Regio- and Stereoselective Hydrophosphorylation of Ynamides for the Synthesis of beta-Aminovinylphosphine Oxides

A metal-free hydrophosphorylation of ynamides with diaryl phosphine oxides has been developed. A highly E-selective and beta-regioselective hydrophosphorylation protocol has been established as a general method for the synthesis of diversely hydrophosphinylated products employing an in situ generated electrophilic phosphorus species. Deuterium incorporation experiments suggest that the amino phosphirenium intermediate undergoes a concerted ring-opening hydrolysis upon treatment with H2O to exclusively furnish beta-aminovinylphosphine oxides.