In recent years, there have been extraordinary developments of organophosphine-catalyzed reactions. This includes progress in the area of [4C+X] annulations, which are of particular interest due to their potential for the rapid construction of 5⁻8-membered cyclic products. In this short overview, we summarize the remarkable progress, emphasizing reaction mechanisms and key intermediates involved in the processes. The discussion is classified according to the type of electrophilic reactants that acted as C₄ synthons in the annulation process, in the order of α-alkyl allenoates, γ-alkyl allenoates, α-methyl allene ketones, β'-OAc allenoate, δ-OAc allenoate, activated dienes and cyclobutenones.
Keywords: C4 synthons; annulation; phosphine catalysis.