Phosphorus nucleophiles, reactions with acetylenic esters

Reactions of several phosphorus-containing nucleophiles with acetylenic esters are reported in the literature. Tertiary phosphines react with acetylenic esters, yielding a variety of products, depending on the reaction conditions. The reaction of triphenylphosphine with DMAD, for example, in ether around —50° gives an unstable 1 2 adduct, formulated as cyclopropenylmethylidenephosphorane (425), which on... 

Highly stabilized phosphorus ylides are prepared from acetylenic esters, a carbon-based nucleophile, and triphenylphosphine in aqueous media.40 In acetone-water (2 1) solvent, the reaction proceeds via the conjugate addition of triphenylphosphine to dialkyl acetylenedicarboxy-lates the resulting vinyl triphenylphosphonium salts undergo Michael addition reaction with a carbon-nucleophile to give the corresponding highly stabilized phosphorus ylides. 

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