An efficient and straightforward synthetic protocol has been developed for the preparation of 6-carbamoylfulvene-6-carboxylates via a cycloaddition reaction between 1-cyanocyclopropane 1-esters and β-nitrostyrenes for the generation of a wide range of structurally interesting and pharmacologically significant compounds. The reaction utilises Et₃N promoted C–C bond cleavage, two new C–C bond formations of 1-cyanocyclopropane 1-ester with β-nitrostyrene and simultaneous conversion of a cyano group into amide in a domino fashion.