Iron‐Catalyzed Asymmetric NH ₂ ‐Amination of Sulfenamides

The increasing prominence of stereogenic‐at‐sulfur motifs in drug discovery and catalysis has created a growing demand for versatile synthetic methods. We describe here an Fe( TIBS PDP)‐catalyzed enantioselective NH 2 ‐amination of sulfenamides to access chiral sulfinamidines. This method accommodates a broad range of sulfenamides, enabling direct access to diverse nitrogenated stereogenic‐at‐sulfur architectures. The synthetic utility is demonstrated by the efficient preparation of pharmaceutically relevant compounds, such as an aza‐analog of drug candidate LY181984 and a PP2A modulator. Moreover, this reaction represents the first example of asymmetric NH 2 transfer using the widely employed bioinspired Fe(PDP)‐type catalysts.