Sequential Ir‐Catalyzed Allylation/ 2‐aza‐Cope Rearrangement Strategy for the Construction of Chiral Homoallylic Amines †

Summary of main observation and conclusion Sequential Ir‐catalyzed asymmetric allylation/2‐aza‐Cope rearrangement of arylidene aminomalonates with allylic carbonates was successfully developed, and a variety of enantioenriched homoallylic amine derivatives were obtained in high yields with good chirality transfer and excellent E / Z ‐geometry control (up to 99% yield, 96% ee). Compared with previous dual catalytic system established for this transformation, the current mono metal catalytic system provides a simpler and more practical protocol employing the readily available starting materials.