Chemistry - A European Journal

Cover image for Vol. 16 Issue 32

Special Issue: In Honor of Professor José Barluenga for his 70th birthday

August 23, 2010

Volume 16, Issue 32

Pages 9693–9923

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
    11. Preview
    1. Cover Picture: Cu and Au Metal–Organic Frameworks Bridge the Gap between Homogeneous and Heterogeneous Catalysts for Alkene Cyclopropanation Reactions (Chem. Eur. J. 32/2010) (page 9693)

      Avelino Corma, Marta Iglesias, Francesc X. Llabrés i Xamena and Félix Sánchez

      Version of Record online: 17 AUG 2010 | DOI: 10.1002/chem.201090157

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      Metal–Organic Framework (MOF) materials containing either Cu or Au centers can act as catalysts for the cyclopropanation of alkenes with diazoacetates. In their Full Paper on on page 9789 ff., A. Corma et al. describe Cu[BOND] and Au[BOND] MOFs that are active and reusable heterogeneous catalysts for cycloproponation of alkenes with high chemo- and diastereoselectivities. This example is the first use of these materials to induce the carbene transfer reactions from diazo compounds.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
    11. Preview
    1. Inside Cover: Enantiomerically Pure Alleno–Acetylenic Macrocycles: Synthesis, Solid-State Structures, Chiroptical Properties, and Electron Localization Function Analysis (Chem. Eur. J. 32/2010) (page 9694)

      Pablo Rivera-Fuentes, José Lorenzo Alonso-Gómez, Ana G. Petrovic, Paul Seiler, Fabrizio Santoro, Nobuyuki Harada, Nina Berova, Henry S. Rzepa and François Diederich

      Version of Record online: 17 AUG 2010 | DOI: 10.1002/chem.201090158

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      Enantiopure alleno–acetylenic macrocycles have been prepared and fully characterized. Their extraordinary intense circular dichrosim (see picture) has been extensively studied and a mechanism for this remarkable response has been proposed. Additionally, the extent of the aromaticity was investigated by using the electron localization function. For more details see the Full Paper by F. Diederich, H. S. Rzepa et al. on page 9796 ff.

  3. Editorial

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
    11. Preview
    1. You have free access to this content
      Congratulations to Professor José Barluenga on his 70th Birthday (pages 9696–9697)

      Nazario Martín and Kilian Muñiz

      Version of Record online: 17 AUG 2010 | DOI: 10.1002/chem.201001986

  4. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
    11. Preview
  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
    11. Preview
  6. Concept

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
    11. Preview
    1. Cyclopropanes

      Selectivity in Metal-Catalyzed Carbon[BOND]Carbon Bond Cleavage of Alkylidenecyclopropanes (pages 9712–9721)

      Ahmad Masarwa and Ilan Marek

      Version of Record online: 6 JUL 2010 | DOI: 10.1002/chem.201001246

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      Complex, but still simple: The ring-opening of strained three-membered rings such as methylene- and alkylidenecyclopropanes generally lead to several products. If one starts with a more functionalized carbon skeleton, a selective reaction is now observed and rationalization as well as synthetic applications are described in this Concept article. This methodology could be used in the preparation of challenging structural motifs possessing quaternary carbon stereocenters in acyclic systems.

  7. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
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    1. Antitumor Analogues

      Recent Synthetic Approaches to 6,15-Iminoisoquino[3,2-b]3-benzazocine Compounds (pages 9722–9734)

      Carmen Avendaño and Elena de la Cuesta

      Version of Record online: 8 JUN 2010 | DOI: 10.1002/chem.201000532

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      New perspectives: This minireview is intended to update the synthetic contributions to obtain saframycin analogues. These compounds constitute the largest subgroup among the tetrahydroisoquinoline antitumor antibiotics. A brief description of the different strategies has been organized according to the order of bonding events that will link the precursors (see scheme).

  8. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
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    1. Domino Reactions

      Domino Diels–Alder Cycloadditions of Arynes: New Approach to Elusive Perylene Derivatives (pages 9736–9740)

      Alejandro Criado, Diego Peña, Agustín Cobas and Enrique Guitián

      Version of Record online: 14 JUL 2010 | DOI: 10.1002/chem.201001057

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      A game of dominos: Domino [4+2]/[4+2] cycloadditions between 1,8-difurylnaphthalene and arynes provide the corresponding adducts in a highly diastereoselective manner. This new synthetic methodology enables the preparation of elusive perylene derivatives with a remarkable reduced HOMO–LUMO gap, a crucial feature for organic semiconductors.

    2. Asymmetric Catalysis

      Benzylic Boron Reagents Behaving as Allylic Boron Reagents towards Aldehydes: A New Asymmetric Reaction Leading to Homoallylic Alcohols with Concomitant Dearomatisation (pages 9741–9745)

      Abel Ros, Antonio Bermejo and Varinder K. Aggarwal

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/chem.201001174

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      Retention of stereochemistry: p-Methoxybenzylic trifluoroborate salts react with aldehydes in the presence of Lewis or Brønsted acids to give homoallylic alcohols with concomitant dearomatisation of the aromatic ring (see scheme). Using enantioenriched benzylic trifluoroborate salts leads to adducts with >98 % retention of the stereochemistry in most cases.

    3. Carbenes

      A New Class of Singlet Carbene Ligands (pages 9746–9749)

      Manuel Alcarazo, Rosa M. Suárez, Richard Goddard and Alois Fürstner

      Version of Record online: 29 JUL 2010 | DOI: 10.1002/chem.201001779

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      What are you? Deprotonation of fluorenylidene phosphonium salts generates reactive intermediates that can be described as push–pull cumulenes or singlet carbenes (see scheme). Whereas the NMR data are ambiguous, the coordination behavior shows the ready availability of a lone pair at the central C atom. The donor ability of singlet carbene ligands of this new class exceeds that of the commonly used N-heterocyclic carbenes (NHCs).

    4. Amide Synthesis

      Selective Palladium-Catalyzed Aminocarbonylation of Aryl Halides with CO and Ammonia (pages 9750–9753)

      Xiao-Feng Wu, Helfried Neumann and Matthias Beller

      Version of Record online: 18 MAY 2010 | DOI: 10.1002/chem.201000090

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      Wake up and smell the ammonia! A palladium-catalyzed aminocarbonylation of aryl halides with CO and ammonia has been developed (see scheme). Primary amides are accessible, under mild reaction conditions, in moderate to excellent yields.

    5. Metallocenes

      Zn–Zn-Bonded Compounds that Contain Monoanionic Oxygen-Donor Ligands (pages 9754–9757)

      Mario Carrasco, Riccardo Peloso, Amor Rodríguez, Eleuterio Álvarez, Celia Maya and Ernesto Carmona

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201001011

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      The zinc connection! Reaction of bulky alcohols with [Zn2Cp*2] in the presence of a Lewis base allowed the isolation of the first zinc–zinc bonded complexes containing a Zn[BOND]O bond (see scheme).

    6. Cyclisation Reactions

      Synthesis of [3.3.1] Bicyclic Compounds by a Brønsted Acid Catalysed Double Intramolecular Michael Addition (pages 9758–9762)

      Abraham Mendoza, Pilar Pardo, Félix Rodríguez and Francisco J. Fañanás

      Version of Record online: 2 JUL 2010 | DOI: 10.1002/chem.201001109

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      Cyclisation sequence: An efficient method for the synthesis of [3.3.1] bicyclic compounds from easily available ynone derivatives has been developed. The reaction is based on an unprecedented double intramolecular Michael addition (DIMA) of an oxygen-centred and a carbon-centred nucleophile to the ynone (see scheme).

    7. Organocatalysis

      Organocatalytic Asymmetric Synthesis of trans-1,3-Disubstituted Tetrahydroisoquinolines via a Reductive Amination/Aza-Michael Sequence (pages 9763–9766)

      Dieter Enders, Jens X. Liebich and Gerhard Raabe

      Version of Record online: 26 JUL 2010 | DOI: 10.1002/chem.201001623

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      Benzothiazoline better than Hantzsch: A stereoselective Brønsted acid catalyzed reductive amination/aza-Michael approach towards the important class of tetrahydroisoquinolines is presented (see scheme). A biphenyl-substituted benzothiazoline is used as the reducing agent and leads to superior yields and enantiomeric excesses compared with the frequently used Hantzsch ester. The cyclization of the amine intermediate occurs smoothly with potassium tert-butoxide as the base and affords the trans-1,3-disubstituted tetrahydroisoquinolines.

    8. Natural Products

      Concise Modular Asymmetric Synthesis of Deguelin, Tephrosin and Investigation into Their Mode of Action (pages 9767–9771)

      José Garcia, Sofia Barluenga, Kristin Beebe, Len Neckers and Nicolas Winssinger

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201001080

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      The concise nature and modularity of the synthesis described for deguelin and tephrosin (retrosynthetic analysis depicted) should facilitate access to labeled analogues to dissect the mechanism of action of this important pharmacophore.

    9. Domino Heck Reaction

      Investigation of a Domino Heck Reaction for the Rapid Synthesis of Bicyclic Natural Products (pages 9772–9776)

      Barry M. Trost, Brendan M. O'Boyle and Daniel Hund

      Version of Record online: 28 JUL 2010 | DOI: 10.1002/chem.201001689

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      Unexpected Heck: During efforts toward the synthesis of FR900482, an unexpected domino Heck product was isolated (see scheme). Although this pathway was ultimately not productive for the aforementioned natural product synthesis, efforts were made to extend the methodology to the synthesis of amurensinine. To our knowledge this domino reaction was the first such tandem Heck-alkylation pathway in the presence of a geometrically favorable β-hydrogen elimination.

  9. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
    11. Preview
    1. Lithiated Compounds

      Lithiated Fluorinated Styrene Oxides: Configurational Stability, Synthetic Applications, and Mechanistic Insight (pages 9778–9788)

      Vito Capriati, Saverio Florio, Filippo Maria Perna and Antonio Salomone

      Version of Record online: 19 JUL 2010 | DOI: 10.1002/chem.201000897

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      Where is the boundary between configurational stability/instability of lithiated fluorinated styrene oxides? It depends upon both the type of fluorinated group and its relative position on the phenyl ring (see figure). Barriers of inversion, activation parameters, and mechanisms of racemization have been discussed for configurationally unstable intermediates, as well the synthesis.

    2. Metal–Organic Frameworks

      Cu and Au Metal–Organic Frameworks Bridge the Gap between Homogeneous and Heterogeneous Catalysts for Alkene Cyclopropanation Reactions (pages 9789–9795)

      Avelino Corma, Marta Iglesias, Francesc X. Llabrés i Xamena and Félix Sánchez

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201000278

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      Transfer of fragments: Metal–organic framework (MOF) materials containing either Cu or Au centers can act as catalysts (i.e., [Cu3(BTC)2] (BTC=benzene-1,3,5-tricarboxylate), and IRMOF-3-SI-Au) for the cyclopropanation of alkenes with diazoacetates (see scheme). This example is the first use of these materials to induce the carbene transfer reactions from diazo compounds.

    3. Chiral macrocycles

      Enantiomerically Pure Alleno–Acetylenic Macrocycles: Synthesis, Solid-State Structures, Chiroptical Properties, and Electron Localization Function Analysis (pages 9796–9807)

      Pablo Rivera-Fuentes, José Lorenzo Alonso-Gómez, Ana G. Petrovic, Paul Seiler, Fabrizio Santoro, Nobuyuki Harada, Nina Berova, Henry S. Rzepa and François Diederich

      Version of Record online: 2 AUG 2010 | DOI: 10.1002/chem.201001087

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      Shaping up! Enantiopure, shape-persistent alleno–acetylenic macrocycles (an example of which is shown here) were prepared by oxidative homocoupling of 1,3-diethynylallenes. The synthesis and solid-state structures are reported, along with a detailed analysis of their chiroptical and electronic properties.

    4. Homogeneous Catalysis

      Bis(allyl)ruthenium(IV) Complexes Containing Water-Soluble Phosphane Ligands: Synthesis, Structure, and Application as Catalysts in the Selective Hydration of Organonitriles into Amides (pages 9808–9817)

      Victorio Cadierno, Josefina Díez, Javier Francos and José Gimeno

      Version of Record online: 28 JUN 2010 | DOI: 10.1002/chem.201001152

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      The power of water: Mono- and dinuclear (2,7-dimethylocta-2,6-diene-1,8-diyl)ruthenium(IV) complexes (see picture), which contain selected water-soluble phosphanes, behave as highly efficient catalysts for the selective hydration of organonitriles into amides in pure aqueous medium under neutral conditions.

    5. Gold Catalysis

      Synthesis of Diverse Indole-Containing Scaffolds by Gold(I)-Catalyzed Tandem Reactions of 3-Propargylindoles Initiated by 1,2-Indole Migrations: Scope and Computational Studies (pages 9818–9828)

      Roberto Sanz, Delia Miguel, Mukut Gohain, Patricia García-García, Manuel A. Fernández-Rodríguez, Adán González-Pérez, Olalla Nieto-Faza, Ángel R. de Lera and Félix Rodríguez

      Version of Record online: 19 JUL 2010 | DOI: 10.1002/chem.201001162

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      Precious-metal catalysis: 3-Propargylindoles are able to participate in 1,2-migrations under gold-catalysis. 3-(Inden-2-yl)indoles could be accessed through gold-iso-Nazarov or gold-Nazarov cyclizations, whereas 3-(1,3-dien-2-yl)indoles are generated when none of these pathways are accessible.

    6. Diastereoselectivity

      Preparation of Organoaluminum Reagents from Propargylic Bromides and Aluminum Activated by PbCl2 and Their Regio- and Diastereoselective Addition to Carbonyl Derivatives (pages 9829–9834)

      Li-Na Guo, Hongjun Gao, Peter Mayer and Paul Knochel

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000523

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      Functional group tolerance: A new and efficient preparation of allenic and propargylic aluminum reagents has been reported. These organoaluminum species react with aldehydes or ketones, giving the homopropargylic or allenic alcohols in good to excellent yields with high selectivity (see scheme). Various functional groups are tolerated in this reaction.

    7. Natural Products

      N-Sulfinyl Amines as a Nitrogen Source in the Asymmetric Intramolecular Aza-Michael Reaction: Total Synthesis of (−)-Pinidinol (pages 9835–9845)

      Santos Fustero, Silvia Monteagudo, María Sánchez-Roselló, Sonia Flores, Pablo Barrio and Carlos del Pozo

      Version of Record online: 11 JUN 2010 | DOI: 10.1002/chem.201000615

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      N-Sulfinyl amines have been successfully employed as nitrogen nucleophiles for the asymmetric intramolecular aza-Michael reaction (IMAMR; see scheme). The synthetic strategy involves a cross-metathesis (CM) reaction followed by the Michael-type cyclization, either in a base-catalyzed two-step procedure or in a tandem fashion.

    8. Heterocycles

      Gold Catalysis: Tandem Reactions of Diyne–Diols and External Nucleophiles as an Easy Access to Tricyclic Cage-Like Structures (pages 9846–9854)

      A. Stephen K. Hashmi, Miriam Bührle, Michael Wölfle, Matthias Rudolph, Marcel Wieteck, Frank Rominger and Wolfgang Frey

      Version of Record online: 14 JUL 2010 | DOI: 10.1002/chem.201001322

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      Gold closes the cage: Diyne–diols and external nucleophiles in gold-catalysed reactions deliver rigid tricyclic heterocyclic compounds in high selectivity by a domino reaction. Eight new bonds are formed by hydroalkoxylation/hydrohydroxylation or hydroamination in good overall yields (see scheme).

    9. Electroluminescence

      Dumbbell-Shaped Dinuclear Iridium Complexes and Their Application to Light-Emitting Electrochemical Cells (pages 9855–9863)

      Rubén D. Costa, Gustavo Fernández, Luis Sánchez, Nazario Martín, Enrique Ortí and Henk J. Bolink

      Version of Record online: 25 JUN 2010 | DOI: 10.1002/chem.201000600

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      Observed quenching pathway: A novel family of dumbbell-shaped dinuclear iridium(III) complexes is presented (see figure). Theoretical and photophysical studies show that the lowest triplet state resides on the molecular spacer and constitutes an efficient quenching pathway that explains the poor photoluminescence quantum yields. Conversely, the presence of the spacer reduces the self-quenching in solid films and a near-quantitative internal electron-to-photon conversion is observed in LEC devices.

    10. Synthetic Methods

      Pyrrole and Oligopyrrole Synthesis by 1,3-Dipolar Cycloaddition of Azomethine Ylides with Sulfonyl Dipolarophiles (pages 9864–9873)

      Rocío Robles-Machín, Ana López-Pérez, María González-Esguevillas, Javier Adrio and Juan Carlos Carretero

      Version of Record online: 22 JUN 2010 | DOI: 10.1002/chem.201000742

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      Keep y-lid-e on it! A range of pyrroles have been prepared by metal-catalyzed 1,3-dipolar cycloaddition of α-iminoesters with readily available sulfonyl dipolarophiles, followed by base-promoted sulfone elimination and aromatization (see scheme). This strategy can also be applied to the construction of n-oligopyrroles (n=2–5).

    11. Asymmetric Synthesis

      2-(p-Tolylsulfinyl)benzyl Halides as Efficient Precursors of Optically Pure trans-2,3-Disubstituted Aziridines (pages 9874–9883)

      Yolanda Arroyo, Ángela Meana, M. Ascensión Sanz-Tejedor, Inés Alonso and José Luis García Ruano

      Version of Record online: 12 APR 2010 | DOI: 10.1002/chem.201000217

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      Get selective! Aziridination of (R)-N-sulfinyl aldimines (aryl, heteroaryl and alkenyl derivatives) with α-iodo-2-(p-tolylsulfinyl)toluene, in the presence of sodium hexamethyl disilazide (NaHMDS), takes place with almost complete control of the stereoselectivity (facial and anti/syn) and with very high yields, affording optically pure N-sulfinyl trans-2,3-disubstituted aziridines (see scheme).

    12. Asymmetric Organocatalysis

      Enantioselective Organocatalytic Addition of Azlactones to Maleimides: A Highly Stereocontrolled Entry to 2,2-Disubstituted-2H-oxazol-5-ones (pages 9884–9889)

      Andrea-Nekane R. Alba, Guillem Valero, Teresa Calbet, Mercé Font-Bardía, Albert Moyano and Ramon Rios

      Version of Record online: 18 MAY 2010 | DOI: 10.1002/chem.201000239

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      Thio-E-urea-KA! The first highly diastereo- and enantioselective organocatalytic synthesis of 2,2-disubstituted-2H-oxazol-5-ones is described. The addition of oxazolones to maleimides is promoted by bifunctional thiourea catalysts, which afford the corresponding 2,2-disubstituted-2H-oxazol-5-ones with total regio- and stereocontrol (see scheme).

    13. Copper Catalysis

      Formation of Quaternary Chiral Centers by N-Heterocyclic Carbene–Cu-Catalyzed Asymmetric Conjugate Addition Reactions with Grignard Reagents on Trisubstituted Cyclic Enones (pages 9890–9904)

      Stefan Kehrli, David Martin, Diane Rix, Marc Mauduit and Alexandre Alexakis

      Version of Record online: 10 JUN 2010 | DOI: 10.1002/chem.201000471

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      Asymmetric chemistry: The copper-catalyzed conjugate addition of Grignard reagents to 3-substituted cyclic enones allows the formation of all-carbon chiral quaternary centers (see scheme). N-Heterocyclic carbenes act as efficient chiral ligands for this transformation. High enantioselectivities (up to 96 % ee) could be obtained for a variety of substrates.

    14. Cross-Coupling Reactions

      Palladium-Catalyzed Cross-Coupling Reactions of Organogold(I) Reagents with Organic Electrophiles (pages 9905–9909)

      Miguel Peña-López, Miguel Ayán-Varela, Luis A. Sarandeses and José Pérez Sestelo

      Version of Record online: 16 JUN 2010 | DOI: 10.1002/chem.201000726

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      Gold C[BOND]C coupling: Organogold(I) reagents (aryl, alkenyl, alkynyl, alkyl) can be used in palladium-catalyzed cross-coupling reactions with different organic electrophiles, such as aryl and alkenyl halides, aryl triflates, benzyl bromide, and benzoyl chloride (see scheme; OTf=trifluoromethane sulfonate). The reaction generally proceeds at room temperature in high yields.

    15. Nitrogen Heterocycles

      Tunable Diastereoselection of Biased Rigid Systems by Lewis Acid Induced Conformational Effects: A Rationalization of the Vinylation of Cyclic Nitrones En Route to Polyhydroxylated Pyrrolidines (pages 9910–9919)

      Ignacio Delso, Eduardo Marca, Vanni Mannucci, Tomás Tejero, Andrea Goti and Pedro Merino

      Version of Record online: 4 AUG 2010 | DOI: 10.1002/chem.201001608

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      Diastereofacial discrimation: The vinylation of cyclic nitrones in the presence of diethylaluminum chloride shows a strong dependence on both temperature and steric hindrance at C3 (see scheme; s=solvent). Experimental, theoretical, and spectroscopic studies have been used for rationalizing the observed inversion of selectivity at low temperature.

  10. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Editorial
    5. Graphical Abstract
    6. News
    7. Concept
    8. Minireview
    9. Communications
    10. Full Papers
    11. Preview
    1. You have free access to this content
      Preview: Chem. Eur. J. 33/2010 (page 9923)

      Version of Record online: 17 AUG 2010 | DOI: 10.1002/chem.201090161

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