Forschungsschwerpunkt: |
Lehrstuhl für Organische Chemie II
Am Hubland, 97074 Würzburg Mail: adam@chemie.uni-wuerzburg.de Url: http://www.organik.chemie.uni-wuerzburg.de |
Wissenschaftliche Mitglieder:
Professoren:
Wissenschaftliche Mitarbeiter:
Sonstige beteiligte Personen und Organisationen:
Forschungsschwerpunkte (und Projekte auf Basis der Grundausstattung):
Aktivierung und präparative Nutzung von Singulettsauerstoff und organischen Peroxiden in der regio- und stereoselektiven Oxyfunktionalisierung:
Die Forschungsinteressen auf diesem Gebiet gelten dem Sauerstoff-, Schwefel-, und Stickstoff-Transfer durch Oxidationsprozesse organischer und metallorganischer Verbindungen, wobei der Hauptschwerpunkt auf Oxyfunktionalisierungen liegt. Für diesen Zweck werden molekularer Sauerstoff und Wasserstoffperoxid sowie dessen Derivate (Hydroperoxide, Perhydrate und Dioxirane) direkt genutzt oder diese werden chemisch oder photochemisch (Generierung von Singulettsauerstoff aus molekularem Sauerstoff) aktiviert für regio- und stereoselektive Oxyfunktionalisierungen. Das vorrangige Ziel ist die mechanistische Aufklärung der Sauerstofftransfer-Prozesse, um somit hoch selektive, effiziente, und bequeme Oxidationsmethoden für präparative Zwecke zu entwickeln.
Ergebnisse:
Für die Ergebnisse dieses Forschungsschwerpunkts siehe folgende Publikationen:
750. Rodriguez, G.; Castedo, L., Dominguez, D.; Saá, C.; Adam, W.; Saha-Möller, C. R. Dioxirane Epoxidation of 10-Membered-Ring Stilbene Lactams as Synthetic Precursors to Protoberberines, J. Org. Chem. 1999, 64, 877-883.
753. Adam, W.; Degen, H.-G.; Saha-Möller, C. R. Regio- and Diastereoselective Catalytic Epoxidation of Chiral Allylic Alcohols with Hexafluoroacetone Perhydrate. Hydroxy-Group Directivity through Hydrogen Bonding, J. Org. Chem. 1999, 64, 1274-1277.
756. Adam, W.; Saha-Möller, C. R.; Schambony, S. B. A Highly Diastereoselective Dioxetane Formation by the Hydroxy-Directed [2+2] Cycloaddition of Singlet Oxygen to a Chiral Allylic Alcohol, J. Am. Chem. Soc. 1999, 121, 1834-1838.
762. Patonay, T.; Adam, W.; Jeko, J.; Kövér, K. E.; Lévai, A.; Németh, M.; Peters, K. Oxazepines and Thiazepines 36. Diastereoselective Sulfoxidation of 2,3-Dihydro-1,5-Benzothiazepin-4(5H)-ones by Dimethyldioxirane, Heterocycles 1999, 51, 85-94.
770. Adam, W.; Bottke, N.; Krebs, O.; Saha-Möller, C. R. Allylic Amidation of Olefins by Ene Reaction of Acylnitroso Compounds Generated in situ by Oxidation of Hydroxamic Acids, Eur. J. Org. Chem. 1999, 1963-1965.
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.
775. Adam, W.; Saha-Möller, C. R.; Zhao, C.-G. Asymmetric Epoxidation of Olefins by Chiral Dioxiranes Generated in situ From Ketones of D-(-)-Quinic Acid, Tetrahedron: Asymmetry 1999, 10, 2749-2755.
779. Adam, W.; Saha-Möller, C. R.; Zhao, C.-G. Asymmetric C-H Oxidation of vic Diols to -Hydroxy Ketones by a Fructose-Derived Dioxirane: Electronic Effects on the Enantioselectivity of Oxygen Transfer, J. Org. Chem. 1999, 64, 7492-7497.
780. Adam, W.; Saha-Möller, C. R.; Schambony, S.; Schmid, K. S.; Wirth, T. Stereocontrolled Photooxygenations: A Valuable Synthetic Tool, Photochem. Photobiol. 1999, 70, 476-483.
791. Adam, W.; Makosza, M.; Zhao, C.-G.; Surowiec, M. On the Mechanism of the Dimethyldioxirane Oxidation of H Adducts (Meisenheimer Complexes) Generated from Nitroarenes and Carbanions, J. Org. Chem. 2000, 65, 1099-1101.
805. Adam, W.; Pastor, A.; Peters, K.; Peters, E.-M. Opposite -Face Selectivity for the DMD and m-CPBA Epoxidations of Chiral 2,2-Dimethyloxazolidine Derivatives of Tiglic Amides: Control by Steric Interactions versus Hydrogen Bonding, Org. Lett. 2000, 2, 1019-1022.
806. Adam, W.; Pastor, A.; Wirth, T. Direct Amination of Olefins through Sequential Triazolinedione Ene Reaction and Carbanion-Assisted Cleavage of the N-N Urazole Bond, Org. Lett. 2000, 2, 1295-1297.
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.
818. Adam, W.; Bottke, N.; Krebs, O. The New skew and the Established cis and gem Regioselectivities in the Ene Reaction of Trisubstituted Olefins: Comparison of the Singlet Oxygen, Triazolinedione, and Nitrosoarene Enophiles, J. Am. Chem. Soc. 2000, 122, 6791-6792.
822. Adam, W.; Peters, K.; Peters, E.-M., Schambony, S. B. Diastereoselective and Regioselective Singlet-Oxygen Ene Reaction of Oxazolidine-Substituted Alkenes: Control through Hydrogen Bonding Mediated by the Urea Functionality of Chiral Auxiliaries, J. Am. Chem. Soc. 2000, 122, 7610-7611.
823. Nava Salgado, V.; Adam, W. The Unexpected Reorganizations of a -Lactone Aldolate to 1,3-Dioxan-4-ones in the Reaction of 4-(1-Methylethyl)-3-[(phenylthio)methyl]-1-oxetan-2-one Lithium Enolate with Acetaldehyde, Eur. J. Org. Chem. 2000, 2529-2533.
826. Adam, W.; Fröhling, B. "An '-Dioxothione in the Reaction of Ninhydrin with Potassium Thiotosylate and its [4+2] Cycloaddition with trans-Cyclooctene", Org. Lett. 2000, 2, 2519-2522.
831. Adam, W.; Balci, M.; Kilic, H. 2,3-Dioxabicyclo[2.2.2]oct-7-en-5-one: Synthesis and Reactions of the Keto Endoperoxide of Phenol, J. Org. Chem. 2000, 65, 5926-5931.
833. Adam, W.; Bottke, N. Hydroxy-Group Directivity in the Nitroso Ene Reaction: Diastereo- and Regioselective Amination of Chiral Allylic Alcohols, J. Am. Chem. Soc. 2000, 122, 9846-9847.
835. Adam, W.; Bach, R. D.; Dmitrenko, O.; Saha-Möller, C. R. A Computational Study of the Hydroxy-Group Directivity in the Peroxyformic Acid Epoxidation of the Chiral Allylic Alcohol (Z)-3-Methyl-3-penten-2-ol: Control of Threo Diastereoselectivity through Allylic Strain and Hydrogen Bonding, J. Org. Chem. 2000, 65, 6715-6728.
836. Adam, W.; Bottke, N.; Krebs, O. Steric and Conformational Control of the Regioselectivities in the Ene Reaction with Trisubstituted Cycloalkenes - Comparison of the Enophiles Singlet Oxygen, Triazolinedione and Nitrosoarene, Org. Lett. 2000, 21, 3293-3296.
840. Adam, W.; Degen, H.-G.; Pastor, A.; Saha-Möller, C. R.; Schambony, S. B.; Zhao, C.-G. Preparative Use of Peroxidic Oxidants for Oxygen-Transfer Reactions. In DFG Research Report on Peroxide Chemistry: Mechanistic and Preparative Aspects of Oxygen Transfer; Adam, W., Ed; Wiley-VCH: Weinheim, 2000.
845. Lévai, A.; Adam, W.; Jekö, J.; Patonay, T.; Székely, A.; Vass, E. B. A Comparative Study of the Epoxidation of 2-Substituted Isoflavones by Dimethyldioxirane, Sodium Hypochlorite, and Alkaline Hydrogen Peroxide (Weitz-Scheffer Reaction), J. Heterocycl. Chem. 2000, 37, 1065-1089.
847. Adam, W. (Ed.), DFG Research Report on Peroxide Chemistry: Mechanistic and Preparative Aspects of Oxygen Transfer; Wiley-VCH: Weinheim, 2000.
848. Adam, W.; Schambony, S. Diastereoselective Epoxidation of Oxazolidine-Substituted Alkenes by Dimethyldioxirane and m-Chlorobenzoic Acid: -Facial Control through Hydrogen Bonding by the Urea Functionality, Org. Lett. 2001, 3, 79-82.
852. Adam, W., Bheema Rao, P.; Degen, H.-G.; Saha-Möller, C. R. Asymmetric Weitz-Scheffer Epoxidation of Conformationally Flexible and Fixed Enones with Sterically Demanding Hydroperoxides Mediated by Optically Active Phase-Transfer Catalysts, Tetrahedron: Asymmetry, 2001, 12, 121-125.
855. Patonay, T.; Adam, W.; Lévai, A.; Köver, P.; Németh, M.; Peters, E.-M.; Peters, K. Chemo- and Diastereoselectivity in the Dimethyldioxirane Oxidation of 2,3-Dihydro-4H-1-benzothiopyran-4-ones and 4H-1-Benzothiopyran-4-ones. Unusual Reactivity of 4H-1-Benzothiopyran-4-one-1-Oxides, J. Org. Chem. 2001, 66, 2275-22280.
856. Adam, W., Bargon, R. M. Episulfidation of Strained Cycloalkenes in the Thermolysis of 5-Aryloxy-1,2,3,4-thiatriazoles, Eur. J. Org. Chem. 2001, 1959-1962.
858. Adam, W.; Bottke, N.; Engels, B.; Krebs, O. An Experimental and Computational Study on the Reactivity and Regioselectivity for the Nitrosoarene Ene Reaction: Comparison with Triazolinedione and Singlet Oxygen, J. Am. Chem. Soc. 2001, 123, 5542-5548.
862. Adam, W.; Peters, K.; Peters, E.-M.; Schambony, S. B. Efficient Control of the Diastereoselectivity and Regioselectivity in the Singlet-Oxygen Ene Reaction of Chiral Oxazolidine-Substituted Alkenes by a Remote Urea NH Functionality. Comparison with Dimethyldioxirane and m-Chorobenzoic Acid Epoxidations, J. Am. Chem. Soc. 2001, 123, 7228-7232.
865. Makosza, M.; Adam, W.; Zhao, C.-G.; Surowiec, M. Oxidation of Nitrobenzylic Carbanions with Dimethyldioxirane. New Synthesis of Quinomethanes and Nitrobenzylic Carbinols. First Examples of Methylation of Carbanions with Dimethyldioxirane, J. Org. Chem. 2001, 66, 55022.
866. Adam, W.; Bargon, R. M. Molybdenum-Catalyzed Episulfidation of (E)-Cycloalkenes with Elemental Sulfur, Chem. Commun. 2001, 1910-1911.
868. Adam, W.; Saha-Möller, C. R.; Ganeshpure, P. A. Synthetic Applications of Nonmetal Catalysts for Homogeneous Oxidation, Chem. Rev. 2001, 101, 3499-3548.
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.
880. Adam, W.; Fröhling, B. Lewis-Acid-Catalyzed Sulfur Transfer from a Sultene to Strained Alkenes, Org. Lett. 2002, 4, 599-602.
881. Voigt, B.; Porzel, A.; Adam, G.; Golsch, D.; Adam, W.; Wagner, C.; Merzweiler, K. Synthesis of 2,24-Diepicastasterone and 3,24-Diepicastasterone as Potential Brassinosteroid Metabolites of the Cockroach Periplaneta Americana, Collect. Czech. Chem. Commun. 2002, 67, 91-102.
883. Adam, W.; Cakmak, O.; Saha-Möller, C. R.; Tutar, A. Highly Brominated Norbornanes by Photobromination as Precursors for the Convenient Synthesis of 2,3,5,6-Tetrabromo- and 2,3,5,6-Tetramethoxy-Substituted Norbornadienes, Synlett 2002, 49-52.
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.
889. Lévai, A.; Kočevar, M.; Tóth, G.; Simon, A.; Vraničar, L.; Adam, W. Synthesis and Dimethyldioxirane Oxidation of Tetrahydrobenzofurans, Eur. J. Org. Chem. 2002, 1830-1833.
893. Adam, W.; Bosio, S.G.; Fröhling, B.; Stalke, D. Unusual Sulfur Chemistry in the Thermal Reaction of Sultene and Thiophene-Endoperoxide Sulfur Donors with Cyclic Alkynes: Reversible Formation of a Persistent Thiirenium Ion and Trapping of a Thiirene by [4+2] Cycloaddition, J. Am. Chem. Soc. 2002, 124, 8316-8320.
895. Adam, W.; Bosio, S.; Turro, N. J. Highly Diastereoselective Dioxetane Formation in the Photooxygenation of Enecarbamates with an Oxazolidinone Chiral Auxiliary: Steric Control in the [2+2] Cycloaddition of Singlet Oxygen through Conformational Alignment, J. Am. Chem. Soc. 2002, 124, 8814-8815.
896. Adam, W.; Bosio,S. G.; Gogonas, E. P.; Hadjiarapoglou; L. P. A Stereoselective and Regioselective Synthesis of trans,trans-Configured 1, 2, 3-Trisubstituted Indanes: Cycloaddition of Alkenes with Iodonium Ylides of -Disulfones, Synthesis 2002, 14, 2084-.
901. Adam, W.; Bargon, R. M.; Bosio, S. G.; Schenk, W. A.; Stalke, D. The Direct Synthesis of Isothiocyanates from Isonitriles by Molybdenum-Catalyzed Sulfur Transfer with Elemental Sulfur, J. Org. Chem. 2002, 67, 7037-7041.
904. Adam, W.; Krebs, O.; Saha-Möller, C. R. Efficient -Facial Control in the Ene Reaction of Nitrosoarene, Triazolinedione and Singlet Oxygen with Tiglic Amides of the Bornane-Derived Sultam as Chiral Auxiliary: An Economical Synthesis of Enantiomerically Pure Nitrogen- and Oxygen-Functionalized Acrylic Acid Derivatives, J. Am. Chem. Soc. 2002, 124, 12938-12939.
905. Adam, W.; Krebs, O.; Orfanopoulos, M.; Stratakis, M. Control of Regioselectivity by the lone Substituent through Steric Electronic Effects in the Nitrosoarene Ene Reaction of Deuterium-Labeled Trisubstituted Alkenes, J. Org. Chem. ASAP
Auszeichnungen und Preise:
Herr R. Bargon: Internationaler Studentenferienkurs der Firma BASF, 2002.
Herr N. Bottke: Procter & Gambel-Förderpreis, 2000 und Fakultätpreis (Dissertation) der Fakultät für Chemie and Pharmazie, 2000.
Frau B. Fröhling: Preisträger der Unterfränkischen Gedenkjahresstiftung für Wissenschaft, 2002.
Herr O. Krebs: Procter & Gambel-Förderpreis, 2000 und DAAD Stipendium für einen Forschungsaufenthalt in Kreta, 2002.
Dr. A. Pastor: Marie-Curie Stipenduim der EU, 1998-1999.
Herr S. Schambony: Fakultätpreis (Dissertation) der Fakultät für Chemie and Pharmazie, 2001.
Herr S. Weinkötz: Preisträger der Unterfränkischen Gedenkjahresstiftung für Wissenschaft, 1999.
Ausstattung:
HPLC, Chiralyser, GC, MS, NMR-Spektrometer (600-, 400-, 250- und 200-MHz), Polarimeter.
Links:
Weitere Publikationen