Photocatalyzed Aminomethylation of Alkyl Halides Enabled by Sterically Hindered N‐Substituents

Abstract The catalytic C(sp 3 )−C(sp 3 ) coupling of alkyl halides and tertiary amines offers a promising tool for the rapid decoration of amine skeletons. However, this approach has not been well established, partially due to the challenges in precisely distinguishing and controlling the reactivity of amine‐coupling partners and their product homologues. Herein, we developed a metal‐free photocatalytic system for the aminomethylation of alkyl halides through radical‐involved C(sp 3 )−C(sp 3 ) bond formation, allowing for the synthesis of sterically congested tertiary amines that are of interest in organic synthesis but not easily prepared by other methods. Mechanistic studies disclosed that sterically hindered N ‐substituents are key to activate the amine coupling partners by tuning their redox potentials to drive the reaction forward.