Selenium-Catalyzed Regioselective Intermolecular Diamination of Dienes and Dienolate Derivatives

We report a selenium-catalyzed diamination of dienes using sulfamates as a convenient nitrogen source. This reaction proceeds regioselectively for 1,2-addition at the less substituted alkene, without the need for a tethered diamine. We also report the first diamination of dienyl phosphates and tosylates, affording synthetically useful α,β-diaminoketone derivatives with high syn diastereoselectivity. Density functional theory calculations support a mechanism proceeding via [4+2] cycloaddition of the diene with a selenium bis(imide), followed by ring-opening aminolysis and [2,3]-sigmatropic rearrangement.