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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.Bioactive compounds featuring an unusual core of spiro[5.5]undecenes and calliviminones were synthesized in very good yield with good regio- and diastereoselecti