Organo-phosphorus compoundsOrgano-phosphorus compounds S 0080 Fragmentation-Related Phosphinylations Using 2-Aryl-2-phosphabicyclo[2.2.2]oct-5-ene-and -octa-5,7-diene 2-Oxides. -New aryl-phosphabicyclooctenes [cf. (I)/(II)] and aryl-phosphabicyclooctadienes [cf. (VII)/(VIII)] are synthesized and utilized in photo-and thermally-induced phosphinylation reactions of alcohols, primary amines and hydroquinone. -(KEGLEVICH*, G.; SZELKE, H.; BALINT, A.; IMRE, T.; LUDANYI, K.; NAGY, Z.; HANUSZ, M.; SIMON, K.; HARMAT, V.; TOEKE, L.; Heteroat. Chem. 14 (2003) 5, 443-451; Dep. Org. Chem. Technol., Budapest Univ. Technol. Econ., H-1521 Budapest, Hung.; Eng.) -F. Santoso 45-153

Pyrazole derivatives R 0180Synthesis of Indazole-N-oxides via the 1,7-Electrocyclization of Azomethine Ylides. -Several indazole-N-oxides are obtained via intermediate 1,2,6-benzoxadiazepines, formed by 1,7-electrocyclization of azomethine ylides onto a nitro group. -(NYERGES*, M.; VIRANYI, A.; ZHANG, W.; GROUNDWATER, P. W.; BLASKO, G.; TOEKE, L.; Tetrahedron 60 (2004) 44, 9937-9944; Dep. Org. Chem. Technol., Tech. Univ. Budapest, H-1521 Budapest, Hung.; Eng.) -Klein 06-123

Enantioselective syntheses Enantioselective syntheses O 0031Enantioselective Michael Addition of 2-Nitropropane to Chalcone Analogues Catalyzed by Chiral Azacrown Ethers Based on α-D-Glucose and D-Mannitol. -Crown ethers (I) and (II) are used as phase-transfer catalysts in the title reaction of chalcone analogues (III) and (VI). While compounds (I) induce the formation of the (+)-antipodes, compound (II) affords excess of the (-)-antipodes although with markedly lower selectivities (14-29% e.e.). Among the crown ethers, compound (Ib) is found to be the most effective, but compound (Ia) induces high asymmetric induction in the case of pyridyl derivative (IIIe). -(BAKO, T.; BAKO*, P.; KEGLEVICH, G.; BATHORI, N.; CZUGLER, M.; TATAI, J.; NOVAK, T.; PARLAGH, G.; TOEKE, L.; Tetrahedron: Asymmetry 14 (2003) 13, 1917-1923; Dep. Org. Chem. Technol., Tech. Univ. Budapest, H-1521 Budapest, Hung.; Eng.) -Klein 42-035

Organo-phosphorus compounds S 0080Catalytic Enantioselective Michael Addition in the Synthesis of α-Aminophosphonates. -The TADDOL derivatives (I) are tested in the preparation of the title compounds starting with phosphoglycines (II)/(V) and alkenes (III)/(VII). Optimized conditions using (Ia) as the most suitable agent render possible an e.e. value up to 72%. -(JASZAY*, Z. M.; NEMETH, G.; PHAM, T. S.; PETNEHAZY, I.; GRUEN, A.; TOEKE, L.; Tetrahedron: Asymmetry 16 (2005) 23, 3837-3840; Org. Chem. Technol. Res. Group, Hung. Acad. Sci., Tech. Univ., H-1521 Budapest, Hung.; Eng.) -Lindner 19-167

Addition of dichlorocarbene, generated from trichloromethane (III), to the chloro‐1‐methoxydihydrophosphinine oxides (I) and (II) gives a mixture of the phosphepin oxide (VI) and the phosphabicyclooctadiene oxide (VII) via the phosphabicycloheptenes (IV) and (V).