Epoxidation and Heterocyclization of Arenesulfonamides of the Norbornene Series

Abstract

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Azacycloalkanes from epoxides and aziridines

“…A large group of azabrendanes 117 was obtained in Unlike ureas, phosphonamides, alkylsulfonamides, the amides of carboxylic acids, fl uorine-containing sulfonamides, and arylsulfonamides with electron-withdrawing substituents in the ortho-position of the benzene ring 116 are incapable of heterocyclization [108,119,120]. The importance of the steric factor is obvious from the absence of the heterocyclization in the epoxidation reactions of compounds 118, 119 [121,122] and the lack of the formation of the azabrendane system at the oxidation of more bulky but also more conformationally labile camphorsulfonamide 120 (Scheme 41) [123].…”

New Tricyclic Amides. Synthesis, Structure, and Oxidation with Peroxyphthalic Acid

“…The optimal epoxidating agent for olefins with a hydrogenated isoindole fragment is peroxyphthalic acid, while more reactive peroxyformic acid seems to be the most appropriate for epoxidation of the fragment containing electron-acceptor carbonyl groups; peroxyformic acid was successfully used in the epoxidation of carboximides of the norbornene series [14]. In the IR spectra of compounds VIa, VIb, and VII we observed a strong absorption band at 855-850 cm -1 due to stretching vibrations of the C-O bond in the epoxynorbornane fragment [16]. As a result, we isolated monoepoxy derivative VII in 83.9% yield (Scheme 5).…”

“…Amides IIIb and IIId were subjected to epoxidation by treatment with peroxyphthalic acid generated in situ from phthalic anhydride and 35% aqueous hydrogen peroxide in ethyl acetate in the presence of urea; the latter was added to control proton-donor and proton-acceptor properties of the medium [13]. Epoxy derivatives VIa and VIb were isolated in 70-80% yield (Scheme 4).…”

10.1007/s11178-008-3005-4

“…The key issue in the synthesis of stereochemically homogeneous exo-(II) and endo-isomeric (IV) amines of the norbornene series was isolation of pure exo-and endo-nitriles IXa and IXb formed by the Diels-Alder reaction of cyclopentadiene with acrylonitrile [ (ArCO 3 H) generated in situ from phthalic anhydride and 30% aqueous hydrogen peroxide [11]. Tetracyclic nitrile IXd was obtained by the Diels-Alder reaction of endo-nitrile IXb with cyclopentadiene in a metal reactor at 170-175°C (10 h).…”