Abstract Donor–acceptor cyclopropanes were reacted with amphiphilic benzodithioloimine to give seven‐membered heterocycles with two sulfur atoms. Formally, this transformation can be regarded as a [4+3] cycloaddition reaction of the three‐membered ring and ortho ‐bisthioquinone. The benzodithioloimine serves as a surrogate for this highly reactive diene. The structure of the products was confirmed by X‐ray crystallography. Broad signals in 13 C NMR studies suggest that several conformers, slowly interconverting on the NMR timescale, are present at room temperature.