Preparation of Polyfunctionalized Aromatic Nitriles from Aryl Oxazolines

A selective ortho,ortho’-functionalization of readily available aryl oxazolines by two successive magnesiations with sBu₂Mg in toluene followed by trapping reactions with electrophiles, such as (hetero)aryl iodides or bromides, iodine, tosyl cyanide, ethyl cyanoformate or allylic bromides (39 examples, 62–99 % yield) is reported. Treatment of these aryl oxazolines with excess oxalyl chloride and catalytic amounts of DMF (50 °C, 4 h) provided the corresponding nitriles (36 examples, 73–99 % yield). Conversions of these nitriles to valuable heterocycles are reported, and a tentative mechanism is proposed.