Selenophosphoramide-catalyzed diamination and oxyamination of alkenes

A new selenophosphoramide-catalyzed diamination of terminal- and trans -1,2-disubstituted olefins is presented. Key to the success of this transformation was the introduction of a fluoride scavenger, trimethylsilyl trifluoromethanesulfonate (TMSOTf), to prevent a competitive syn -elimination pathway, as was the use of a phosphoramide ligand on selenium to promote the desired substitution reaction. A screen of catalysts revealed that more electron-rich phosphine ligands resulted in higher yields of the desired product, with selenophosphoramides giving the optimal results. A broad range of substrates and functional groups were tolerated and yields were generally good to excellent. For ( E )-1,2-disubstituted olefins, diastereoselectivities were always high, giving exclusively anti products. The conditions were also applied to substrates bearing internal nucleophiles such as esters and carbonates, giving rise to 1,2-aminoesters and cyclic carbonates, respectively. Scavenging fluoride from a selenophosphoramide-catalyzed alkene oxidation reaction suppresses the known syn -elimination pathway, enabling alkene diamination/oxyamination reactions via substitution.