Microwave-assisted reactions of nitroheterocycles with dienes. Diels-Alder and tandem hetero Diels-Alder/[3,3] sigmatropic shift

摘要

Diels-Alder cycloaddition of 3-nitro-1-(p-toluenesulfonyl)indole 1 with dienes 2-6 under microwave irradiation in solvent-free conditions gave carbazole derivatives after elimination of the nitro group and in situ aromatization. While 3-nitro-1-(p-toluenesulfonyl)pyrrole 11 afforded indole derivatives, 4-nitro-1-(p-toluenesulfonyl)pyrazole 13 with cyclohexadiene 2 did not afford the expected cycloadduct but instead gave 1-cyclohexen-2-ylpyrazole 16. This Process occurred by hydrolysis of the 1-(p-toiuenesulfonyl) group, protonation of the diene and nucleophilic addition of the pyrazolate ion, as elucidated by computational studies. Reaction of nitroindole I with cyclohexadiene 2 afforded exclusively the endo stereoisomer (10endo) in a tandem hetero Diels-Alder/[3,3] sigmatropic shift, as determined by computational calculations.