0000000000059911
AUTHOR
Kathrin Wehming
ChemInform Abstract: Powerful Fluoroalkoxy Molybdenum(V) Reagent for Selective Oxidative Arene Coupling Reaction.
A novel dinuclear fluoroalkoxy Mo(V)-complex is efficient as reagent for the oxidative arene coupling of electron-rich arenes with superior reactivity compared to MoCl5 and MoCl5/TiCl4.
Leistungsstarkes Fluoralkoxy-Molybdän(V)-Reagens für die selektive oxidative Arenkupplung
Wir stellen ein neues Fluoralkoxy-Molybdan(V)-Reagens 1, mit im Vergleich zu MoCl5 oder MoCl5/TiCl4 hoherer Reaktivitat und Selektivitat in der oxidativen Kupplung von Arenen vor. Haufige Nebenreaktionen wie Chlorierung und/oder Oligomerenbildung werden erheblich reduziert, sodass ein leistungsstarkes und nutzliches Reagens fur die oxidative Kupplung erhalten wird. Theoretische Untersuchungen der Wechselwirkung des Reagens mit 1,2-Dimethoxybenzol-artigen Substraten deuten auf einen Innenspharen-Elektronentransfer gefolgt von einem radikalkationischen Reaktionspfad fur den oxidativen Kupplungsprozess hin. ESR-spektroskopische und elektrochemische Untersuchungen, Rontgenkristallstrukturanalys…
Oxidative cyclization reaction of 2-aryl-substituted cinnamates to form phenanthrene carboxylates by using MoCl5.
The oxidative cyclization reaction of 2-aryl cinnamates and derivatives thereof can be easily performed with MoCl5 as the oxidant. This powerful reagent allows oxidative coupling reactions for which other reagents fail. The best results are obtained when the 2-phenyl substituent of the cinnamate is equipped with two methoxy groups. Even iodo moieties in the bay region of phenanthrene are tolerated under the reaction conditions. If naphthalene moieties are involved, a rearrangement of the skeleton occurs, providing an elegant route to highly functionalized angular arenes. The cyclization is demonstrated for 15 example substrates with isolated yields of up to 99 % for the phenanthrene derivat…
ChemInform Abstract: Oxidative Cyclization Reaction of 2-Aryl-Substituted Cinnamates to Form Phenanthrene Carboxylates by Using MoCl5.
The reagent mixture MoCl5/TiCl4 is successfully applied for the oxidative cyclization of α-aryl substituted cinnamates to the corresponding phenanthrenes.
Molybdenum Pentachloride Mediated Synthesis of Spirocyclic Compounds by Intramolecular Oxidative Coupling
The oxidative treatment of (m)ethyl 2-aryl cinnamates equipped with methoxy groups in position 4 of the phenyl moiety promote the formation of cyclohexadienone substructures. This dealkylative oxidative C–C coupling gives access to spirocyclic compounds and avoids the construction of the corresponding phenanthrenes. Furthermore, the transformation can be expanded to other spirocyclic systems.
Cover Picture: Oxidative Cyclization Reaction of 2-Aryl-Substituted Cinnamates To Form Phenanthrene Carboxylates by Using MoCl5 (Chem. Eur. J. 39/2014)
ChemInform Abstract: Molybdenum Pentachloride Mediated Synthesis of Spirocyclic Compounds by Intramolecular Oxidative Coupling.
Oxidative treatment of 4-methoxy substituted 2-aryl cinnamates leads to an dealkylative C—C coupling and gives access to spirocyclic compounds.
Powerful Fluoroalkoxy Molybdenum(V) Reagent for Selective Oxidative Arene Coupling Reaction
We introduce the novel fluoroalkoxy molybdenum(V) reagent 1 which has superior reactivity and selectivity in comparison to MoCl5 or the MoCl5 /TiCl4 reagent mixture in the oxidative coupling reactions of aryls. Common side reactions, such as chlorination and/or oligomer formation, are drastically diminished creating a powerful and useful reagent for oxidative coupling. Theoretical treatment of the reagent interaction with 1,2-dimethoxybenzene-type substrates indicates an inner-sphere electron transfer followed by a radical cationic reaction pathway for the oxidative-coupling process. EPR spectroscopic and electrochemical studies, X-ray analyses, computational investigations, and the experim…
CCDC 1415863: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Kathrin Wehming, Anton Kehl, Martin Nieger, Gregor Schnakenburg, Roland Fröhlich, Dieter Schollmeyer, Siegfried R. Waldvogel|2016|Eur.J.Org.Chem.|2016|60|doi:10.1002/ejoc.201501384
CCDC 966311: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Jana Leppin, Kathrin Wehming, Dieter Schollmeyer, Katja Heinze and Siegfried R. Waldvogel|2014|Angew.Chem.,Int.Ed.|53|2494|doi:10.1002/anie.201309287
CCDC 804368: Experimental Crystal Structure Determination
Related Article: Kathrin Wehming, Moritz Schubert, Gregor Schnakenburg, Siegfried R. Waldvogel|2014|Chem.-Eur.J.|20|12463|doi:10.1002/chem.201403442
CCDC 1415860: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Kathrin Wehming, Anton Kehl, Martin Nieger, Gregor Schnakenburg, Roland Fröhlich, Dieter Schollmeyer, Siegfried R. Waldvogel|2016|Eur.J.Org.Chem.|2016|60|doi:10.1002/ejoc.201501384
CCDC 1415861: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Kathrin Wehming, Anton Kehl, Martin Nieger, Gregor Schnakenburg, Roland Fröhlich, Dieter Schollmeyer, Siegfried R. Waldvogel|2016|Eur.J.Org.Chem.|2016|60|doi:10.1002/ejoc.201501384
CCDC 1427184: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Kathrin Wehming, Anton Kehl, Martin Nieger, Gregor Schnakenburg, Roland Fröhlich, Dieter Schollmeyer, Siegfried R. Waldvogel|2016|Eur.J.Org.Chem.|2016|60|doi:10.1002/ejoc.201501384
CCDC 1415862: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Kathrin Wehming, Anton Kehl, Martin Nieger, Gregor Schnakenburg, Roland Fröhlich, Dieter Schollmeyer, Siegfried R. Waldvogel|2016|Eur.J.Org.Chem.|2016|60|doi:10.1002/ejoc.201501384
CCDC 1427185: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Kathrin Wehming, Anton Kehl, Martin Nieger, Gregor Schnakenburg, Roland Fröhlich, Dieter Schollmeyer, Siegfried R. Waldvogel|2016|Eur.J.Org.Chem.|2016|60|doi:10.1002/ejoc.201501384
CCDC 1419863: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Kathrin Wehming, Anton Kehl, Martin Nieger, Gregor Schnakenburg, Roland Fröhlich, Dieter Schollmeyer, Siegfried R. Waldvogel|2016|Eur.J.Org.Chem.|2016|60|doi:10.1002/ejoc.201501384
CCDC 966309: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Jana Leppin, Kathrin Wehming, Dieter Schollmeyer, Katja Heinze and Siegfried R. Waldvogel|2014|Angew.Chem.,Int.Ed.|53|2494|doi:10.1002/anie.201309287
CCDC 804367: Experimental Crystal Structure Determination
Related Article: Kathrin Wehming, Moritz Schubert, Gregor Schnakenburg, Siegfried R. Waldvogel|2014|Chem.-Eur.J.|20|12463|doi:10.1002/chem.201403442
CCDC 966310: Experimental Crystal Structure Determination
Related Article: Moritz Schubert, Jana Leppin, Kathrin Wehming, Dieter Schollmeyer, Katja Heinze and Siegfried R. Waldvogel|2014|Angew.Chem.,Int.Ed.|53|2494|doi:10.1002/anie.201309287