Iron(II)-Catalyzed Intramolecular Olefin Aminofluorination

An iron(II)-catalyzed diastereoselective olefin aminofluorination is reported (dr up to >20:1). This new transformation applies a functionalized hydroxylamine and Et3N center dot 3HF as the nitrogen and fluorine source, which facilitates the efficient synthesis of beta-fluoro primary amines and amino acids from allylic alcohol derivatives. Preliminary mechanistic studies reveal that an iron-nitrenoid is a possible intermediate and that its reactivity and enantioselectivity can be efficiently modulated by ligands.