Recent Progress in the Photocatalytic Synthesis of α‐Tertiary Primary Amines

Abstract

α‐Tertiary primary amines (α‐TPAs) bearing a fully substituted carbon center adjacent to the N‐unsubstituted amino group (‐NH2) exhibit unique biochemical and physicochemical activities. While due to the sterically congested structure and strong nucleophilic and alkaline natures of these N‐unsubstituted primary amine compounds, their facile synthesis remains an inherent challenge. Traditional methods commonly rely on tedious N‐protection/deprotection operations and highly reactive organometallic reagents, thus leading to poor atom and step‐economy and limited functional group compatibility. Modern photoredox catalysis offers a robust tool to prepare such structurally unique and synthetically valuable amine architectures via a radical pathway under extremely mild conditions. In this review, the recent progress in photocatalytic synthesis of α‐TPAs is systematically reviewed, and the reaction scope, limitations, and mechanisms for the reactions are discussed.