Iron-Catalyzed Asymmetric NH2-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(TIBSPDP)-catalyzed enantioselective NH2-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 NH2 transfer using the widely employed bioinspired Fe(PDP)-type catalysts.