An efficient one‐pot synthesis of highly substituted pyrroles from donor–acceptor cyclopropanes, salicylaldehydes, and ammonium acetate has been developed. This reaction involves a domino sequence involving the ring‐opening of donor–acceptor cyclopropanes, [3+2] annulation, and aromatization as the key steps. This elegant methodology readily afforded functionalized pyrroles under mild reaction conditions and with a wide substrate scope.

A DBU-promoted cascade annulation of nitroarylcyclopropane-1,1-dicarbonitriles and 3-aryl-2-cyanoacrylates for the synthesis of highly functionalized cyclopenta­[b]­furan derivatives is described. High stereoselectivity, fused cyclopentane and furan can be established in a single reaction, highlighting the high efficiency and step-economy of this protocol. This reaction offers a novel and straightforward protocol to the synthesis of cyclopenta­[b]­furans featuring the [3 + 2] cycloadditions of nitroarylcyclopropane-1,1-dicarbonitriles with 3-aryl-2-cyanoacrylates.

The diversity-oriented synthesis of fully substituted aniline derivatives via the DBU-mediated [4 + 2] annulation of donor-acceptor 1,1-dicyanocyclopropanes with 3-aryl-2-cyanoacrylate has been developed.

DBU-mediated [4 + 1] annulations of donor-acceptor cyclopropanes with carbon disulfide or thiourea to form 2-aminothiophene-3-carboxylate derivatives have been discovered. This reaction proceeds via the ring opening of donor-acceptor cyclopropanes to produce a 2-(iminomethylene)but-3-enoate intermediate, followed by the attack of an S-nucleophile for regioselective intermolecular nucleophilic addition, intramolecular S-nucleophilic addition, and final aromatization. A variety of functional groups could be tolerated under the reaction conditions.

An eco-friendly and efficient straightforward method has been developed for the synthesis of ethyl 3-amino-1-aryl-1 H-benzo[ f]chromene-2-carboxylate derivatives via 1,4-diazabicyclo[2.2.2]octane (DABCO)-catalysed cyclisation of β-naphthol and 3-aryl-2-cyanoacrylates using water as a green solvent. All products precipitated from the reaction mixture and were isolated by simple filtration. No further work-up nor purification was necessary. The structure of ethyl 3-amino-1-aryl-1 H-benzo[ f]chromene-2-carboxylate was further confirmed by X-ray single crystal analysis.