A new strategy has been established for the [2,3]-sigmatropic rearrangement of quaternary allylic ammonium ylides via in situ activation of tertiary allylic amines with arynes under mild conditions. Using 2-(trimethylsilyl)aryl triflates as aryne precursors, a range of tertiary allylic amines bearing electron-withdrawing groups underwent [2,3]-sigmatropic rearrangement to furnish structurally diverse homoallylic amines in moderate to good yields. The reaction enabled construction of quaternary stereocenters with excellent enantiopurity and functionalized cyclopropanes with extremely high diastereoselectivity.