We study the transition state of pericyclic reactions at elevated temperature with unbiased ab initio molecular dynamics. We find that the transition state of the intramolecular rearrangements for barbaralane and bullvalene remains aromatic at high temperature despite the significant thermal atomic motions. Structural, magnetic, and electronic properties of the dynamical transition state show the concertedness and aromatic character. Free-energy Calculations also support the validity of the transition state theory for the present rearrangement reactions. The calculations demonstrate that cyclic delocalization represents a strong force to synchronize the thermal atomic motions even at high temperatures.