Toward anti-Markovnikov 1‑Alkyne O‑Phosphoramidation: Exploiting Metal–Ligand Cooperativity in a 1,3‑N,O‑Chelated Cp*Ir(III) Complex

Metal–ligand cooperation between iridium­(III) and a 1,3-N,O-chelating phosphoramidate ligand has been used to develop a protocol for the intermolecular O-phosphoramidation of 1-alkynes. This selective C–O bond-forming reaction differs from that of standard amidation reactions, highlighting the ability to control N- or O-functionalization based on judicious choice of N,O-chelating ligand and metal center. Advances toward the development of catalytic anti-Markovnikov O-phosphoramidation using iridium­(III), including characterization of rare reactive intermediates that invoke 1,3-bidentate donor ligand hemilability, are disclosed.