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

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 -toluenesulfonyl) group, protonation of the diene and nucleophilic addition of the pyrazolate ion, as elucidated by computational studies. Reaction of nitroindole 1 with cyclohexadiene 2 afforded exclusively the endo stereoisomer ( 10 endo ) in a tandem hetero Diels–Alder/[3,3] sigmatropic shift, as determined by computational calculations.