The versatile isocyanide building block Asmic, anisylsulfanylmethylisocyanide, reacts with aldehydes and ketones in a BF3·OEt2-mediated condensation to afford thioimidoyl-substituted 2,5-dihydrooxazoles. The condensation is distinguished from related base and transition-metal-catalyzed [3 + 2] processes in proceeding via the condensation of aldehydes and ketones with 2 equiv of an isocyanide followed by a molecular rearrangement that installs four new bonds. BF3·OEt2 mediates an analogous condensation of Asmic with imines to generate N-substituted dihydroimidazoles. Mechanistically, BF3·OEt2 activates the isocyanide to facilitate deprotonation evolving to a zwitterion that traps π-electrophiles in a formal [3 + 2] process. A second deprotonation-condensation with Asmic initiates a structural rearrangement involving a sulfanyl elimination-addition transposition sequence. The resulting dihydrooxazoles and dihydroimidazoles contain a thioimidate that serves as a diversification point for further elaboration.