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Forschungsschwerpunkt:  

Lehrstuhl für Organische Chemie II
Am Hubland, 97074 Würzburg
Mail: adam@chemie.uni-wuerzburg.de
Url: http://www.organik.chemie.uni-wuerzburg.de

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Forschungsschwerpunkte (und Projekte auf Basis der Grundausstattung):
Metall- und Enzym-katalysierte stereoselektive Reaktionen:
In diesem Forschungsschwerpunkt befassen wir uns mit Metall- und Enzym-katalysierten selektiven Oxidationen. Das Ziel ist die Ausarbeitung von effizienten und umweltschonenden Methoden zur chemo-, regio-, diastereo- und enantioselektiven Darstellung von synthetisch wertvollen und Industrie-relevanten oxyfunktionalisierten Produkten durch Metallkomplexe und Enzyme sowie Mikroorganismen. Für Oxyfunktionalisierungen durch Metallkatalyse werden Oxokomplexe von Mn, Fe und Cr, Peroxokomplexe von Re, Mo und W sowie Peroxykomplexe von Ti und V verwendet. Als Sauerstoffdonoren werden unter anderem Wasserstoffperoxid und dessen Derivate eingesetzt. In Biotransformationen werden vorzugsweise Metalloenzyme, insbesondere Peroxidasen und Oxidasen, als Katalysatoren eingesetzt. Außerdem werden Mikroorganismen (Bodenbakterien und Pilze) mit Peroxidase- oder Oxidase-Aktivität, anstelle der isolierten Enzyme, direkt für biokatalytische Transformationen genutzt.

Ergebnisse:
Für Ergebnisse siehe folgende publikationen:

749. Häring, D.; Schüler, E.; Adam, W.; Saha-Möller, C. R.; Schreier, P. Semisynthetic Enzymes in Asymmetric Synthesis: Enantioselective Reduction of Racemic Hydroperoxides Catalyzed by Seleno-Subtilisin, J. Org. Chem. 1999, 64, 832-835.

754. Adam, W.; Saha-Möller, C. R.; Schmid, K. S. Lipase-Catalyzed Kinetic Resolution of Z-Configured Homoallylic Alcohols, Tetrahedron: Asymmetry 1999, 10, 315-322.

755. Adam, W.; Stegmann, V. R.; Saha-Möller, C. R. Regio- and Diastereoselective Epoxidation of Chiral Allylic Alcohols Catalyzed by Manganese(salen) and Iron(porphine) Complexes, J. Am. Chem. Soc. 1999, 121, 1879-1882.

757. Adam, W.; Mitchell, C. M.; Saha-Möller, C. R.; Weichold, O. Host-Guest Chemistry in a Urea Matrix: Catalytic and Selective Oxidation of Triorganosilanes to the Corresponding Silanols by Methyltrioxorhenium and the Urea/Hydrogen Peroxide Adduct, J. Am.Chem. Soc. 1999, 121, 2097-2103.

759. Adam, W.; Mitchell, C. M.; Saha-Möller, C. R. Steric and Electronic Effects in the Diastereoselective Catalytic Epoxidation of Cyclic Allylic Alcohols with Methyltrioxorhenium (MTO), Eur. J. Org. Chem. 1999, 785-790.

764. Adam, W.; Lukacs, Z.; Saha-Möller, C. R.; Schreier, P. Biotransformation of (1-Phenyl)ethyl Hydroperoxide with Aspergillus Niger: A Model Study on Enzyme Selectivity and on the Induction of Peroxidase Activity, Biochim. Biophys. Acta 1999, 1427, 236-244.

69. Adam, W.; Mitchell, C. M.; Saha-Möller, C. R. Regio- and Diastereoselective Catalytic Epoxidation of Acyclic Allylic Alcohols with Methyltrioxorhenium: A Mechanistic Comparison with Metal (Peroxy and Peroxo Complexes) and Nonmetal (Peracids and Dioxirane) Oxidants, J. Org. Chem. 1999, 64, 3699-3707.

772. Adam, W.; Wirth, T. Hydroxy Group Directivity in the Epoxidation of Chiral Allylic Alcohols: Control of Diastereoselectivity through Allylic Strain and Hydrogen Bonding, Acc. Chem. Res. 1999, 32, 703-710.

781. Adam, W.; Lazarus, M.; Saha-Möller, C. R.; Schreier, P. Biocatalytic Synthesis of Optically Active -Oxyfunctionalized Carbonyl Compounds, Acc. Chem. Res. 1999, 32, 837-845.

786. Adam, W.; Lukacs, Z.; Viebach, K.; Humpf, H.-U.; Saha-Möller, C. R.; Schreier, P. Microscale Determination of the Absolute Configuration of -Aryl-substituted Alcohols by the CD Exciton Chirality Method, J. Org. Chem. 2000, 65, 186-190.

787. Adam, W.; Lukacs, Z.; Harmsen, D.; Saha-Möller, C. R.; Schreier, P. Biocatalytic Asymmetric Hydroxylation of Hydrocarbons with the Topsoil-Microorganism Bacillus megaterium, J. Org. Chem. 2000, 65, 878-882.

788. Adam, W.; Roschmann, K. J.; Saha-Möller, C. R. Catalytic Asymmetric Aziridination of Enol Derivatives in the Presence of Chiral Copper Complexes to give Optically Active -Amino Ketones, Eur. J. Org. Chem. 2000, 557-561.

790. Adam, W.; Saha-Möller, C. R.; Schmid, K. S. Preparation of Optically Active Allylic Hydroperoxy Alcohols and 1,3 Diols by Enzyme-Catalyzed Kinetic Resolution and Photooxygenation of Chiral Homoallylic Alcohols, J. Org. Chem. 2000, 65, 1431-1433.

793. Adam, W.; Gadissa Gelalcha, F.; Saha-Möller, C. R., Stegmann, V. Chemoselective C-H Oxidation of Alcohols to Carbonyl Compounds with Iodosobenzene Catalyzed by (Salen)chromium Complex, J. Org. Chem. 2000, 65, 1915-1918.

801. Li, W.; Lei, X-G.; Lem, G.; McDermott, A. E.; Turro, N. J.; Bottke, N.; Adam, W. Oxygen and Structural Effects on Silicalite 29Si Spin-Lattice Relaxation Studied by High-Resolution 29Si Solid-State NMR Spectroscopy, Chem. Mat. 2000, 12, 731-737.

807. Adam, W.; Mitchell, C. M.; Saha-Möller, C. R.; Selvam, T. Titanium-Catalysed Oxidation of Thianthrene 5-Oxide in Heterogeneous (Zeolites) versus Homogeneous Media: Electrophilic versus Template-Mediated Oxygen Transfer, J. Mol. Cat. A: Chem. 2000, 154, 251-255.

809. Akita, M.; Miyaji, T.; Muroga, N.; Mock-Knoblauch, C.; Adam, W.; Hikichi, S.; Moro-oka, Y. Synthesis and Dehydrative Condensation of Square-Planar Mono- and Dinuclear Hydroxopalladium Complexes with the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (TpiPr2), Tp iPr2 (Py)Pd-OH, and (-OH)2{PdTpiPr2 (H2O)}2, Inorg. Chem. 2000, 39, 2096-2102.

810. Adam, W.; Mitchell, C. M.; Saha-Möller, C. R.; Weichold, O. Structure, Reactivity, and Selectivity of Metal-Peroxo Complexes versus Dioxiranes. In Structure and Bonding, Metal-Oxo and Metal-Peroxo Species in Catalytic Oxidations; Meunier, B., Ed.; Springer-Verlag: Berlin-Heidelberg-New York-Tokyo, 2000; Vol. 97, pp 237-285.

811. Adam, W.; Saha-Möller, C. R. , Weichold, O. NaY Zeolite as Host for the Selective Heterogeneous Oxidation of Silanes and Olefins with Hydrogen Peroxide Catalyzed by Methyltrioxorhenium (MTO), J. Org. Chem. 2000, 65, 2897-2899.

813. Adam, W.; Lukacs, Z.; Saha-Möller, C. R.; Schreier, P. Biocatalytic Kinetic Resolution of Racemic Hydroperoxides through the Enantioselective Reduction with Free and Immobilized Microorganisms, J. Am. Chem. Soc. 2000, 122, 4887-4892.

814. Adam, W.; Bheema Rao, P.; Degen, H.-G., Saha-Möller, C. R. Metal-Template Effect in the Asymmetric Weitz-Scheffer Epoxidation of  Enones by an Optically Active Hydroperoxide, J. Am. Chem. Soc. 2000, 122, 5654-5655.

815. Adam, W.; Saha-Möller, C. R.; Weichold, O. Synthesis of Optically Active -Methyl -Hydroperoxy Esters by Diastereoselective Singlet-Oxygen Ene Reaction and Horseradish-Peroxidase Catalyzed Kinetic Resolution, Chemical Monthly 2000, 131, 697-705.

819. Adam, W.; Groer, P.; Saha-Möller, C. R. Synthesis of Optically Active -Methylene -Lactones Through Lipase-Catalyzed Kinetic Resolution, Tetrahedron: Asymmetry 2000, 11, 2239-2243.

820. Adam, W.; Casades, I.; Fornés, V.; Garcia, H.; Weichold, O. UV-vis and IR Spectral Characterization of Persistent Carbenium Ions, Generated upon Incorporation of Cinnamyl Alcohols in the Acid Zeolites HZSM-5 and HMor, J. Org. Chem. 2000, 65, 3947-3951.

824. Adam, W. Groer, P.; Humpf, H.-U.; Saha-Möller, C. R. Synthesis of Optically Active -Methylene -Lactams through Lipase-Catalyzed Kinetic Resolution, J. Org. Chem. 2000, 65, 4919-4922.

825. Adam, W.; Saha-Möller, C. R.; Weichold, O. Epoxidation of trans-Cyclooctene by Methyltrioxorhenium (MTO)/H2O2: Reaction of trans Epoxide with the Monoperoxo Complex , J. Org. Chem. 2000, 65, 5001-5004.

827. Adam, W.; Lukacs, Z.; Saha-Möller, C. R.; Weckerle, B.; Schreier, P. Microbial Asymmetric CH Oxidations of Simple Hydrocarbons: A Novel Monooxygenase Activity of the Topsoil Microorganism Bacillus megaterium, Eur. J. Org. Chem. 2000, 2923-2926.

830. Adam, W.; Hajra, S.; Herderich, M.; Saha-Möller, C. R. A Highly Chemoselective Oxidation of Alcohols to Carbonyl Products with Iodosobenzene Diacetate Mediated by Chromium(III)(salen) Complexes: Synthetic and Mechanistic Aspects, Org. Lett. 2000, 2, 2773-2776.

832. Adam, W.; Mock-Knoblauch, C.; Saha-Möller, C. R.; Herderich, M. Are MnIV Species Involved in Mn(Salen)-Catalyzed Jacobsen-Katsuki Epoxidations? A Mechanistic Elucidation of Their Formation and Reaction Modes by EPR Spectroscopy, Mass-Spectral Analysis, and Product Studies: Chlorination versus Oxygen Transfer, J. Am. Chem. Soc. 2000, 122, 9685-9691.

838. Adam, W.; Roschmann, K. J.; Saha-Möller, C. R. A Novel Counterion Effect on the Diastereoselectivity in the MnIII(salen)-Catalyzed Epoxidation of Phenyl-Substituted cis Alkenes, Eur. J. Org. Chem. 2000, 3519-3521.

843. Adam, W.; Corma, A.; Garcia, H.; Weichold, O. Titanium-Catalyzed Heterogeneous Oxidations of Silanes, Chiral Allylic Alcohols, 3-Alkylcyclohexanes, and Thianthrene 5-Oxides: A Comparison of the Reactivities and Selectivities for the Large-Pore Zeolite Ti-, the Mesoporous Ti-MCM-41, and the Layered Alumosilicate Ti-ITQ-2, J. Catal. 2000, 196, 339-344.

853. Adam, W.; Lukacs, Z.; Kahle, C.; Saha-Möller, C. R., Schreier, P. Biocatalytic Asymmetric Hydroxylation by Free and Immobilized Bacillus Megaterium Cells, J. Mol. Cat. B 2001, 377-385.

864. Adam, W.; Humpf, H.-U., Roschmann, K. J.; Saha-Möller, C. R. Enantioselective Epoxidation with Chiral MnIII(salen) Catalysts: Kinetic Resolution of Aryl-Substituted Allylic Alcohols, J. Org. Chem. 2001, 66, 5796-5800.

867. Adam, W.; Saha-Möller, C. R.; Schmid, K. S. The Synthesis of 4,6-Dideoxyfuranoses through the Regioselective and Diastereoselective Oxyfunctionalization of a Dimethylphenylsilyl-Substituted Chiral Homoallylic Alcohol, J. Org. Chem. 2001, 66, 7365-7371.

869. Bolm, C.; Beckmann, O.; Kühn, T.; Palazzi, C.; Adam, W.; Bheema Rao, P.; Saha-Möller, C. R. Influence of Hydroperoxides on the Enantioselectivity of the Metal-Catalyzed Asymmetric Baeyer-Villiger Oxidation and Epoxidation with Chiral Ligands, Tetrahedron: Asymmetry 2001, 12, 2441-2446.

870. Adam, W.; Prikhodovski, S.; Roschmann, K. J., Saha-Möller, C. R. Oxidation of Aryl-Substituted Allylic Alcohols by an Optically Active FeIII(Porph*) Catalyst: Enantioselectivity, Diasteroselectivity and Chemoselectivity in the Epoxide versus Enone Formation, Tetrahedron: Asymmetry 2001, 12, 2677-2681.

873. Adam, W.; Bheema Rao, P.; Degen, H.-G.; Lévai, A.; Patonay, T.; Saha-Möller, C. R. Asymmetric Weitz-Schefffer Epoxidation of Isoflavones with Hydroperoxides, Mediated by Optically Active Phase-Transfer Catalysts, J. Org. Chem. 2002, 67, 259-264.

875. Adam, W.; Bheema, Rao; P.; Degen, H.-G.; Saha-Möller, C. R. Asymmetric Weitz-Scheffer Epoxidation of -Enones by Optically Active Hydroperoxides: Control of Enantioselectivity through Metal-Coordinated or Hydrogen-Bonded Templates, Eur. J. Org. Chem. 2002, 630-639.

876. Adam, W.; Herold, M.; Hill, C. L.; Saha-Möller, C. R. Allylic CH Oxidation versus Epoxidation of 2-Cyclohexenols, Catalyzed by Chromium- and Manganese-Substituted Polyoxometalates and Salen Complexes, Eur. J. Org. Chem. 2002, 941-946.

882. Cui, M.; Adam, W.; Shen, J. H.; Luo, X. M.; Tan, X. J.; Chen, K. X; Ji, R. Y.; Jiang, H. L. A Density-Functional Study of the Mechanism for the Diastereoselective Epoxidation of Chiral Allylic Alcohols by the Titanium Peroxy Complexes, J. Org. Chem. 2002, 67, 1427-1435.

884. Adam, W.; Kilic, H.; Saha-Möller, C. R. An Efficient Regioselective and Diastereoselective Synthesis of the Epoxy-Quinol Functionality as Building Block for the Manumycin Antibiotics by the Sequence of Photooxygenation, Reduction and Weitz-Scheffer Epoxidation, Synlett 2002, 510-512.

887. Adam, W.; Roschmann, K.; Saha-Möller, C. R.; Seebach, D. cis-Stilbene and (1,2,3)-(2-Ethenyl-3-methoxy-cyclopropyl)benzene as Mechanistic Probes in the MnIII(salen)-Catalyzed Epoxidation: Influence of the Oxygen Source and the Counterion on the Diastereoselectivity of the Competitive Concerted and Radical-Type Oxygen Transfer, J. Am. Chem. Soc. 2002, 124, 5068-5073.

897. Lazarus, M.; Adam, W.; Saha-Möller, C.R.; Schreier, P. Biotransformations with Oxidases and Peroxidases for the Synthesis of Optically Active Building Blocks. In 3rd International Conference on Oxygen and Life, Kyoto, Japan; Ishimura, Y., Ed.; Elsevier Science, Amsterdam International Congress Series: 2002, 1233, 45-49.

Auszeichnungen und Preise:
Frau C. Mock-Knoblauch: DAAD-Stipendium für einen Forschungsaufenthalt in Japan, 1997; Fakultätspreis (Dissertation) der Fakultät für Chemie und Pharmazie, 2000.
Herr Z. Lukacs: Fakultätspreis (Dissertation) der Fakultät für Chemie und Pharmazie, 2000.
Dr. S. Hajra: Alexander-von-Humboldt Stipendium, 1999-2000.
Dr. P. Bheema Rao: Alexander-von-Humboldt Stipendium, 1999-2000.
Dr. O. Weichold: Lynen Stipendium, 2001.
Dr. R. Zhang: Alexander-von-Humboldt Stipendium, 2001-2002.

Ausstattung:
HPLC, Chiralyser, GC, MS, NMR-Spektrometer (600-, 400-, 250- und 200-MHz), Polarimeter.

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