Experimental and theoretical studies of Diels-Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2-propenoate and cyclopentadiene

Abstract

The Diels-Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2- propenoate and cyclopentadiene yields a mixture of carbodiene Diels-Alder adducts. B3LYP/6-31G(d) simulations indicate that the conversion of addends into methyl (1R*,2S*,3S*,4R*)-2-nitro-3-(4-nitrophenyl)- bicyclo[2.2.1]hept-5-ene-2-carboxylate occurs via two-stage heterodiene Diels-Alder reaction and (in a second step) skeleton rearrangement of the primary cycloadduct, whereas the reaction leading to methyl (1R*, 2R*,3R*,4R*)-2-nitro-3-(4-nitrophenyl)-bicyclo[2.2.1] hept-5-ene-2-carboxylate is a single-step process. © 2012 The Author(s).