AbstractWe describe the use of tetrabutylammonium fluoride as a basic trigger for reactions capable of generating structurally diverse products from methyl propiolate and carbonyl derivatives. The processes are based on either chemodifferentiating multicomponent ABB′ three‐component reactions or bimolecular domino reactions, and they operate through three different and well‐defined autocatalytic cycles. These catalytic cycles share a common property: they are launched by the acid–base reaction of fluoride ions to give catalytic amounts of acetylide or enolate salts, but they are maintained by the autocatalytic generation of these salts.