Abstract: | We report the combination of transition‐metal‐catalyzed diversified cycloisomerization of 1,6‐enynes with chiral Lewis acid promoted asymmetric Diels–Alder reaction to realize asymmetric cycloisomerization/Diels–Alder relay reactions of 1,6‐enynes with electron‐deficient alkenes. A broad spectrum of chiral 5,6]‐bicyclic products could be acquired in high yields (up to 99 %) with excellent diastereoselectivy (>19:1 dr) and enantioselectivity (up to 99 % ee). |