Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 28

July 8, 2013

Volume 52, Issue 28

Pages 7045–7320

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: A Cyclic Silylone (“Siladicarbene”) with an Electron-Rich Silicon(0) Atom (Angew. Chem. Int. Ed. 28/2013) (page 7045)

      Dr. Yun Xiong, Dr. Shenglai Yao, Prof. Dr. Shigeyoshi Inoue, Dr. Jan Dirk Epping and Prof. Dr. Matthias Driess

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201304199

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      A rare pearl of a neutral silicon atom in the formal oxidation state zero seems to evolve best in the oyster-like coordination environment of a bidentate N-heterocyclic carbene ligand. In their Communication on page 7147 ff., M. Driess and co-workers present the strikingly facile formation of this silicon pearl, which belongs to the novel class of theoretically predicted compounds termed silylones. (Graphics: Wernerwerke.)

    2. You have free access to this content
      Inside Cover: A Bioorthogonal Raman Reporter Strategy for SERS Detection of Glycans on Live Cells (Angew. Chem. Int. Ed. 28/2013) (page 7046)

      Liang Lin, Xiangdong Tian, Senlian Hong, Peng Dai, Qiancheng You, Ruyi Wang, Lianshun Feng, Prof. Can Xie, Prof. Zhong-Qun Tian and Prof. Xing Chen

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201304257

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      Raman detection of glycans on surfaces of live cells has been achieved, as described in the Communication by Z.-Q. Tian, X. Chen, and co-workers on page 7266 ff. A bioorthogonal Raman reporter (for alkyne, azide, and nitrile groups, or carbon–deuterium bonds) was installed onto the monosaccharide analogues, which were metabolically incorporated into cell surface glycans. The Raman reporter is detected using surface-enhanced Raman scattering with the aid of gold nanoparticles.

    3. You have free access to this content
      Inside Back Cover: Theoretical Considerations on the Electroreduction of CO to C2 Species on Cu(100) Electrodes (Angew. Chem. Int. Ed. 28/2013) (page 7321)

      Dr. Federico Calle-Vallejo and Prof. Marc T. M. Koper

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201304905

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      How carbon oxides are reduced by copper electrodes is a mystery. In their Communication on page 7282 ff., F. Calle-Vallejo and M. T. M. Koper use DFT calculations to elucidate a mechanism for the electroreduction of CO on Cu(100) to C2 species. The electron-transfer-mediated coupling of CO molecules is found to be the rate-limiting step. The most abundant C2 products, namely ethylene, ethanol, and acetaldehyde, are formed in a common pathway. This mechanism explains why the formation of C2 species is pH-independent.

    4. You have free access to this content
      Back Cover: Design and Synthesis of a Universal Antigen to Detect Brucellosis (Angew. Chem. Int. Ed. 28/2013) (page 7322)

      Dr. Julie Guiard, Dr. Eugenia Paszkiewicz, Joanna Sadowska and Prof. David R. Bundle

      Article first published online: 21 JUN 2013 | DOI: 10.1002/anie.201304907

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      Brucellose causes contagious abortion in cattle. The cell-wall lipopolysaccharide O-antigen of Brucella species is a homopolymer of 4,6-dideoxy-4-formamido-α-D-mannose joined by 1,2 and 1,3 linkages to create A- and M-antigenic determinants, respectively. In their Communication on page 7181 ff., D. R. Bundle and co-workers describe a glycoconjugate with both antigenic features. This antigen (red) detects A-specific (green) and M-specific (turquoise) antibodies from infected cattle.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 28/2013 (pages 7049–7064)

      Article first published online: 4 JUL 2013 | DOI: 10.1002/anie.201390028

  3. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Corrigendum: A Supramolecular Complex in Small-Molecule Solar Cells based on Contorted Aromatic Molecules (page 7063)

      Dr. Seok Ju Kang, Dr. Jong Bok Kim, Chien-Yang Chiu, Dr. Seokhoon Ahn, Dr. Theanne Schiros, Stephanie S. Lee, Dr. Kevin G. Yager, Dr. Michael F. Toney, Prof. Yueh-Lin Loo and Prof. Colin Nuckolls

      Article first published online: 4 JUL 2013 | DOI: 10.1002/anie.201303818

      This article corrects:

      A Supramolecular Complex in Small-Molecule Solar Cells based on Contorted Aromatic Molecules1

      Vol. 51, Issue 34, 8594–8597, Article first published online: 13 JUL 2012

  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Xile Hu (page 7070)

      Article first published online: 28 FEB 2013 | DOI: 10.1002/anie.201210109

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      “My greatest achievement has been getting paid to do what I do. Guaranteed to make me laugh is the comedy series “Absolutely Fabulous”. …” This and more about Xile Hu can be found on page 7070.

  6. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Biocatalysts and Enzyme Technology. 2nd Edition. By Klaus Buchholz, Volker Kasche and Uwe Theo Bornscheuer. (page 7073)

      Stephan Lütz

      Article first published online: 20 JUN 2013 | DOI: 10.1002/anie.201304275

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      Wiley-Blackwell, Hoboken, 2012. 626 pp., softcover, € 90.00.—ISBN 978-3527329892

  8. Correspondence

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Phase Transitions

      Comment on Ferroelectricity in Bis(imidazolium) L-Tartrate (pages 7076–7078)

      Prof. Marek Szafrański

      Article first published online: 11 JUN 2013 | DOI: 10.1002/anie.201208952

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      Ferroelectric properties verified: Recent results presented for the complex of imidazole and L-tartaric acid are based on improper analysis and interpretation of the experimental dielectric and crystallographic data. In particular, it has now been shown that a ferroelectric-to-paraelectric phase transition in this compound occurs at 351 K, namely at a temperature 100 K higher than reported previously.

  9. Highlight

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Nitroso Aldol Reactions

      The Electrophilic α-Amination of α-Alkyl-β-Ketoesters with In Situ Generated Nitrosoformates (pages 7080–7082)

      Philipp Selig

      Article first published online: 6 MAY 2013 | DOI: 10.1002/anie.201301282

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      Lewis acid and oxidation catalysis are merged in the reaction discussed here, which provides access to diversely substituted N-hydroxycarbamates (see scheme). This reaction highlights the potential of nitrosoformates as electrophilic amination reagents as well as the benefits of aerobic oxidation for the formation of highly reactive species.

  10. Minireview

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Isocyanide Insertion

      Palladium-Catalyzed Migratory Insertion of Isocyanides: An Emerging Platform in Cross-Coupling Chemistry (pages 7084–7097)

      Tjøstil Vlaar, Dr. Eelco Ruijter, Prof. Dr. Bert U. W. Maes and Prof. Dr. Romano V. A. Orru

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201300942

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      R you in? Isocyanides (R-NC) have recently gained attention as novel, versatile C1 building blocks in palladium catalysis. This Minireview highlights the recent progress in palladium-catalyzed reactions involving isocyanide insertion (imidoylative cross-couplings), thus illustrating their potential for the rapid construction of a variety of heterocycles and functional groups.

  11. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. Biosynthesis

      Nonproteinogenic Amino Acid Building Blocks for Nonribosomal Peptide and Hybrid Polyketide Scaffolds (pages 7098–7124)

      Prof. Christopher T. Walsh, Dr. Robert V. O'Brien and Prof. Chaitan Khosla

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201208344

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      Microbes have a remarkable capacity to build amino acid frameworks that are not incorporated into proteins. This Review summarizes the biosynthetic routes to and metabolic logic for the major classes of the noncanonical amino acid building blocks that end up in both nonribosomal peptide frameworks and in hybrid nonribosomal peptide/polyketide scaffolds.

  12. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Correspondence
    10. Highlight
    11. Minireview
    12. Review
    13. Communications
    1. As–N Triple Bond

      Arsa-Diazonium Salts With an Arsenic–Nitrogen Triple Bond (pages 7126–7130)

      Marcus Kuprat, Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201302725

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      Arsenic triply bound: Arsa-diazonium salts containing a cation with an arsenic–nitrogen triple bond ([R-N≡As]+), which is stable at room temperature, are isolated and fully characterized for the first time. Analogous to the diazonium salts, arsa-diazonium salts can be used in [3+2] dipolar cycloaddition reactions with azides to prepare arsenic analogues (RAsN4) of pentazoles (RN5).

    2. Redox Umpolung

      Convenient Titanium(III)-Catalyzed Synthesis of Cyclic Aminoketones and Pyrrolidinones—Development of a Formal [4+1] Cycloaddition (pages 7131–7134)

      Georg Frey, Hieu-Trinh Luu, Plamen Bichovski, Markus Feurer and Dr. Jan Streuff

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201302460

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      Have it both ways: α-Aminated ketones can be prepared by the titanium(III)-catalyzed reductive radical cyclization of iminonitriles. Depending on the position of the nitrile at the imine carbon or nitrogen, cyclic aminoketones or pyrrolidin-3-ones with a tetrasubstituted α-carbon can be formed in up to quantitative yield. In the latter case, the imine condensation and TiIII catalysis correspond to a formal [4+1] cycloaddition.

    3. Lewis Pairs

      An Aluminum–Nitrogen Based Lewis Pair as an Effective Catalyst for the Oligomerization of Cyanamides: Formation of Acyclic C[BOND]N Oligomers Instead of Thermodynamically Favored Cyclic Aromatic Trimers (pages 7135–7138)

      Dr. Thorsten Holtrichter-Rößmann, Dipl.-Chem. Jennifer Isermann, Dr. Christian Rösener, Dr. Benedikt Cramer, Dr. Constantin-Gabriel Daniliuc, Jutta Kösters, Matthias Letzel, Ernst-Ulrich Würthwein and Prof. Dr. Werner Uhl

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301970

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      Put in chains: Acyclic oligomers and not the thermodynamically strongly preferred aromatic trimers are formed on treatment of cyanamides with catalytic quantities of an Al–N based Lewis pair (see scheme; n=0 to >22). These oligomers have delocalized electronic systems in their backbone and are long-sought nitrogen-containing analogues of polyethyne.

    4. Spin-Crossover Nanoparticles

      Photoinduced Relaxation Dynamics in Iron(II) Spin-Crossover Nanoparticles: The Significance of Crystallinity (pages 7139–7142)

      Dr. Pradip Chakraborty, Dr. Marie-Laure Boillot, Dr. Antoine Tissot and Prof. Andreas Hauser

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301562

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      A switch in time: A fast precipitation technique was used to prepare 75 nm FeII spin-crossover nanocrystals. Their photoswitching dynamics, based on the light-induced excited spin-state trapping effect, has been investigated by means of optical spectroscopy. A significant variation of the switching proprieties is observed compared to similar but amorphous nanoparticles.

    5. NMR Spectroscopy

      You have full text access to this OnlineOpen article
      Simplifying Proton NMR Spectra by Instant Homonuclear Broadband Decoupling (pages 7143–7146)

      Dr. N. Helge Meyer and Prof. Klaus Zangger

      Article first published online: 3 JUN 2013 | DOI: 10.1002/anie.201300129

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      Shift work: The new NMR technique, instant homonuclear decoupling, which is achieved by slice-selective homo-decoupling during acquisition, yields pure-shift NMR spectra (see picture) which can be recorded like regular 1D spectra. No special data processing is necessary and this approach can also be easily adapted for the direct dimension of two- and multidimensional spectra, giving improved resolution.

    6. Silicon Chemistry

      A Cyclic Silylone (“Siladicarbene”) with an Electron-Rich Silicon(0) Atom (pages 7147–7150)

      Dr. Yun Xiong, Dr. Shenglai Yao, Prof. Dr. Shigeyoshi Inoue, Dr. Jan Dirk Epping and Prof. Dr. Matthias Driess

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201302537

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      King of donor: The chelating bis(carbene) 1 enabled the synthesis of the new silyliumylidene salt 2. This salt can be dechlorinated with sodium naphthalenide to give the first cyclic siladicarbene 3, which bears a single Si0 atom with strikingly high basicity. The small C-Si-C angle of 89.1° and the average C[BOND]Si distance of 1.869 Å are consistent with results from theoretical calculations, which revealed that 3 is best described as a silylone.

    7. Oxidative Radical Coupling

      Iron-Catalyzed Oxidative Radical Cross-Coupling/Cyclization between Phenols and Olefins (pages 7151–7155)

      Zhiliang Huang, Dr. Liqun Jin, Ye Feng, Pan Peng, Hong Yi and Prof. Aiwen Lei

      Article first published online: 3 JUN 2013 | DOI: 10.1002/anie.201210023

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      Selectively free: A highly efficient and selective iron-catalyzed oxidative radical cross-coupling/cyclization to prepare dihydrobenzofurans under mild conditions had been established. Phenols and olefins are directly utilized as clean nucleophiles. Mechanistic investigations revealed that the reaction proceeds through a radical pathway, and the high selectivity is due to the Lewis acid.

    8. Dioxygen Activation

      Aerobic Oxysulfonylation of Alkenes Leading to Secondary and Tertiary β-Hydroxysulfones (pages 7156–7159)

      Qingquan Lu, Jian Zhang, Fuliang Wei, Yue Qi, Huamin Wang, Zhiliang Liu and Prof. Aiwen Lei

      Article first published online: 23 MAY 2013 | DOI: 10.1002/anie.201301634

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      New channel! A novel and attractive dioxygen activation by sulfinic acids was explored that is capable of performing efficiently without the assistance of transition metals or radical initiators. This reaction furnishes secondary and tertiary β-hydroxysulfones under mild conditions; β-hydroperoxysulfone was isolated as an important intermediate.

    9. Gold Complexes

      Direct syn Insertion of Alkynes and Allenes into Au[BOND]Si Bonds (pages 7160–7163)

      Maximilian Joost, Dr. Pauline Gualco, Sonia Mallet-Ladeira, Dr. Abderrahmane Amgoune and Dr. Didier Bourissou

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201303450

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      Complete control: Alkynes and allenes are shown to insert into Au[BOND]Si bonds with complete stereocontrol and in most cases complete regiocontrol. The ensuing β-silyl vinylgold complexes have been characterized by spectroscopic and crystallographic means. These results provide unequivocal evidence for syn insertion reactions at gold.

    10. Porphyrinoids

      Metal-Assisted Cyclomerization of N-Confused Dipyrrins into Expanded Norroles (pages 7164–7167)

      Santosh C. Gadekar, Baddigam Kiran Reddy and Prof. Dr. Venkataramanarao G. Anand

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201303184

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      Neoconfusion: In contrast to metal ligation by dipyrrin (see scheme, left), N-confused dipyrrin undergoes cyclomerization with various metal salts to form NCNCNC and NCNCNCNC expanded norroles (see scheme, right), novel isomers of 24 π rosarin and 32 π octaphyrin with C–N linked bipyrrole units with near-planar conformations in the solid state. They also exhibit paratropic ring-current effects typical of antiaromatic porphyrinoids.

    11. Natural Products

      Protecting-Group-Free Total Synthesis of (−)-Rhazinilam and (−)-Rhazinicine using a Gold-Catalyzed Cascade Cyclization (pages 7168–7171)

      Dr. Kenji Sugimoto, Kazuki Toyoshima, Shiori Nonaka, Kenta Kotaki, Dr. Hirofumi Ueda and Prof. Dr. Hidetoshi Tokuyama

      Article first published online: 6 JUN 2013 | DOI: 10.1002/anie.201303067

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      ‘Rhaz'zmatazz: A total synthesis of (−)-rhazinilam and the first asymmetric total synthesis of (−)-rhazinicine were accomplished by using constructing the indolizinone core through the gold-catalyzed cyclization of a fully elaborated linear ynamide. The scope and generality of this cascade reaction for the construction of highly substituted indolizinones were also investigated.

    12. Synthetic Methods

      Asymmetric Ruthenium-Catalyzed Hydrogenation of 2- and 2,9-Substituted 1,10-Phenanthrolines (pages 7172–7176)

      Tianli Wang, Fei Chen, Jie Qin, Yan-Mei He and Prof. Dr. Qing-Hua Fan

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301830

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      A ‘Phen'atic: The title reaction proceeds in the presence of the chiral cationic ruthenium diamine catalyst (R,R)-1 (Tf=trifluoromethanesulfonyl, Ts=4-toluenesulfonyl). Both chiral 1,2,3,4-tetrahydro- and 1,2,3,4,7,8,9,10-octahydro-1,10- phenanthroline derivatives could be obtained in high yields with excellent enantio- and diastereoselectivity.

    13. Asymmetric Catalysis

      In situ Catalytic Generation of Allylcopper Species for Asymmetric Allylation: Toward 1H-Isochromene Skeletons (pages 7177–7180)

      Junya Kawai, Dr. Prasanna Kumara Chikkade, Dr. Yohei Shimizu and Prof. Dr. Motomu Kanai

      Article first published online: 3 JUN 2013 | DOI: 10.1002/anie.201302027

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      Stay active: Allylcopper species can be generated in situ through catalytic intramolecular oxycupration of allenic alcohol. The allylcopper can react with various aldehydes and a ketone to give 1H-isochromene derivatives in an enantioselective manner (see scheme; HMPA=hexamethylphosphoramide, THF=tetrahydrofuran). The protocol is atom-economical, highly regioselective, stereoconvergent, and tolerant to free hydroxy groups.

    14. Brucellosis Detection

      Design and Synthesis of a Universal Antigen to Detect Brucellosis (pages 7181–7185)

      Dr. Julie Guiard, Dr. Eugenia Paszkiewicz, Joanna Sadowska and Prof. David R. Bundle

      Article first published online: 11 JUN 2013 | DOI: 10.1002/anie.201302303

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      Upgrading diagnostics: A universal antigen has been prepared for the detection of brucellosis caused by any Brucella species that express a smooth lipopolysaccharide. This nonasaccharide, which encompasses Brucella A- and M-antigenic determinants, is uniquely available only by chemical synthesis.

    15. Gas-Phase Chemistry

      A Combined Experimental and Theoretical Study on the Gas-Phase Synthesis of Toluene under Single Collision Conditions (pages 7186–7189)

      Dr. Beni B. Dangi, Dr. Dorian S. N. Parker, Prof. Ralf I. Kaiser, Dr. Adeel Jamal and Prof. Alexander M. Mebel

      Article first published online: 3 JUN 2013 | DOI: 10.1002/anie.201302344

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      Reaction dynamics: Crossed molecular beam experiments and ab initio electronic structure calculations on the reaction of the ethynyl radical with isoprene are reported. The picture shows a flux contour map of the reaction of [D1]ethynyl with isoprene forming [D1]toluene and atomic hydrogen at a collision energy of 51.3 kJ mol−1.

    16. Homogeneous Catalysis

      You have full text access to this OnlineOpen article
      Modifying Alkylzinc Reactivity with 2,2′-Dipyridylamide: Activation of tBu[BOND]Zn Bonds for para-Alkylation of Benzophenone (pages 7190–7193)

      Dr. David R. Armstrong, Jennifer A. Garden, Dr. Alan R. Kennedy, Prof. Robert E. Mulvey and Dr. Stuart D. Robertson

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201302426

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      Undercover agent: Masquerading as a simple donor-acceptor complex (1), sodium amide substoichiometrically activates tBu2Zn for the challenging 1,6-addition of a tert-butyl group to benzophenone. In contrast, the nonactivated tBu2Zn is ineffectual.

    17. Synthetic Methods

      Three-Component Metal-Free Arylation of Isocyanides (pages 7194–7197)

      Unnamatla M. V. Basavanag, Aurélie Dos Santos, Dr. Laurent El Kaim, Dr. Rocio Gámez-Montaño and Dr. Laurence Grimaud

      Article first published online: 29 MAY 2013 | DOI: 10.1002/anie.201302659

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      Mumm's the word: The title reaction can be performed by the addition of isocyanides to benzenediazonium salts in the presence of sodium or potassium carboxylates. The reaction involves nitrilium intermediates which may be trapped by water or carboxylic acids to form amides and imides, respectively, after Mumm rearrangement.

    18. The Supersilyl Group as a Carboxylic Acid Protecting Group: Application to Highly Stereoselective Aldol and Mannich Reactions (pages 7198–7202)

      Jiajing Tan, Prof. Dr. Matsujiro Akakura and Prof. Dr. Hisashi Yamamoto

      Article first published online: 29 MAY 2013 | DOI: 10.1002/anie.201300102

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      Silyl superpowers: The supersilyl group was investigated as a superior carboxylic acid protecting group. Supersilyl esters were also utilized as stable carboxylic acid synthetic equivalents in highly stereoselective aldol and Mannich reactions (see scheme). The value of this method lies in easy photodeprotection and in the rapid synthesis of polyketide subunits.

    19. Self-Assembled Nanostructures

      Bottom-Up-Assembled Nanostar Colloids of Gold Cores and Tubes Derived From Tobacco Mosaic Virus (pages 7203–7207)

      Dr. Fabian J. Eber, Dr. Sabine Eiben, Prof. Holger Jeske and Prof. Christina Wege

      Article first published online: 12 JUN 2013 | DOI: 10.1002/anie.201300834

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      Twinkle, twinkle little star: Directed self-assembly of bioinorganic hybrid nanostars with a high protein surface area was achieved by encapsidating immobilized RNA on metal beads with a plant viral protein. The selectivity of RNA hybridization to oligodeoxynucleotides exposed on the gold allowed the simultaneous fabrication of star colloids with distinct predetermined arm-length distributions in single-batch processes.

    20. Micromotors

      Self-Propelled Micromotors Driven by the Magnesium–Water Reaction and Their Hemolytic Properties (pages 7208–7212)

      Dr. Fangzhi Mou, Chuanrui Chen, Prof. Huiru Ma, Dr. Yixia Yin, Prof. Qingzhi Wu and Prof. Jianguo Guan

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201300913

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      Get your motor running: A hemocompatible Mg/Pt Janus micromotor is propelled by hydrogen bubbles generated by the magnesium–water reaction (see picture). Aqueous NaHCO3 reacts with the Mg(OH)2 passivation layer on the Mg surface to form water-soluble MgCO3 and expose the active metal. Since the micromotor is biocompatible, it has potential applications in drug delivery and cell separation.

    21. Metallocavitands

      NHC-Capped Cyclodextrins (ICyDs): Insulated Metal Complexes, Commutable Multicoordination Sphere, and Cavity-Dependent Catalysis (pages 7213–7218)

      Maxime Guitet, Pinglu Zhang, Dr. Filipa Marcelo, Coralie Tugny, Prof. Jesús Jiménez-Barbero, Dr. Olivier Buriez, Prof. Christian Amatore, Dr. Virginie Mouriès-Mansuy, Dr. Jean-Philippe Goddard, Prof. Louis Fensterbank, Dr. Yongmin Zhang, Dr. Sylvain Roland, Dr. Mickaël Ménand and Prof. Matthieu Sollogoub

      Article first published online: 3 JUN 2013 | DOI: 10.1002/anie.201301225

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      Don't slam the door! Cyclodextrins capped with an N-heterocyclic carbene (ICyDs) entrapped metal ions within their cavity through a novel set of interactions, including X⋅⋅⋅π, which enabled the cavity to be closed by ligand exchange (see scheme; Bn=benzyl). Although insulated from an electrode, the deeply buried metal ions retained catalytic activity. The cavity influenced the regio- and stereochemical outcome of the catalyzed reactions.

    22. Synthetic Methods

      Regioselective One-Step Synthesis of Pyrazoles from Alkynes and N-Tosylhydrazones: [3+2] Dipolar Cycloaddition/[1,5] Sigmatropic Rearrangement Cascade (pages 7219–7223)

      M. Carmen Pérez-Aguilar and Dr. Carlos Valdés

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301284

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      Rearrangement under control: A wide variety of 3,4,5- and 1,3,5-trisubstituted pyrazoles can be prepared from tosylhydrazones of ketones and terminal alkynes through the title reaction sequence (see scheme; Ts=4-toluenesulfonyl). The rearrangement, and therefore, the regioselectivity of the reaction is controlled by the nature of the substituents of the tosylhydrazone.

    23. Heterogeneous/Homogeneous Catalysis

      Sustained Water Oxidation by a Catalyst Cage-Isolated in a Metal–Organic Framework (pages 7224–7227)

      Binod Nepal and Dr. Siddhartha Das

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201301327

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      Keep 'em separated: Pores of a MOF were used to isolate a highly reactive water-oxidation catalyst (MnIII(μ-O)2MnIV; spheres in picture). The resulting construct shows highly sustained water oxidation, with minimized intermolecular degradative side-reactions. This system provides a simple path to extend the lifetime of reactive catalysts without compromising their molecular definition and reactivity.

    24. Asymmetric Catalysis

      Peptide-Catalyzed Stereoselective Conjugate Addition Reactions Generating All-Carbon Quaternary Stereogenic Centers (pages 7228–7232)

      Robert Kastl and Prof. Dr. Helma Wennemers

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201301583

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      A powerful catalyst: Quaternary stereogenic centers adjacent to tertiary stereocenters were formed with high diastereoselectivities and enantioselectivities in conjugate addition reactions between aldehydes and β,β-disubstituted nitroolefins by using a peptidic catalyst (see scheme). γ-Amino acids and heterocyclic compounds bearing quaternary stereogenic centers are easily accessible from the products.

    25. Biofuel Cells

      Epidermal Biofuel Cells: Energy Harvesting from Human Perspiration (pages 7233–7236)

      Dr. Wenzhao Jia, Dr. Gabriela Valdés-Ramírez, Amay J. Bandodkar, Dr. Joshua R. Windmiller and Prof. Joseph Wang

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201302922

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      No sweat, no gain: Flexible biofuel cells functionalized with lactate oxidase (LOx) and platinum as anode and cathode materials harvested biochemical energy from human perspiration (see picture). Substantial power was generated from human sweat in real-life scenarios.

    26. Thulium Diiodide

      You have full text access to this OnlineOpen article
      Uncovering the Importance of Proton Donors in TmI2-Promoted Electron Transfer: Facile C[BOND]N Bond Cleavage in Unactivated Amides (pages 7237–7241)

      Dr. Michal Szostak, Malcolm Spain and Prof. Dr. David J. Procter

      Article first published online: 12 JUN 2013 | DOI: 10.1002/anie.201303178

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      Nonclassical lanthanide(II) iodides are modern reagents for the development of challenging electron-transfer processes. It was demonstrated that alcohols are critical for the formation of a thermodynamically more powerful reductant from TmI2 (thulium diiodide), the first nonclassical lanthanide(II) iodide in the series (TmI2, DyI2, NdI2). The TmI2(ROH)n reagent promotes an unprecedented cleavage of the σ C[BOND]N bond in amides.

    27. Synthetic Methods

      Addressing Challenges in Palladium-Catalyzed Cross-Couplings of Aryl Mesylates: Monoarylation of Ketones and Primary Alkyl Amines (pages 7242–7246)

      Pamela G. Alsabeh and Prof. Dr. Mark Stradiotto

      Article first published online: 12 JUN 2013 | DOI: 10.1002/anie.201303305

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      Mor(DalPhos) for Me(sylates): Described are the first examples of ketone mono-α-arylation and primary aliphatic amine monoarylation employing aryl methanesulfonate coupling partners. A range of functionalized aryl mesylates were employed with dialkyl ketones, and also with primary and secondary amines as well as the otherwise challenging coupling partners acetone and methylamine. Ad=adamantyl.

    28. Coordination Chemistry

      Formation of Bismuth(V) Thiolates: Protolysis and Oxidation of Triphenylbismuth(III) with Heterocyclic Thiols (pages 7247–7251)

      Ahmad Luqman, Dr. Victoria L. Blair, Prof. Alan M. Bond and Prof. Philip C. Andrews

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301200

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      Stressing bismuth: Two monophenyl tetrathiolato BiV complexes, [BiPh(SR)4], have been prepared upon treating BiPh3 in toluene/ethanol under reflux conditions with an excess of N-heterocyclic thiols (see scheme), indicating oxidation of the bismuth center. Crystallization from DMSO over several months leads to reduction of bismuth back to BiIII through protonation of two of the thiolato ligands.

    29. Macrocyclic Hosts

      Twisted Cucurbit[14]uril (pages 7252–7255)

      Xiao-Jie Cheng, Li-Li Liang, Kai Chen, Ning-Ning Ji, Prof. Xin Xiao, Prof. Jian-Xin Zhang, Prof. Yun-Qian Zhang, Prof. Sai-Feng Xue, Prof. Dr. Qian-Jiang Zhu, Dr. Xin-Long Ni and Prof. Dr. Zhu Tao

      Article first published online: 28 MAY 2013 | DOI: 10.1002/anie.201210267

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      All in a twist: The largest cucurbit[n]uril, namely tQ[14] (see picture; colors indicate sides of the molecule) contains 14 normal glycoluril units linked by 28 methylene bridges. However, it contains a 360° twist. As a consequence, it does not have a normal cavity like the most cucurbit[n]urils, and instead has a folded, figure-of-eight conformation.

    30. In-Flow Purification

      Steady-State Continuous-Flow Purification by Electrophoresis (pages 7256–7260)

      Fletcher J. Agostino, Dr. Leonid T. Cherney, Dr. Victor Galievsky and Prof. Sergey N. Krylov

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201300104

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      Bubble and sweep: Free-flow electrophoresis (FFE) could allow continuous-flow purification of products from continuous-flow microsynthesis. However, gas bubbles distort the separation. An open-electrolyte FFE system avoids this problem. Electrodes placed in chimneys open to the atmosphere mean bubbles are vented directly from the system and cannot enter the separation channel (see picture).

    31. Pigments

      Production of Colored Pigments with Amorphous Arrays of Black and White Colloidal Particles (pages 7261–7265)

      Prof. Yukikazu Takeoka, Prof. Shinya Yoshioka, Prof. Atsushi Takano, Dr. Shigeo Arai, Khanin Nueangnoraj, Prof. Hirotomo Nishihara, Midori Teshima, Yumiko Ohtsuka and Prof. Takahiro Seki

      Article first published online: 27 MAY 2013 | DOI: 10.1002/anie.201301321

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      Sprayed: Pigments with various angle-independent colors were prepared by a spray method (see picture), which is a remarkably simple method using submicrometer-sized silica particles and carbon black. The use of a polyelectrolyte that adheres to the particles can stabilize the structure of the colloidal amorphous arrays to create highly stressable, nonfading pigments.

    32. Detection of Glycans

      A Bioorthogonal Raman Reporter Strategy for SERS Detection of Glycans on Live Cells (pages 7266–7271)

      Liang Lin, Xiangdong Tian, Senlian Hong, Peng Dai, Qiancheng You, Ruyi Wang, Lianshun Feng, Prof. Can Xie, Prof. Zhong-Qun Tian and Prof. Xing Chen

      Article first published online: 23 MAY 2013 | DOI: 10.1002/anie.201301387

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      Direct detection of glycans on live cells using surface-enhanced Raman scattering (SERS) has been shown. A bioorthogonal Raman reporter was directly installed onto the monosaccharide analogs. Once metabolically incorporated into cell surface glycans, the Raman reporter was detected using SERS (see picture).

    33. Polyrotaxanes

      Synthesis of Paclitaxel-Conjugated β-Cyclodextrin Polyrotaxane and Its Antitumor Activity (pages 7272–7277)

      Shuling Yu, Yajun Zhang, Xin Wang, Xu Zhen, Zhaoheng Zhang, Dr. Wei Wu and Prof. Xiqun Jiang

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201301397

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      Cap it all: A β-cyclodextrin polyrotaxane was synthesized by using poly(propylene glycol) as the axle and β-cyclodextrin as the end cap. An antitumor agent, paclitaxel, was conjugated to it. The drug-conjugated polyrotaxane penetrates deep into tumors, impedes tumor growth, and prolongs the life of tumor-bearing mice better than Taxol.

    34. RNA–Protein Complexes

      The Structure of FemXWv in Complex with a Peptidyl-RNA Conjugate: Mechanism of Aminoacyl Transfer from Ala-tRNAAla to Peptidoglycan Precursors (pages 7278–7281)

      Dr. Matthieu Fonvielle, Dr. Inés Li de La Sierra-Gallay, Dr. Afaf H. El-Sagheer, Maxime Lecerf, Delphine Patin, Dr. Dénia Mellal, Dr. Claudine Mayer, Dr. Didier Blanot, Dr. Nittaya Gale, Dr. Tom Brown, Dr. Herman van Tilbeurgh, Dr. Mélanie Ethève-Quelquejeu and Dr. Michel Arthur

      Article first published online: 6 JUN 2013 | DOI: 10.1002/anie.201301411

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      To gain insight into the catalytic mechanism of non-ribosomal amino acid transferases, peptidyl-RNA conjugates were synthesized for co-crystallization with FemXWv of Weissella viridescens, which transfers L-Ala from Ala-tRNAAla to the peptidoglycan precursor UDP-MurNAc-pentapeptide. The structure of the resulting complex and mutational studies revealed the mechanism by which FemXWv binds its substrates for substrate-assisted catalysis and stabilization of the tetrahedral intermediate.

    35. CO Reduction Mechanism

      Theoretical Considerations on the Electroreduction of CO to C2 Species on Cu(100) Electrodes (pages 7282–7285)

      Dr. Federico Calle-Vallejo and Prof. Marc T. M. Koper

      Article first published online: 3 JUN 2013 | DOI: 10.1002/anie.201301470

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      CO-products: DFT calculations are used to construct a mechanism for the electrochemical reduction of CO on Cu(100) that agrees with the experimental observations (see picture) of pH independence in the formation of C2 species. The rate-determining step is an electron-transfer-mediated CO dimerization. Ethylene, acetaldehyde, and ethanol are formed through a common pathway, and adsorbed ethylene oxide is one of the reaction intermediates.

    36. Nanosolvation

      Nanosolvation-Induced Stabilization of a Protonated Peptide Dimer Isolated in the Gas Phase (pages 7286–7290)

      Dr. Aleksandar R. Milosavljević, Dr. Viktor Z. Cerovski, Dr. Francis Canon, Dr. Laurent Nahon and Dr. Alexandre Giuliani

      Article first published online: 6 JUN 2013 | DOI: 10.1002/anie.201301667

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      A dash of water: Nanosolvation of a leucine–enkephalin peptide dimer by only three water molecules has a dramatic impact on its stability to VUV photon irradiation. A drastic reduction of the fragmentation abundance of the hydrated protonated peptide dimer precursor, isolated in the gas phase, was observed. Calculations show that hydration in fact stabilizes the dimer structure.

    37. Marangoni Tweezers

      Particle Manipulation Based on Optically Controlled Free Surface Hydrodynamics (pages 7291–7295)

      Subramanyan Namboodiri Varanakkottu, Dr. Sajan Daniel George, Dr. Tobias Baier, Prof. Steffen Hardt, Martina Ewald and Prof. Markus Biesalski

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201302111

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      Microparticle manipulation: The photoisomerization of surfactants adsorbed at a gas–liquid interface drives a Marangoni flow that can be used for the trapping and manipulation of small particles. By switching the laser wavelength, a flow either into or away from the focal spot can be induced. The picture shows a microparticle trapped in the focal region by the inflow.

    38. Photonic Crystals

      A Multi-stopband Photonic-Crystal Microchip for High-Performance Metal-Ion Recognition Based on Fluorescent Detection (pages 7296–7299)

      Yu Huang, Fengyu Li, Meng Qin, Lei Jiang and Yanlin Song

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201302311

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      Twelve metal ions are analyzed by a microchip that was developed for high-performance recognition and analysis. The microchip enhances fluorescence at multiple channels and improves the discriminability of multi-analyte testing. The facile fabrication of the microchip and insights into sensing efficiency will be of great importance for the development of advanced discriminant analysis for complex analytes.

    39. Polymersomes

      One-Pot Synthesis of an Acid-Labile Amphiphilic Triblock Copolymer and its pH-Responsive Vesicular Assembly (pages 7300–7305)

      Krishna Dan and Dr. Suhrit Ghosh

      Article first published online: 4 JUN 2013 | DOI: 10.1002/anie.201302722

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      An amphiphilic triblock copolymer segmented by an acid-labile β-thiopropionate linker was synthesized from a dithiol, a diacrylate, and an acrylate-terminated hydrophilic polymer in two steps in one pot. It showed spontaneous vesicular assembly, and the stimuli-responsive disassembly at mild acidic pH values resulted in sustained release of noncovalently encapsulated guest molecules.

    40. Metalloporphyrinoids

      η5-Cyclopentadienyliron(II)–[14]Triphyrin(2.1.1) Sandwich Compounds: Synthesis, Characterization, and Stable Redox Interconversion (pages 7306–7309)

      Dr. Zhaoli Xue, Dr. Daiki Kuzuhara, Dr. Shinya Ikeda, Yuka Sakakibara, Prof. Kei Ohkubo, Prof. Naoki Aratani, Prof. Tetsuo Okujima, Prof. Hidemitsu Uno, Prof. Shunichi Fukuzumi and Prof. Hiroko Yamada

      Article first published online: 29 MAY 2013 | DOI: 10.1002/anie.201302815

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      A semiferrocene complex with a [14]triphyrin(2.1.1) (TriP) ligand has been synthesized. The structure and properties are characterized by X-ray crystallographic analysis, UV/Vis spectroscopy, and variable-temperature 1H NMR spectroscopy. The FeII and FeIII complexes are electrochemically reversible.

    41. Asymmetric Catalysis

      Direct Catalytic Asymmetric Vinylogous Mannich-Type Reaction of γ-Butenolides with Ketimines (pages 7310–7313)

      Dr. Liang Yin, Dr. Hisashi Takada, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 29 MAY 2013 | DOI: 10.1002/anie.201303119

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      A cooperative catalyst consisting of a soft Lewis acid and a hard Brønsted base promoted the title reaction. The N-thiophosphinoyl group on the ketimines was critical to surpass the high activation barrier through the soft–soft interaction of sulfur and copper. Mannich adducts with a tetrasubstituted stereogenic center were produced with excellent diastereo- and enantioselectivities. TANIAPHOS= ferrocenyl ligand.

    42. Through-Bond Interactions

      Stereoelectronic Effect of Curved Aromatic Structures: Favoring the Unexpected endo Conformation of Benzylic-Substituted Sumanene (pages 7314–7316)

      Prof. Dr. Shuhei Higashibayashi, Satoru Onogi, Dr. Hemant Kumar Srivastava, Dr. G. Narahari Sastry, Prof. Dr. Yao-Ting Wu and Prof. Dr. Hidehiro Sakurai

      Article first published online: 10 JUN 2013 | DOI: 10.1002/anie.201303134

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      Throwing a curve: The first example of a through-bond stereoelectronic effect for curved aromatic compounds is described for buckybowls, that is, benzylic-substituted sumanenes. Methyl- and hydroxysumanene favor the endo-R conformer because of a difference in the strength, between the conformers, of the hyperconjugation of the benzylic C[BOND]H bond with the bowl.

    43. Synthesis Design

      C[BOND]H Functionalization Logic Enables Synthesis of (+)-Hongoquercin A and Related Compounds (pages 7317–7320)

      Brandon R. Rosen, Leah R. Simke, Peter S. Thuy-Boun, Dr. Darryl D. Dixon, Prof. Dr. Jin-Quan Yu and Prof. Dr. Phil S. Baran

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201303838

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      The specifics: A synthesis of the sesquiterpenoid antibiotic (+)-hongoquercin A using sequential site-specific C[BOND]H methylation and oxidation reactions is described. A key advancement toward this goal was the development of a ligand-accelerated C[BOND]H methylation reaction, and enabled the generation of a library of eight structurally diverse analogues.

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