A Germanium Catalyst Accelerates the Photoredox α-C(sp 3 )-H Alkylation of Primary Amines.

Site-selective C(sp 3 )-H functionalizations using photoredox catalysis (PC) and hydrogen atom transfer (HAT) catalysis have received increasing attention. Here, we report a Ph 2 GeCl 2 cocatalyst that greatly improves the yield of α-C(sp 3 )-H alkylation of primary amines catalyzed by a PC-HAT hybrid system. The α-position of the amino group selectively reacted even when weaker C-H bonds existed in the substrates. This finding may help the design of a novel site-selective hybrid catalysis.