European Journal of Organic Chemistry

Cover image for Vol. 2013 Issue 5

February 2013

Volume 2013, Issue 5

Pages 795–1008

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. You have free access to this content
      An Efficient and Reliable Catalyst System Using Hemilabile Aphos for B-Alkyl Suzuki–Miyaura Cross-Coupling Reaction with Alkenyl Halides (Eur. J. Org. Chem. 5/2013)

      Ning Ye and Wei-Min Dai

      Article first published online: 6 FEB 2013 | DOI: 10.1002/ejoc.201390009

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      The cover picture shows a snapshot of the blooming canola field in Southwest China. The catalytic cycle illustrates the P,O-chelating and P-monodentate complexation modes of the hemilabile Aphos-Y with palladium(0) and the reductive elimination of the P,O-chelating palladium(II) species derived from an alkyl borinate and an alkenyl halide under mild conditions (K3PO4·3H2O, THF/H2O, r.t.). It is considered that switching between the P,O-chelating and P-monodentate complexation modes facilitates various steps in the whole catalytic cycle. The usefulness of the Aphos-Y–Pd(OAc)2 catalyst in the “9-MeO-9-BBN variant” of the Suzuki–Miyaura cross-coupling reaction used for the total synthesis of complex natural products has been demonstrated. Details are discussed in the Short Communication by N. Ye and W.-M. Dai on p. 831 ff.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
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    1. Graphical Abstract: Eur. J. Org. Chem. 5/2013 (pages 795–802)

      Article first published online: 6 FEB 2013 | DOI: 10.1002/ejoc.201390011

  3. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
  4. Microreview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. Functionalized Piperidines

      Synthesis of 3-Hydroxypipecolic Acids (pages 809–829)

      Anne Cochi, Domingo Gomez Pardo and Janine Cossy

      Article first published online: 14 JAN 2013 | DOI: 10.1002/ejoc.201201415

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      This article reviews the total syntheses of all four stereoisomers of 3-hydroxypipecolic acids 14 from 1996 to the present.

  5. Short Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. Cross-Coupling

      An Efficient and Reliable Catalyst System Using Hemilabile Aphos for B-Alkyl Suzuki–Miyaura Cross-Coupling Reaction with Alkenyl Halides (pages 831–835)

      Ning Ye and Wei-Min Dai

      Article first published online: 2 JAN 2013 | DOI: 10.1002/ejoc.201201602

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      One ligand acts for two: Aphos-Y and Pd(OAc)2 enable the cross-coupling of the 9-alkyl-9-MeO-9-BBN species formed from an alkyl iodide (step a: tBuLi, 9-MeO-9-BBN) and an alkenyl halide with excellent yield under mild conditions (step b: K3PO4·3H2O, THF/H2O, room. temp.). Aphos-Y substitutes two ligands, dppf and Ph3As, popularly used in the “9-MeO-9-BBN variant” of Suzuki–Miyaura cross-coupling.

    2. Modified Julia Olefination

      On the Origin of E/Z Selectivity in the Modified Julia Olefination – Importance of the Elimination Step (pages 836–840)

      Raphaël Robiette and Jiří Pospíšil

      Article first published online: 8 JAN 2013 | DOI: 10.1002/ejoc.201201634

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      A detailed investigation of the modified Julia olefination of aromatic aldehydes shows that the elimination step occurs through a concerted antiperiplanar and synperiplanar mechanism in the case of anti-5 and syn-5, respectively. The high experimental E selectivity is thus explained by the fact that both syn and anti diastereomeric pathways lead preferentially to the (E)-alkene.

    3. Tandem Reactions

      Substituted 3(2H)-Furanones by a Tandem Michael Addition/Palladium-Catalyzed Ring-Closing Protocol (pages 841–845)

      Jubi John and Henning Hopf

      Article first published online: 4 JAN 2013 | DOI: 10.1002/ejoc.201201253

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      Substituted 3(2H)-furanones are synthesized in good to excellent yields by the palladium-catalyzed reaction of 4-chloroacetoactate with activated styrenes. The tandem reaction starts with Michael addition of an acetoacetate to the activated alkene followed by palladium-catalyzed ring closing of the primary adduct to form the furanone.

    4. Azanucleotide Analogues

      Tuning the Stereoselectivity in One-Pot Scission/Addition Processes: Synthesis of Azanucleotide Analogues from Proline Derivatives (pages 846–852)

      Javier Miguélez-Ramos, Venkateswara Rao Batchu and Alicia Boto

      Article first published online: 15 JAN 2013 | DOI: 10.1002/ejoc.201201443

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      The one-pot conversion of proline derivatives into azanucleotide analogues has been achieved in good yields by a sequential radical decarboxylation/phosphorylation process. The stereoselectivity of the reaction can be controlled by using different oxygen and nitrogen substituents at C-4 and in this way the 2,4-cis/2,4-trans ratio can be shifted from 98:2 to 15:85.

    5. Synthetic Methods

      Approaches to the Synthesis of a Water-Soluble Carboxy Nitroxide (pages 853–857)

      Komba Thomas, Benjamin A. Chalmers, Kathryn E. Fairfull-Smith and Steven E. Bottle

      Article first published online: 8 JAN 2013 | DOI: 10.1002/ejoc.201201551

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      Several synthetic approaches to an important water-soluble nitroxide antioxidant are described. Each provides the final product in a comparable overall yield, however, the copper-mediated cyanation of an aryl halide followed by hydrolysis employs the fewest steps and provides the greatest synthetic convenience.

    6. Cross-Dehydrogenative Coupling

      Iodide-Ion-Catalyzed Carbon–Carbon Bond-Forming Cross-Dehydrogenative Coupling for the Synthesis of Indole Derivatives (pages 858–861)

      Zhenhua Jia, Takashi Nagano, Xingshu Li and Albert S. C. Chan

      Article first published online: 4 JAN 2013 | DOI: 10.1002/ejoc.201201585

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      We have found that the intramolecular oxidative coupling of N-arylenamines proceeds well in the presence of catalytic amounts of nBu4NI (TBAI) using tert-butyl hydroperoxide as oxidant to afford the corresponding 1H-indole derivatives. This is one of the rare examples of TBAI-catalyzed C–C bond-forming CDC reactions.

    7. Cross-Coupling

      An Easy Route to N,N-Diarylhydrazines by Cu-Catalyzed Arylation of Pyridine-2-carbaldehyde Hydrazones with Aryl Halides (pages 862–867)

      Wei Wu, Xin-Le Li, Xin-Heng Fan and Lian-Ming Yang

      Article first published online: 7 JAN 2013 | DOI: 10.1002/ejoc.201201445

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      A Cu-catalyzed C–N coupling reaction is described for the synthesis of pyridine-2-carbaldehyde N,N-diarylhydrazones by the arylation of hydrazones with aryl bromides/iodides, and the subsequent conversion of the hydrazones into N,N-diarylhydrazines by a transimination process with an aqueous solution of H2NNH2. The reaction features the use of CuI as catalyst without external ligands.

  6. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Microreview
    6. Short Communications
    7. Full Papers
    1. Molecular Electronics

      Post-Cycloaddition–Retroelectrocyclization Transformations of Polycyanobutadienes (pages 869–879)

      Adam R. Lacy, Anna Vogt, Corinne Boudon, Jean-Paul Gisselbrecht, W. Bernd Schweizer and François Diederich

      Article first published online: 17 DEC 2012 | DOI: 10.1002/ejoc.201201371

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      The use of ethynylated anilines as activated alkynes in cycloaddition–retroelectrocyclization reactions with tetracyanoethene and tetracyanoquinodimethane provides access to novel, highly electron-deficient polycyanobutadienes and unprecedented chromophores. Electrochemical studies show that the electron-accepting abilities are strongly enhanced upon elimination of the amino donor substituent.

    2. Drug Design

      5-Substituted (1-Thiolan-2-yl)cytosines as Inhibitors of A. aeolicus and E. coli IspE Kinases: Very Different Affinities to Similar Substrate-Binding Sites (pages 880–887)

      Andri P. Schütz, Sebastian Locher, Bruno Bernet, Boris Illarionov, Markus Fischer, Adelbert Bacher and François Diederich

      Article first published online: 3 JAN 2013 | DOI: 10.1002/ejoc.201201454

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      We report the design, synthesis, and biological evaluation of N(1)-thiolan-2-ylated and C(5)-substituted ligands. The compounds were used to explore the molecular recognition properties of the methylerithritol sub-pocket of the substrate binding site in IspE proteins from Escherichia coli and Aquifex aeolicus, which are model enzymes for Plasmodium falciparum IspE, the causative agent of malaria.

    3. Imaging Agents

      A Chloroacetate-Caged Fluorescein Chemodosimeter for Imaging Cysteine/Homocysteine in Living Cells (pages 888–893)

      Baocun Zhu, Yunzhou Zhao, Qi Zhou, Bing Zhang, Lunying Liu, Bin Du and Xiaoling Zhang

      Article first published online: 3 JAN 2013 | DOI: 10.1002/ejoc.201201407

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      A chloroacetate-caged fluorescein chemodosimeter (CACFC) employing a double molecular recognition mechanism was designed and synthesized to selectively detect cysteine (Cys) and homocysteine (Hcy) over glutathione (GSH) and other amino acids.

    4. Marine Alkaloids

      Alkaloids from the Sponge-Associated Fungus Aspergillus sp. (pages 894–906)

      Yaming Zhou, Abdessamad Debbab, Attila Mándi, Victor Wray, Barbara Schulz, Werner E. G. Müller, Matthias Kassack, WenHan Lin, Tibor Kurtán, Peter Proksch and Amal H. Aly

      Article first published online: 11 DEC 2012 | DOI: 10.1002/ejoc.201201220

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      Seven new alkaloids including tryptoquivaline K (1) and fumiquinazolines K–P (2–7), bearing a rare 1-aminocyclopropane-1-carboxylic acid residue, together with six known compounds, were isolated from the sponge-associated fungus Aspergillus sp. The structures of the new compounds were assigned by spectral analysis, and their absolute configurations were determined by calculations.

    5. Chemoselectivity in Cycloaddition

      Gold(I)-Catalysed Alkene Cycloaddition Reactions of Propargyl Acetals (pages 907–914)

      Naseem Iqbal, Christian A. Sperger and Anne Fiksdahl

      Article first published online: 2 JAN 2013 | DOI: 10.1002/ejoc.201201328

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      A study of chemoselective gold(I)-catalysed cycloaddition of propargyl acetals or esters with alkenes and indoles showed them to follow two different pathways. Whereas the esters underwent cyclopropanation, the acetals showed two important features: (i) the favoured pathway is an atypical [2+3] cycloaddition, and (ii) these complexes showed significantly higher reactivities than the ester counterparts.

    6. Spiroketal Synthesis

      A Concise and Efficient Synthesis of Spiroketals – Application to the Synthesis of SPIKET-P and a Spiroketal from Bactrocera Species (pages 915–920)

      Loic Tomas, Benjamin Bourdon, Jean Claude Caille, David Gueyrard and Peter G. Goekjian

      Article first published online: 10 JAN 2013 | DOI: 10.1002/ejoc.201201199

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      We report the synthesis of spiroketals by a sequence of enol ether synthesis and cyclization. The enol ethers were prepared from lactones by a Julia olefination, and the starting chiral lactone was prepared from an industrial intermediate. This route allows the synthesis of naturally occurring and biologically interesting spiroketals, including SPIKET-P and a spiroketal from Bactrocera species.

    7. Tetrathiafulvalenes

      Amino Acid Derivatives of Tetrathiafulvalene and Their N–H···O Peptide Bond Dipoles-Templated Solid State Assemblies (pages 921–928)

      Abdelkrim El-Ghayoury, Leokadiya Zorina, Sergey Simonov, Lionel Sanguinet and Patrick Batail

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejoc.201201330

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      The synthesis of a new series of amino acid-appended ethylenedithiotetrathiafulvalene or dimethyltetrathiafulvalene cores reveals three characteristic hydrogen-bonding types of interactions that effectively direct self-assembly in the solid state.

    8. Phthalimide Photochemistry

      Photoinduced H-Abstraction in Homo- and Protoadamantylphthalimide Derivatives in Solution and in Organized and Constrained Media (pages 929–938)

      Nikola Cindro, Ivan Halasz, Kata Mlinarić-Majerski and Nikola Basarić

      Article first published online: 7 JAN 2013 | DOI: 10.1002/ejoc.201201332

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      Photochemical reactions of phthalimide derivatives 5, 9 and 10 afford different polycyclic rearrangement products as a function of irradiation conditions.

    9. Glycomimetics

      A Protection-Free Synthetic Access to (±)-1-Deoxy-6-epi-castanospermine and (±)-1-Deoxy-6,8a-di-epi-castanospermine (pages 939–943)

      Angeliki-Theodora Serafidou, Efthymia G. Yioti and John K. Gallos

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejoc.201201334

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      A protecting-group-free approach to the title compounds has been developed. Starting from the hetero-Diels–Alder adduct of ethyl 2-nitrosoacrylate and ethyl vinyl ether, two isomeric terminal dienes were prepared, which, upon RCM followed by dihydroxylation and catalytic Raney Ni hydrogenation, led to the target compounds, which are of significant biological interest.

    10. Arylation of α-Hydroxyphosphonates

      FeCl3-Mediated Arylation of α-Hydroxyphosphonates with Unactivated Arenes: Pseudo-Umpolung in Allylic Phosphonates (pages 944–951)

      Gangaram Pallikonda and Manab Chakravarty

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejoc.201201352

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      A facile and solvent-free synthesis of γ-aryl-substituted vinylphosphonates and diethyl (diarylmethyl)phosphonates has been developed under mild conditions. The reaction was performed with inexpensive FeCl3 and easily accessible α-hydroxyphosphonates and unactivated arenes. In this atom-economic approach, hard-to-achieve allylphosphonate cations are stabilized through extended conjugation.

    11. Heterocyclic Chemistry

      Stereoselective Synthesis of Tetrahydroquinolines Through an Imino-Ene Cyclization Reaction (pages 952–956)

      Somasekhar Bondalapati, Kiran Indukuri, Priya Ghosh and Anil K. Saikia

      Article first published online: 3 JAN 2013 | DOI: 10.1002/ejoc.201201363

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      An efficient methodology has been developed for the synthesis of tetrahydroquinolines in good yields and with excellent diastereoselectivity. The reaction between α-allylic anilines and aldehydes proceeds through an imino-ene cyclization that is mediated by boron trifluoride–diethyl ether.

    12. Azulene Chemistry

      Synthesis, Properties and Redox Behavior of Ene–Diyne Scaffolds Bearing 1- and 2-Azulenyl Groups at the Periphery (pages 957–964)

      Taku Shoji, Erika Shimomura, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima and Noboru Morita

      Article first published online: 3 JAN 2013 | DOI: 10.1002/ejoc.201201397

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      Ene–diyne systems possessing 1- and 2-azulenyl groups at the periphery, were prepared by Sonogashira–Hagihara reactions. The redox behavior of the ene–diyne compounds was examined by cyclic voltammetry and differential pulse voltammetry. Significant color changes of the ene–diyne derivatives were observed by visible spectroscopy under electrochemical reduction conditions.

    13. Friedel–Crafts-Type Cyclization

      Synthesis of 3,4-Dihydroisoquinolin-1-ones from N-Boc-(β-Arylethyl)carbamates via Isocyanate Intermediates (pages 965–971)

      Jinkyung In, Soonho Hwang, Changhun Kim, Jae Hong Seo and Sanghee Kim

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejoc.201201408

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      Isoquinolin-1-ones and related fused-ring heterocycles have been prepared from N-Boc-protected (β-arylethyl)carbamates. The N-Boc-carbamates were first converted into isocyanates by using the reagents Tf2O and 2-chloropyridine. These isocyanates were then subjected to in situ intramolecular Friedel–Crafts-type reaction to give the products in good yields and with high regioselectivities.

    14. Double Clicked Thiolactosides

      Efficient Synthesis of Thiolactoside Glycoclusters by Ruthenium-Catalyzed Cycloaddition Reaction of Disubstituted Alkynes on Carbohydrate Scaffolds (pages 972–983)

      Alejandro J. Cagnoni, Oscar Varela, María Laura Uhrig and José Kovensky

      Article first published online: 13 DEC 2012 | DOI: 10.1002/ejoc.201201412

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      Ruthenium-catalyzed cycloaddition of symmetric disubstituted alkynes bearing two thiosugar units and azide-containing carbohydrate scaffolds afforded multivalent thiolactosides. A tetravalent glycoconjugate based on a trehalose scaffold displayed the best multivalent effect on binding to plant lectin, peanut agglutinin.

    15. Catalytic Aziridination

      Intermolecular Alkene Aziridination: An Original and Efficient CuI···CuI Dinuclear Catalyst Deriving from a Phospha-Amidinate Ligand (pages 984–990)

      Noel Nebra, Camille Lescot, Philippe Dauban, Sonia Mallet-Ladeira, Blanca Martin-Vaca and Didier Bourissou

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejoc.201201478

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      Original NPN CuI catalysts: Phospha-amidinates form CuI complexes whose structure and behavior strongly depend on the substituents at phosphorus (mononuclear 1 for R = tBu, dinuclear 2 for R = Ph). The complexes have been evaluated in catalytic aziridination. Dinuclear complex 2 proved to be a robust and efficient catalyst for the aziridination of alkenes.

    16. Thioether Formation

      One-Pot Synthesis of Alkyl Styryl Sulfides Free from Transition Metal/Ligand Catalyst and Thiols (pages 991–997)

      Adrián A. Heredia and Alicia B. Peñéñory

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejoc.201201163

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      We have developed a one-pot methodology for the synthesis of alkyl arylvinyl sulfides in good to excellent yields, free of any metal/ligand systems and from malodorous and air-sensitive alkyl thiols. This procedure uses commercially available potassium thioacetate, low temperatures, and short reaction times.

    17. Aromatic Fluoroalkylation

      Heterogeneous Photoinduced Homolytic Aromatic Substitution of Electron-Rich Arenes with Perfluoroalkyl Groups in Water and Aqueous Media – A Radical-Ion Reaction (pages 998–1008)

      Sebastián Barata-Vallejo, Marina Martín Flesia, Beatriz Lantaño, Juan E. Argüello, Alicia B. Peñéñory and Al Postigo

      Article first published online: 19 DEC 2012 | DOI: 10.1002/ejoc.201201271

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      Electron-rich aromatic compounds react in aqueous media by PET with RfX to render substitution products in reasonable yields. The proposed mechanism is a homolytic aromatic substitution, followed by ET and (PT) steps, in the absence of base; radical cations of the substrates are formed in the initiation step. The reaction is compared with radical and electrophilic aromatic substitutions.

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