Compounds bearing both boryl and amino groups at distal positions are invaluable synthons for synthesizing pharmaceuticals, drug candidates, and natural products, but their catalytic enantioselective synthesis remains rarely explored. We developed an enantioselective 1,4-borylamination reaction through a copper-catalyzed cascade hydroborylation and hydroamination of arylidenecyclopropanes. This reaction combines four readily available components in a highly chemo-, site-, and enantioselective fashion (>20:1 r.r. and up to 99% ee). The value of the reaction is demonstrated by their diverse transformations and wide applications in pharmaceutical synthesis and drug discovery.

Congratulations to Yushen, Yalin, and Yingying! I deeply appreciate your dedication and significant effort in this work.