Photoredox Copper-Catalyzed Asymmetric C(sp3)–H Glycosylation for Access to Chiral Heterobenzylic Amines

Chiral primary amines, particularly chiral heterobenzylic amines, represent a pivotal class of bioactive molecules that serve as ubiquitous structural motifs in pharmaceuticals and agrochemicals. The asymmetric C(sp³)–H glycosylation is one of the most attractive strategies in asymmetric synthesis. Herein, we disclose the first example of photoinduced and Cu-catalyzed asymmetric α-C(sp³)–H glycosylation of oxadiazole methylamines to access chiral heterobenzylic amines. Notably, the oxadiazole directing group not only demonstrates remarkable catalytic efficacy as a pharmaceutically relevant directing group but also serves as a bioactive pharmacophore, thereby eliminating the need for postsynthetic removal.