1‐Alkynylphosphorus Compounds in Organic Synthesis, 2010–2024

Abstract Since the review of Yorimitsu and Oshima in 2010, the past 15 years have witnessed significant progresses in the application of 1‐alkynylphosphorus compounds in organic synthesis. Owing to the reactive carbon‐carbon triple bond in association with the electron‐withdrawing phosphoryl group, they easily undergo transition metal‐catalyzed nucleophilic addition reactions at the β‐position with carbon‐ and heteroatom‐based nucleophiles to afford structurally diverse 1‐alkenyl phosphorus compounds. Especially, when 1‐alkynylphosphonates or phosphinates are used, intramolecular substitution reactions on P‐atom might occur in some cases, which would result in the formation of P ‐based heterocycles. In addition, the existing triple bond makes them prone to go through addition reaction initiated cyclization reactions and [2+2], [2+3], [2+4], [2+5] and [2+2+2] cycloaddition reactions with other unsaturated bonds, which provides an efficient access to various P ‐based heterocycles and phosphorylated carbon‐ and heterocycles.