Nucleophilic Phosphine Organocatalysis

Abstract Phosphines have recently become popular choices as nucleophilic catalysts in organic synthesis. The unique reactivity of phosphines compared to amines has allowed the discovery of new nucleophilic addition reactions at the α‐ and γ‐positions of unsaturated carbonyl compounds, as well as novel [3+2] and [4+2] cycloaddition reactions of activated alkynes and alkenes. The accessibility of chiral phosphines has rendered several of these transformations enantioselective and has made possible the kinetic resolution of racemic secondary alcohols by phosphine‐catalyzed acylation. This mini‐review presents recent advances in nucleophilic phosphine organocatalysis for carbon‐carbon bond formation.