Palladium/PC‐Phos‐Catalyzed Asymmetric Heck/Tsuji–Trost Reactions of Amino‐Tethered 1,3‐Cyclohexadiene with Aryl and Alkenyl Halides

Abstract

Chiral perhydroindoles are found in a number of natural products and biologically active compounds. Therefore, the development of new asymmetric methodology for rapid access to this core is of high importance. Herein, we reported a highly regio- and diastereo-selective palladium/PC-Phos-catalyzed asymmetric Heck/Tsuji-Trost reactions of readily available amino tethered 1,3-cyclohexadienes with aryl and alkenyl halides, delivering various functionalized chiral hexahydroindoles in good yields with high enantioselectivity. The application of this reaction to the concise synthesis of (-)-α-Lycorane was demonstrated. DFT computation results indicate that the difference in ΔE_dis of two migration insertion transition states determines the enantioselectivity of the reaction.