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Drittmittelprojekt

Titel:
"Metall-induzierte Synthese und Nutzbarmachung axial-chiraler Biaryle" (TP B-1) im Rahmen des Sonderforschungsbereiches 347 "Selektive Reaktionen Metall-aktivierter Moleküle"

Projektleitung an der Universität Würzburg:

• Prof. Dr. Gerhard Bringmann ,Tel: +49(0)931 888 5323,Fax: +49(0)931 888 4755,Mail: bringman@chemie.uni-wuerzburg.de

Beteiligte Wissenschaftlerinnen und Wissenschaftler:

• Dr. Thomas Pabst
• Dr. Jürgen Hinrichs
• Dr. Wael Saeb
• Dr. Dirk Menche
• Dr. Matthias Breuning
• Dr. Andreas Wuzik
• Dr. Stefan Tasler
• Dipl.-Chem. Robert-Michael Pfeifer
• Prof. Dr. Lutz Gade , Institut für Anorganische Chemie der Universität Strasbourg, Frankreich
• Prof. Dr. Jörg Sundermeyer , Fachbereich Chemie, Universität Marburg
• Prof. Dr. Wolfdieter Schenk , Institut für Anorganische Chemie der Universität Würzburg
• Prof. Dr. Wolfgang Kiefer , Institut für Physikalische Chemie der Universität Würzburg
• Prof. Dr. Berhanu M. Abegaz , Chemistry Department, University of Botswana, Gaborone, Botswana
• Prof. Dr. Joseph D. Connolly , Chemistry Department, University of Glasgow, Scotland, UK
• Prof. Dr. Bruce Lipshutz , Department of Chemistry and Biochemistry, University of California, Santa Barbara, USA
• Prof. Dr. Motokazu Uemura , Department of Chemistry, Faculty of Integrated Arts and Sciences, Osaka Prefecture University, Sakai, Osaka, Japan

Kurzbeschreibung:
Axial-chirale Biarylverbindungen gewinnen zunehmend an Bedeutung als attraktive Syntheseziele, da einige dieser Substanzen als Auxiliare in der asymmetrischen Synthese eingesetzt werden können bzw. andere als pharmakologisch aktive Naturstoffe erkannt wurden. Wir haben ein methodisch neues Konzept zur Synthese hochgradig rotationsgehinderter axial-chiraler Biaryle entwickelt, das auf der atropselektiven Öffnung konfigurativ labiler Lacton-verbrückter Biaryle durch Metall-aktivierte chirale O-, N- oder H-Nucleophile beruht.

Schlagworte:
    Mastigophorene
    Axial-chirale Biaryle
    Stereoselektive Biarylsynthese
    Lacton-verbrückte Biaryle
    Lacton-Konzept
    Dimere Carbazol-Alkaloide
    Knipholon-artige 1-Phenylanthrachinone
    Naphthylisochinolin-Alkaloide

Laufzeit: von 01.1999 bis 12.2001

Förderinstitution:
DFG ( Sonderforschungsbereich 347, vierte Förderperiode )

Vorläuferprojekt:
Sonderforschungsbereich 347, dritte Förderperiode

Publikationen:

• G. Bringmann, S. Tasler. (1999). The Atropisomer-Selective Synthesis of Biologically Active and Synthetically Useful Chiral Biaryls. (Monographie)
• G. Bringmann, M. Breuning, P. Henschel, J. Hinrichs. (2002). Asymmetric Synthesis of (M)-2-Hydroxymethyl-1-(2-hydroxy-4,6-dimethylphenyl)naphthalene via a Configurationally Unstable Biaryl Lactone. (Monographie)
• G. Bringmann, S. Tasler. (2001). Synthesis of methylene-bridged binary carbazole alkaloids and a related tricarbazole. Tetrahedron 57: 2337-2343, (Wissenschaftl. Artikel)
• G. Bringmann, J. Hinrichs, T. Pabst, P. Henschel, K. Peters, E.-M. Peters. (2001). From Dynamic to Non-Dynamic Kinetic Resolution of Lactone-Bridged Biaryls: Synthesis of Mastigophorene B. Synthesis, 155-167, (Wissenschaftl. Artikel)
• G. Bringmann, M. Heubes, M. Breuning, L. Göbel, M. Ochse, B. Schöner, O. Schupp. (2000). Atropisomerization Barriers of Configurationally Unstable Biaryl Compounds, Useful Substrates for Atroposelective Conversions to Axially Chiral Biaryls. J. Org. Chem. 65: 722-728, (Wissenschaftl. Artikel)
• G. Bringmann, W. Saeb, M. Rübenacker. (1999). Directed Joint Total Synthesis of the Three Naphthylisoquinoline Alkaloids Dioncolactone A, Dioncopeltine A, and 5'-O-Demethyldioncophylline A. Tetrahedron 55: 423-432, (Wissenschaftl. Artikel)
• G. Bringmann, M. Breuning, S. Tasler. (1999). The Lactone Concept: An Efficient Pathway to Axially Chiral Natural Products and Useful Reagents. Synthesis, 525-558, (Wissenschaftl. Artikel)
• G. Bringmann, T. Pabst, D.S. Rycroft, J.D. Conolly. (1999). First Synthesis of Mastigophorenes A and B, by Biomimetic Oxidative Coupling of Herbertenediol. Tetrahedron Lett: 40: 483-486, (Wissenschaftl. Artikel)
• G. Bringmann, M. Breuning. (1999). Atropo-enantioselective Reduction of Configurationally Unstable Biaryl Lactones with BINAL-H. Tetrahedron: Asymmetry 10: 385-390, (Wissenschaftl. Artikel)
• G. Bringmann, J. Kraus, D. Menche, K. Messer. (1999). Elucidation of the Absolute Configuration of Knipholone and Knipholone Anthrone by Quantum Chemical CD Calculations. Tetrahedron 55: 7563-7572, (Wissenschaftl. Artikel)
• G. Bringmann, A. Wuzik, M. Breuning, P. Henschel, K. Peters, E.-M. Peters. (1999). Atropo-enantioselective synthesis of an axially chiral C1-symmetric phosphine ligand and its application in the asymmetric hydrosilylation of styrenes. Tetrahedron: Asymmetry 10: 3025-3031, (Wissenschaftl. Artikel)
• W.A. Schenk, J. Kümmel, I. Reuther, N. Burzlaff, A. Wuzik, O.Schupp, G. Bringmann. (1999). Atropo-Diastereoselective Ring Opening of Biaryl Thionolactones Using [CpRu{(S,S)-CHIRAPHOS}]+ as a Chiral Auxiliary. Eur. J. Inorg. Chem., 1745-1756, (Wissenschaftl. Artikel)
• G. Bringmann, M. Breuning, S. Tasler, H. Endress, C.L:J. Ewers, L. Göbel, K. Peters, E.-M. Peters. (1999). Atropo-Diastereoselective Cleavage of Configurationally Unstable Biaryl Lactones with Alkali Metal Activated Primary 1-Arylethylamines. Chem. Eur. J. 5: 3029-3038, (Wissenschaftl. Artikel)
• G. Bringmann, M. Breuning, R. Walter, A. Wuzik, K. Peters, E.-M. Peters. (1999). Synthesis of Axially Chiral Biaryls by Atropo-Diastereoselective Cleavage of Configurationally Unstable Biaryl Lactones with Menthol-Derived O-Nucleophiles. Eur. J. Org. Chem., 3047-3055, (Wissenschaftl. Artikel)
• G. Wahl, D. Kleinhenz, A. Schorm, J. Sundermeyer, R. Stowasser, C. Rummey, G. Bringmann, C. Fickert, W. Kiefer. (1999). Peroxomolybdenum Complexes as Epoxidation Catalysts in Biphasic Hydrogen Peroxide Activation: Raman Spectroscopic Studies and Density Functional Calculations. Chem. Eur. J. 5: 3237-3251, (Wissenschaftl. Artikel)
• G. Bringmann, A. Wuzik, R. Stowasser, C. Rummey, L. Göbel, D. Stalke, M. Pfeiffer, W. A. Schenk. (1999). Synthesis and Atropo-diastereoselective Ring Cleavage of a [Cp*Ru]-Complexed Biaryl Lactone: Experimental and Computational Investigations. Organometallics 18: 5017-5021, (Wissenschaftl. Artikel)
• G. Bringmann, M. Ochse, R. Götz. (2000). First Atropo-Divergent Total Synthesis of the Antimalarial Korupensamines A and B by the Lactone Method. J. Org.Chem. 65: 2069-2077, (Wissenschaftl. Artikel)
• G. Bringmann, J. Hinrichs, J. Kraus, A. Wuzik, T. Schulz. (2000). Nondynamic Kinetic Resolution of Configurationally Stable Biaryl Lactones by Reduction with Oxazaborolidine-Activated Borane: AM1 Studies and Experimental Verification. J. Org. Chem. 65: 2517-2527, (Wissenschaftl. Artikel)
• G. Bringmann, T. Pabst, P. Henschel, J. Kraus, K. Peters, E.-M. Peters, D.S. Rycroft, J.D. Connolly. (2000). Nondynamic and Dynamic Kinetic Resolution of Lactones with Stereogenic Centers and Axes: Stereoselective Total Synthesis of Herbertenediol and Mastigophorenes A and B. J. Am. Chem. Soc. 122, 9127-9133, (Wissenschaftl. Artikel)
• G. Bringmann, J. Hinrichs, P. Henschel, K. Peters, E.-M. Peters. (2000). Synthesis of Constitutionally Unsymmetric 7-Membered Biaryl Lactones by Ni-Mediated Intramolecular Coupling. Synlett, 1822-1824, (Wissenschaftl. Artikel)
• G. Bringmann, J. Hinrichs, K. Peters, E.-M. Peters. (2001). Synthesis of a Chiral Aryl-Ferrocenyl-Ligand, by Intramolecular Coupling to a Biaryl-Related Lactone. J. Org. Chem. 66, 629-632, (Wissenschaftl. Artikel)
• G. Bringmann, S. Tasler, H. Endress, J. Kraus, K. Messer, M. Wohlfarth, W. Lobin. (2001). Murrastifoline-F: First Total Synthesis, Atropo-Enantiomer Resolution, and Stereoanalysis of an Axially Chiral N,C-Coupled Biaryl Alkaloid. J. Am. Chem. Soc. 123: 2703-2711, (Wissenschaftl. Artikel)
• G. Bringmann, T. Pabst, P. Henschel, M. Michel. (2001). First total synthesis of the mastigophorenes C and D and of simplified unnatural analogs. Tetrahedron 57: 1269-1275, (Wissenschaftl. Artikel)
• G. Bringmann, A. Wuzik, O. Schupp, J. Kümmel, W.A. Schenk. (2001). Atropo-Enantioselective Ring Cleavage of Lewis Acid Modified Biaryl Thionolactones. Organometallics 20: 1692-1694, (Wissenschaftl. Artikel)
• G. Bringmann, S. Tasler, H. Endress, J. Mühlbacher. (2001). En route to the first stereoselective synthesis of axially chiral biscarbazole alkaloids. J. Chem. Soc., Chem. Commun., 761-762, (Wissenschaftl. Artikel)
• G. Bringmann, D. Menche. (2001). Erste, atrop-enantioselektive Totalsynthese der axial-chiralen Phenylanthrachinon-Naturstoffe Knipholon und 6'-O-Methylknipholon. - First, Atropo-enantioselective Total Synthesis of the Axially Chiral Phenylanthraquinone Natural Products Knipholone and 6'-O-Methylknipholone. Angew. Chem. 113: 1733-1736. - Angew. Chem. Int. Ed. 40: 1687-1690, (Wissenschaftl. Artikel)
• G. Bringmann, D. Menche. (2001). Stereoselective Total Synthesis of Axially Chiral Natural Products via Biaryl Lactones. Acc. Chem. Res. 34: 615-624, (Wissenschaftl. Artikel)
• S. Tasler, H. Endress, G. Bringmann. (2001). Synthesis of 2,2'-Biscarbazoles by Reductive Biaryl Coupling. Synthesis, 1993-2002, (Wissenschaftl. Artikel)
• K. Kamikawa, M. Furusyo, T. Uno, Y. Sato, A. Konoo, G. Bringmann, M. Uemura. (2001). Diastereoselective Ruthenium-Cp Complexation of Enantiopure Arene Compounds Possessing Stereogenic Benzylic Alcohol Functionalities. Org. Lett. 3: 3667-3670, (Wissenschaftl. Artikel)
• G. Bringmann, J. Hinrichs, P. Henschel, J. Kraus, K. Peters, E.-M. Peters. (2002). Atropo-Enantioselective Synthesis of the Natural Bicoumarin (+)-Isokotanin A via a Configurationally Stable Biaryl Lactone. Eur. J. Org. Chem., 1096-1106, (Wissenschaftl. Artikel)
• G. Bringmann, D. Menche, J. Mühlbacher, M. Reichert, N. Saito, S.S. Pfeiffer, B.H. Lipshutz. (2002). On the Verge of Axial Chirality: Atroposelective Synthesis of the AB-Biaryl Fragment of Vancomycin. Org. Lett. 4: 2833-2836, (Wissenschaftl. Artikel)
• G. Bringmann, D. Menche, J. Kraus, J. Mühlbacher, K. Peters, E.-M. Peters, R. Brun, M. Bezabih, B.M. Abegaz. (2002). Atropo-Enantioselective Total Synthesis of Knipholone and Related Antiplasmodial Phenylanthraquinones. J. Org. Chem. 67: 5595-5610, (Wissenschaftl. Artikel)
• G. Bringmann, M. Breuning, R.M. Pfeifer, W.A. Schenk, K. Kamikawa, M. Uemura. (2002). The lactone concept - a novel approach to the metal-assisted atroposelective construction of axially chiral biaryl systems. J. Organomet. 661: 31-47, (Wissenschaftl. Artikel)
• G. Bringmann, S. Tasler, R.M. Pfeifer, M. Breuning. (2002). The directed synthesis of axially chiral ligands, reagents, catalysts, and natural products: through the 'lactone methodology'. J. Organomet. 661: 49-65, (Wissenschaftl. Artikel)
• G. Bringmann, R.-M. Pfeifer, C. Rummey, T. Pabst, D. Leusser, D. Stalke. (2002). Structural Investigation of a Configurationally Stable Seven-Membered Bridged Biaryl of Relevance for Atroposelective Biaryl Synthesis. Z. Naturforsch., in press, (Wissenschaftl. Artikel)

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