N‐Oxyl‐Radical‐Catalyzed Intermolecular Aminooxygenation of Styrenes and Inter/intramolecular Aminoalkoxylation of Homoallylic Alcohols

Abstract By taking advantage of the redox cycle between the reductive N ‐oxyl radical and its oxidative oxoammonium counterpart, the N ‐oxyl‐radical‐catalyzed intermolecular aminohydroxylation of styrenes with N ‐fluorobenzenesulfonimide was developed. Various vinyl arenes were aminohydroxylated in moderate to excellent yields with high regio‐ and diastereoselectivities by using environmentally benign H 2 O as the oxygen source. In addition, the sequential inter/intramolecular aminoalkoxylation of homoallylic alcohols was also achieved under anhydrous conditions, which allowed the exclusive synthesis of pharmaceutically useful 2‐aryl‐3‐amino‐disubstituted tetrahydrofurans.