Reaction mechanisms of the 6-Benzyl-6-azabicyclo[2.2.1]hept-2-ene with benzoyl isocyanate have been investigated using density functional theory (DFT) at the B3LYP/6-31G(d,p) level of theory. The reaction proceeding along six competitive channels includes two categories. That is, two channels are formally [3,3]-sigmatropic rearrangements and four channels are [4+2] cycloadditions. For urea, the formally [3,3]-sigmatropic rearrangement channels and the [4+2] cycloaddition channels are competitive since they have similar barriers. However, the [4+2] cycloaddition channels are energetically favorable pathways to lead to isourea, with the highest barrier of 12.77 kcal/mol. These polar Diels-Alder (P-DA) reactions are controlled by the charge transfer (CT) at the transition states. Moreover, the main products of this reaction include urea and isourea. Furthermore, difference of two new bond lengths at transition states indicate that the [4+2] cycloadditions in this reaction are asynchronous processes, which is in good agreement with the experiment.