Copper-Catalyzed Enantioselective 1,3-Borylamination of 1,3-dienes

1,3-Stereogenic motifs are valuable structural elements in organic synthesis, yet their catalytic enantioselective construction remains a significant challenge. Herein, we report an unprecedented copper-catalyzed enantioselective 1,3-borylamination of conjugated dienes, enabled by a sequential hydroboration/hydroamination cascade and delivering products with up to 99% ee. The resulting chiral 1,3-borylamines serve as versatile building blocks for the rapid assembly of structurally diverse amines bearing nonadjacent stereocenters. The synthetic utility of this strategy is further illustrated through the concise preparation of several pharmaceutically relevant scaffolds. Preliminary mechanistic studies provide insight into the reaction pathway and the origins of the observed chemo-, regio-, and diastereoselectivity.