Diversified Cycloisomerization/Diels-Alder Reactions of 1,6-Enynes through Bimetallic Relay Asymmetric Catalysis.

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).