Synthese und Reaktivität von benzylischen und allylischen Zinkverbindungen

• Antragsteller: Professor Dr. Paul Knochel
• Fachliche Zuordnung: Organische Molekülchemie - Synthese, Charakterisierung
• Förderung: Förderung von 2002 bis 2011
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 5394413

• Erstellungsjahr: 2011

Zusammenfassung der Projektergebnisse

Im Rahmen dieses DFG-Projektes haben wir eine Reihe neuer benzylischer und allylischer Zinkorganylen erzeugt und ihre Nützlichkeit in der Synthese zeigen können. Wir haben eine neue effiziente Ibuprofensynthese entwickelt und patentiert.

Projektbezogene Publikationen (Auswahl)

• “A General Preparation of Polyfunctional Benzylic Zinc Organometallic Compounds”. Chem. Asian J. 2008, 3, 1678-1691
  Metzger, A.; Schade, M. A.; Manolikakes, G.; Knochel, P.
  
• “Highly Diastereoselective Addition of Cinnamylzinc Derivatives to α-Chiral Carbonyl Compounds”. Org. Lett. 2008, 10, 117-120
  Dunet, G.; Mayer, P.; Knochel, P.
  
• “LiCl-Mediated Preparation of Highly Functionalized Benzylic Zinc Chlorides”. Org. Lett. 2008, 10, 1107-1110
  Metzger, A.; Schade, M. A.; Knochel, P.
  
• “Nickel-catalyzed cross-coupling reactions of benzylic zinc reagents with aromatic bromides, chlorides and tosylates”. Chem. Comm. 2008, 3046-3048
  Schade, M. A.; Metzger, A.; Hug, S.; Knochel, P.
  
• “Palladium- and Nickel-Catalyzed Cross-Couplings of Unsaturated Halides Bearing Relatively Acidic Protons with Organozinc Reagents”. J. Org. Chem. 2008, 73, 8422-8436
  Manolikakes, G.; Munoz Hernandez, C.; Schade, M. A.; Metzger, A.; Knochel, P.
  
• “Polyfunctional benzylic zinc chlorides by the direct insertion of magnesium into benzylic chlorides in the presence of LiCl and ZnCl2”. Chem. Comm. 2008, 5824-5826
  Metzger, A.; Piller, F. M.; Knochel, P.
  
• Transition-Metal Catalyzed Cross-Coupling Reactions of Functionalized Organometallic Reagents, Nickel-Catalyzed Amination of Aryl Chlorides and Preparation and Reactions of Organozinc Reagents. Dissertation, 2009
  Georg Manolikakes
  
• „Preparation of Polyfunctional Arylmagnesium, Arylzinc, and Benzylic Zinc Reagents by Using Magnesium in the Presence of LiCl”. Chem. Eur. J. 2009, 15, 7192-7202
  Piller, F. M.; Metzger, A.; Schade, M. A.; Haag, B. A.; Gavryushin, A.; Knochel, P.
  
• LiCl-Mediated Direct Insertion of Magnesium Into Aryl, Heteroaryl and Benzylic Halides. Dissertation, 2010
  Fabian Piller
  
• Preparation and Application of Benzylic Zinc Chlorides. Lewis-Acid Promoted Additions of Organomagnesium and Organozinc Reagents to Carbonyl Derivatives. Transition Metal-Catalyzed Cross-Coupling Reactions with Methylthio-Substitutes N-Heterocycles. Dissertation, 2010
  Albrecht Metzger
  
• “Direct addition of functionalized organozinc reagents to carbon dioxide, ketones, and aldehydes in the presence of MgCl2”. Synthesis 2010, 3802-3810
  Bernhardt, S.; Metzger, A.; Knochel, P.
  
• “Large-scale preparation of polyfunctional benzylic zinc reagents by direct insertion of zinc dust into benzylic chlorides in the presence of lithium chloride”. Synthesis 2010, 882-891
  Metzger, A.; Argyo, C.; Knochel, P.
  
• “MgCl2-Accelerated Addition of Functionalized Organozinc Reagents to Aldehydes, Ketones, and Carbon Dioxide”. Angew. Chem. Int. Ed. 2010, 49, 4665-4668
  Metzger, A.; Bernhardt, S.; Manolikakes, G.; Knochel, P.
  
• Cross-Coupling of Benzylic Zinc Reagents, Preparation and Applications of Alkenyl Zinc Reagents, Preparation of Primary Amides and Synthesis of Functionalized Allenes. Dissertation, 2011
  Matthias Schade
  
• Preparation of Di- and Tri-Functionalized Aromatics and Heterocycles Transition Metal-Catalyzed Cross-Coupling Reactions of Thioethers. Chlorine-Zinc Exchange Reactions. Dissertation, 2011
  Laurin Melzig
  
• Synthesis, Functionalization, and Polymerization of Heterocycles Using Frustrated Lewis Pairs, Boron, Magnesium, and Zinc Organometallics. Dissertation, 2011
  Benjamin Haag
  
• „Pd- and Ni-Catalyzed Cross-Coupling Reactions of Functionalized Organozinc Reagents with Unsaturated Thioethers”. Chem. Eur. J. 2011, 17, 2948-2956
  Melzig, L.; Metzger, A.; Knochel, P.