme; coe=cyclooctene).

    32. Natural Product Synthesis

      Total Synthesis and Stereochemical Reassignment of (±)-Indoxamycin B (pages 3474–3477)

      Oliver F. Jeker and Prof. Dr. Erick M. Carreira

      Article first published online: 17 FEB 2012 | DOI: 10.1002/anie.201109175

      Thumbnail image of graphical abstract

      Revised version: The first total synthesis of indoxamycin B leads to a stereochemical reassignment of the natural product (see picture). The synthetic route features an efficient carboannulation sequence to rapidly access the dihydroindenone system. Moreover, a series of AuI-catalyzed transformations served in the construction of the sterically congested core framework.

    33. Organotin Compounds

      Intramolecularly Coordinated Organotin Tellurides: Stable or Unstable? (pages 3478–3482)

      Marek Bouška, Dr. Libor Dostál, Zdeňka Padělková, Prof. Dr. Antonín Lyčka, Prof. Dr. Sonja Herres-Pawlis, Prof. Dr. Klaus Jurkschat and Dr. Roman Jambor

      Article first published online: 29 FEB 2012 | DOI: 10.1002/anie.201107666

      Thumbnail image of graphical abstract

      The step-wise oxidation of an organotin(I) compound with elemental tellurium gave a variety of unprecedented organotin tellurides containing tin atoms in the oxidation states +II and +IV (see examples).

    34. Gas-Phase Reactions

      C[BOND]N and C[BOND]C Bond Formations in the Thermal Reactions of “Bare” Ni(NH2)+ with C2H4: Mechanistic Insight on the Metal-Mediated Hydroamination of an Unactivated Olefin (pages 3483–3488)

      Dipl.-Chem. Robert Kretschmer, Dr. Maria Schlangen and Prof. Dr. Helmut Schwarz

      Article first published online: 10 FEB 2012 | DOI: 10.1002/anie.201104433

      Thumbnail image of graphical abstract

      Strike! While pure ammonia is out of luck, Ni(NH2)+ gets one strike after another at the “ethylene bowling championship”. In fact, Ni(NH2)+ is so effective that no pin, not even at the neighboring lane, is safe from it.

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      Article first published online: 27 MAR 2012 | DOI: 10.1002/anie.201290025

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