Hydrosilylation of Nitrones With Trichlorosilane: Preparation of Hydroxylamines

Herein, we describe a novel catalyst‐ and transition‐metal‐free method for the hydrosilylation of nitrones with trichlorosilane. A variety of hydroxylamines (38 examples) were obtained in moderate to good yields (28%–88%) with broad substrate compatibility under mild and operationally simple conditions. Control experiments confirm that the inherent directing groups of nitrones plays a pivotal role in bridging the reactants and facilitating the reaction. Furthermore, the synthetic utility of this method is demonstrated by gram‐scale synthesis and elaboration of the products.