Primary allylic amines serve as suitable allylic electrophiles for the allylation reactions of hypophos-A C H T U N G T R E N N U N G phorous acid and H-phosphinic acids. In the presence of tris(dibenzylideneacetone)dipalladium(0) ([Pd 2 A C H T U N G T R E N N U N G (dba) 3 ], 0.1 mol %) and Xantphos (0.2 mol %), aqueous hypophosphorous acid was allylated by a-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 a-unbranched primary allylic amines to proceed to give disubstituted phosphinic acids in good to excellent yields.Allylic halides and alcohol derivatives frequently serve as electrophilic components in the Tsuji-Trost reaction, which is powerful for the synthesis of unsaturated compounds. [1] While allylic amines have rarely been used directly as allylic electrophiles because of the poor leaving ability of amino groups, [2] it would be rewarding to develop the Tsuji-Trost reaction with allylic amines to explore new reactivity and selectivity. It is noteworthy that, in general, the synthetic routes to allylic amines are not longer than those to allylic halides and alcohol derivatives. Allylic amines can be prepared by reduction of a,b-unsaturated amides or nitriles by reductive amination of a,b-unsaturated carbonyl compounds or by modification of allylamines through the Heck reaction.[3] Moreover, the basicity of allylic amines permits their purification in large quantities by simple extractive procedures instead of routine chromatography. Sporadic studies have shown that allylic amines, in most cases secondary and tertiary ones, can undergo the Tsuji-Trost reaction with a few types of carbon, [3b-d, 4] nitrogen, [5] and sulfur nucleophiles. [3a,e, 6, 7] To the best of our knowledge, there is no previous report on the Tsuji-Trost reaction of allylic amines with phosphorus nucleophiles. Herein, we report efficient allylation reactions of hypophosphorous acid and Hphosphinic acids with primary allylic amines, which are more atom-economic relative to those with commonly used allylic electrophiles because ammonia is the sole byproduct.The Tsuji-Trost reaction has been successfully extended to the allylation of a few phosphorus nucleophiles for the synthesis of allylic-(H)-phosphinic acids and their derivatives.[8] Montchamp and co-workers reported that hypophosphorous acid, hypophosphite salts, [9] and H-phosphinic acids [10] could undergo palladium-catalyzed allylation with allylic alcohols, esters, and carbonates.[11] When allylic alcohols were used as the allylic electrophiles, they underwent Fischer-like esterification prior to palladium-catalyzed C À O bond cleavage. Inspired by these reports, together with our interest in exploring new reactions through CA C H T U N G T R E N N U N G (sp 3 ) À N bond cleavage...