Total Synthesis of (+)-Minfiensine: Construction of the Tetracyclic Core Structure by an Asymmetric Cascade Cyclization

A new method for one‐step construction of the tetracyclic core structure of the indole alkaloid (+)‐minfiensine was developed utilizing a palladium‐catalyzed asymmetric indole dearomatization/iminium cyclization cascade. An efficient total synthesis of (+)‐minfiensine was realized using this strategy. The present method enables access to the common core structure of a series of monoterpene indole alkaloids, such as vincorine, echitamine, and aspidosphylline A. All at once: A palladium‐catalyzed asymmetric cascade cyclization enabled one‐step construction of the tetracyclic core framework of the indole alkaloid (+)‐minfiensine. A palladium‐catalyzed Heck‐type cyclization completed its total synthesis efficiently.