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.

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