Enantioselective Three-Component Photochemical 1,4-Bisalkylation of 1,3-Butadiene with Pd/Cu Catalysis

Catalysis by excited-state palladium has emerged as an active area of research, but controlling the enantioselectivity remains a challenge. Herein, we report the use of synergistic Pd/Cu catalysis to accomplish the first three-component photochemical 1,4-bisalkylation reactions of 1,3-butadiene. Consequently, alpha-amino acid esters bearing quaternary stereocenters were expeditiously synthesized from three simple starting materials: an alkyl bromide, butadiene, and an aldimine ester. Experimental and computational investigation of the reaction mechanism confirmed a radical pathway involving catalysis by an excited-state palladium species. The stereochemistry is mainly controlled by the chiral Cu catalyst.

Automated summary

In this study, the use of synergistic Pd/Cu catalysis in the photochemical 1,4-bisalkylation reactions was reported, resulting in the efficient synthesis of α-amino acid esters bearing quaternary stereocenters. Experimental and computational investigation confirmed a radical pathway involving catalysis by an excited-state palladium species, with the stereochemistry mainly controlled by the chiral Cu catalyst.