Synthesis of P‐Arylphosphinecarboxamide Derivatives by Addition of N‐Arylphosphinecarboxamides with Aryne Precursors

A reliable method for preparing P(III)‐arylphosphinecarboxamide derivatives from N‐arylphosphinecarboxamides and aryne precursors has been developed. This reaction was carried out without transition‐metal catalysts, and a series of unsymmetrically structured phosphinecarboxamide derivatives were obtained under mild conditions. In addition, the reaction is carried out under air atomosphere, and the corresponding P(III)‐aryl phosphinecarboxamide compounds are also stable in air. Metal‐free‐catalyzedP‐arylation with novel primary or secondary phosphines was developed. This transformation undergoes an addition of the P‐H bond into the aryne that was generated by fluoride anion‐induced activation of 2‐trimethylsilylaryl triflate to produce the corresponding P‐arylated product.