Palladium/Xu‐Phos‐Catalyzed Enantioselective Cascade Heck/Intermolecular Direct Heteroarylation Reaction

Comprehensive Summary Asymmetric cascade Heck/C–H functionalization has emerged as an appealing strategy for activating inert C–H bonds and conveniently synthesizing heterocycles with quaternary centers, owing to the domino sequence of carbopalladation followed by C–H functionalization enabling efficient construction of multiple bonds in one pot. Herein, a palladium‐catalyzed enantioselective cascade Heck/intermolecular direct heteroarylation reaction of unactivated alkenes with heteroarenes is developed, providing a facile access to diverse bis‐heterocycles of great practicality bearing an all‐carbon quaternary stereocenter with excellent levels of yields and enantioselectivities under mild conditions. Moreover, the synthetic utility of this strategy is further demonstrated by the versatile transformations of product.