The straightforward synthesis of α-amino phosphine oxides via three-component reactions involving arynes, formamides and diarylphosphine oxides is disclosed. This method employs the aryne to activate formamide, without an external activating reagent, which is operationally simple under mild conditions with high efficiency. Furthermore, mechanistic perception suggests a cascade sequence including formal [2 + 2] cycloaddition of the aryne with a CO bond, and a 1,4-addition of the H-P(O) compounds to the enamine intermediates.