Enantioselective Construction of 1,3-Stereogenic Centers via 1,3-Borylamination of Conjugated Dienes

Abstract

1,3-Stereocenters are important structural motifs in organic synthesis, yet their catalytic enantioselective construction remains a formidable challenge. We report an unprecedented enantioselective 1,3-borylamination of conjugated dienes (up to 99% ee) via a copper-catalyzed cascade hydroboration/hydroamination strategy. The resulting 1,3-borylamines serve as a versatile platform for the synthesis of structurally diverse chiral amines featuring 1,3-stereocenters. Their synthetic utility is showcased through concise access to various pharmaceutically relevant scaffolds. Preliminary mechanistic studies elucidate the reaction pathway and the origins of its chemo-, regio-, and diastereoselectivity.