Using a diamido-bis(amidate) titanium precatalyst, the hydroamination of alkynylphosphines afforded phosphinoenamine products. After reduction, 2-aminophosphines are prepared in excellent yield and on gram scale. A broad variety of alkynylphosphines and primary amines with different electronic and steric features are tolerated in this sequential transformation, enabling the rapid assembly of a collection of ligands. Additionally, intermediate phosphinoenamines can be used directly as proligands for coordination to transition metals using protonolysis or salt metathesis reactions. These transformations result in easy-to-use one pot protocols to prepare metal P,N-complexes for catalysis or small molecule activation.