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

• DOI: 10.1016/j.tet.2009.04.065
• Publication Date: 2009-04-25T05:23:26Z
• Authors: M. Victoria Gómez; Ana I. Aranda; Andrés Moreno; Fernando P. Cossío; Abel de Cózar; Ángel Díaz-Ortiz; Antonio de la Hoz; Pilar Prieto
• Keywords: 01 natural sciences; 0104 chemical sciences

Abstract 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.