Figure 1. Current approaches to primary arylamine and phenol synthesis from arylmetals in the absence of transition-metal catalysts, impact of steric hindrance on kinetic acidity and the discovery of multifunctional oxaziridine reagents for heteroatom-transfer reactions.

a–c, Known two-step procedures for the synthesis of primary arylamines (4) from the corresponding arylmetals (2 and 2c) using electrophilic aminating agents (1, 5 and 7). d, Conversion of arylmagnesium halides (2a) into phenols (12) using molecular oxygen in a flow system. e, Non-hindered amines undergo rapid proton exchange with arylmetals. f, Sterically bulky secondary amines, such as 13, do not undergo proton exchange with arylmetals. g, Our hypothesis: a sterically hindered electrophilic N source, such as an N–H oxaziridine, will undergo NH transfer rather than proton exchange when reacted with arylmetals. h,i, Camphor-derived N–Me and N–benzyl oxaziridine (19a (h) and 19b (i), respectively) react with 15 directly to give 2-naphthol (20) on workup. j,k, Camphor- and fenchone-derived N–H oxaziridines (16 (j) and 18 (k), respectively) react with 2-naphthylmagnesium bromide (15) directly at low temperature and under a protective argon atmosphere to afford 2-naphthylamine (17) on simple aqueous workup. Bn, benzyl; TMDEA, tetramethylethylenediamine.