In the presence of 2-(trimethylsilyl)aryl triflates as aryne precursors under mild conditions, a range of tertiary propargylic amines bearing electron-withdrawing groups were converted to quaternary propargylic ammonium ylides followed by a [2,3]-sigmatropic rearrangement to afford structurally diverse amino-substituted allenes or conjugated dienes, depending on their structure, in moderate to good yields.