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 (10endo) in a tandem hetero Diels–Alder/[3,3] sigmatropic shift, as determined by computational
calculations.

Advertisements

Comments are closed.

%d bloggers like this: