Modular Access to α-Tertiary Amines: Electrochemical Tandem Di-Functionalization of Olefins With Ammonia Surrogates...

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-NH₂ 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(sp³)-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 (> 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.