Possible reaction mechanisms of 1,3-silyl and 1,3-hydrogen thermal rearrangements of trimethylsilyl-1-pyrazoline and its model systems were theoretically explored using B3LYP, MP2, CR-CCSD(T), CASSCF(6,5), and MRMP2(6,5) theories. Nitrogen substitution at the center position of allylic moiety turned out to have a special stabilizing effect on diradical intermediates, allowing a stepwise pathway. This substitutional effect was attributed to the nitrogen lone pair electrons, which form strong pi-conjugations with diradicals. The second nitrogen substitution at the terminal allylic position selectively reduces the reaction barrier of antarafacial retention pathway, creating a competition between concerted and stepwise channels. The introduction of a five-membered ring imposes ring strain on the allylic moiety and increases steric hindrance, allowing no antarafacial channels. The combined effect of the nitrogen substitution and the five-membered ring further removes the possibility of concerted reaction pathways. Therefore 1,3-silyl migrations of 3-trimethylsilyl-1-pyrazoline were found to occur only through stepwise mechanisms, implying that the Woodward-Hoffmann rule is not operative. The 1,3-hydrogen migration also occur via a stepwise mechanism; however, it would not occur easily because its reaction barrier is much higher than that of 1,3-silyl migrations. Current study shows that a stepwise mechanism can be the dominant reaction pathway of some particular [1,3]-sigmatropic rearrangements.