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Third-party-funded project

Title:
"Metal-induced Synthesis and Utilization of Axially Chiral Biaryls" within the Center Grant (Sonderforschungsbereich 347) "Selective Reactions of Metal-Activated Molecules"

Project management at the University of Würzburg:

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

Participating scientists:

• 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

Abstract:
Axially chiral biaryl compounds are of increasing importance as auxiliaries in asymmetric synthesis and as pharmacologically active natural products, and thus constitute attractive synthetic goals. We have detected a new principle for the directed construction of stereochemically homogeneous biaryl systems, by atropisomer-selective cleavage of configuratively unstable lactone-bridged biaryls using metal-activated chiral O-, N-, or H-nucleophiles to give biaryls with high stereocontrol.

Key words:
    Mastigophorenes
    Axially Chiral Biaryls
    Stereoselective Biaryl Synthesis
    Lactone-Bridged Biaryls
    Lactone Concept
    Knipholone-Type 1-Phenylanthraquinones
    Naphthylisoquinoline Alkaloids

Projekt period: from 01.1999 to 12.2001

Funding institution:
DFG ( Sonderforschungsbereich 347, vierte Förderperiode )

Preceding project:
Sonderforschungsbereich 347, dritte Förderperiode

Publications:

• G. Bringmann, S. Tasler. (1999). The Atropisomer-Selective Synthesis of Biologically Active and Synthetically Useful Chiral Biaryls. (monograph)
• 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. (monograph)
• G. Bringmann, S. Tasler. (2001). Synthesis of methylene-bridged binary carbazole alkaloids and a related tricarbazole. Tetrahedron 57: 2337-2343, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• G. Bringmann, M. Breuning, S. Tasler. (1999). The Lactone Concept: An Efficient Pathway to Axially Chiral Natural Products and Useful Reagents. Synthesis, 525-558, (scientific article)
• 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, (scientific article)
• G. Bringmann, M. Breuning. (1999). Atropo-enantioselective Reduction of Configurationally Unstable Biaryl Lactones with BINAL-H. Tetrahedron: Asymmetry 10: 385-390, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• G. Bringmann, D. Menche. (2001). Stereoselective Total Synthesis of Axially Chiral Natural Products via Biaryl Lactones. Acc. Chem. Res. 34: 615-624, (scientific article)
• S. Tasler, H. Endress, G. Bringmann. (2001). Synthesis of 2,2'-Biscarbazoles by Reductive Biaryl Coupling. Synthesis, 1993-2002, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)
• 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, (scientific article)

Links:
Research Group Prof. Bringmann - Homepage