Catalytic Allylation of Hypophosphorous Acid and H‐Phosphinic Acids with Primary Allylic Amines

Abstract

AbstractPrimary allylic amines serve as suitable allylic electrophiles for the allylation reactions of hypophosphorous acid and H‐phosphinic acids. In the presence of tris(dibenzylideneacetone)dipalladium(0) ([Pd2(dba)3], 0.1 mol %) and Xantphos (0.2 mol %), aqueous hypophosphorous acid was allylated by α‐unbranched primary allylic amines in a highly regioselective fashion to give structurally diverse allylic H‐phosphinic acids in good to excellent yields with exclusive E selectivity. Moreover, increasing the catalyst loading to 1 mol % and adding aqueous phosphoric acid (1.2 equiv.) permitted the allylation of H‐phosphinic acids with α‐unbranched primary allylic amines to proceed to give disubstituted phosphinic acids in good to excellent yields.