Modular Access to <i>α</i> ‐Tertiary Amines: Electrochemical Tandem Di‐Functionalization of Olefins With Ammonia Surrogates and Amino Acids

ABSTRACT Quaternary carbon centers, especially those bearing nitrogen, are highly valued in drug discovery, imparting three‐dimensionality, selectivity, and metabolic stability. Yet, accessing α ‐tertiary, primary amines ( α ‐TPAs) remains challenging due to steric congestion and the intrinsic basicity of amine nucleophiles. Although classical nucleophilic α ‐amination, α ‐C–H functionalization, and photocatalytic α ‐NH 2 radical strategies offer useful platforms, they often suffer from limited functional‐group tolerance and poor stereocontrol. Here, we report a streamlined electrochemical difunctionalization strategy that directly transforms 1,1‐disubstituted alkenes into C( sp 3 )‐rich α ‐TPAs using inexpensive and bench‐stable ammonium surrogates. This metal‐ and oxidant‐free aminochalcogenation employs thiophenols as the most user‐friendly thiolating agents, avoiding pre‐activated sulphur reagents and enabling efficient aminosulfenylation and aminoselenylation in a single operation. The strategy accommodates diverse N ‐sources, including ammonia surrogate, amino acids, dipeptides, aliphatic amines, and N ‐heterocycles, enabling the synthesis of α ‐tertiary, primary as well as secondary amines and facilitating late‐stage functionalization of pharmaceutically relevant scaffolds (&gt; 71 examples and up to 82% yield). The robustness of the strategy was further demonstrated by an efficient gram‐scale electrolysis. This work provides a modular, sustainable route to free alkyl amines that remain difficult to access by conventional methods.