Construction of N-Acyliminophosphoranes via Iron(II)-Catalyzed Imidization of Phosphines with N-Acyloxyamides

Employing FeCl₂ as a cheap and readily available catalyst, a facile imidization of phosphines with N-acyloxyamides is described, affording synthetically useful N-acyliminophosphoranes with high functional group tolerance. The transformation is easily performed under an air atmosphere at room temperature and could be scaled up to gram scale with a catalyst loading of 1 mol %. The iminophosphoranyl moiety in the product was further utilized as an effective directing group for controllable ortho C(sp²)-H bond amidations under Rh(III) catalysis.