Selenium-Catalyzed Regioselective Intermolecular Diamination\nof Dienes and Dienolate Derivatives

We\nreport a selenium-catalyzed diamination of dienes using sulfamates\nas a convenient nitrogen source. This reaction proceeds regioselectively\nfor 1,2-addition at the less substituted alkene, without the need\nfor a tethered diamine. We also report the first diamination of dienyl\nphosphates and tosylates, affording synthetically useful α,β-diaminoketone\nderivatives with high <i>syn</i> diastereoselectivity. Density\nfunctional theory calculations support a mechanism proceeding via\n[4+2] cycloaddition of the diene with a selenium bis(imide), followed\nby ring-opening aminolysis and [2,3]-sigmatropic rearrangement.