Stereocontrolled Microwave-Assisted Domino [3,3]-Sigmatropic Reactions: A Winstein-Overman Rearrangement for the Formation of Differentiated Contiguous C-N Bonds.

A domino [3,3]-sigmatropic rearrangement sequence employing a sequential reversible allylic azide rearrangement followed by an irreversible Overman reaction provides a new route to the formation of two contiguous C-N bonds. The reaction occurs in a stereocontrolled fashion in two steps from readily available alkenyl epoxides via initial azide anion ring opening of the epoxides.