Homopropargyl alcohols react with t-BuONO to form acyloximes which can be oxidatively cyclized to yield ioxazoles. The mechanism for the initial reaction of HONO with alkynes to form acyloximes (e.g., 13c) has been explored at the B3LYP/6-31G(d,p) + ZPVE level of theory. The observed chemoselectivity and regioselectivity are explained via an acid-catalyzed mechanism. Furthermore, the potential energy surface revealed numerous surprising features. The addition of HONO (8) to protonated 1-phenylpropyne (18) is calculated to follow a reaction pathway involving sequential transition states (TS6 and TS8), for which reaction dynamics likely play a role. This reaction pathway can bypass the expected addition product 21 as well as transition state TS8, directly forming the rearranged product 23. Nevertheless, TS8 is key to understanding the potential energy surface; there is a low barrier for the pseudopericylic [1,3]-NO shift, calculated to be only 8.4 kcal/mol above 21. This places TS8 well below TS6, making the valley-ridge inflection point (VRI or bifurcation) and direct formation of 23 possible. The final tautomerization step to the acyloxime can be considered to be a [1,5]-proton shift. However, the rearrangement in the case of 17h to 13c is calculated to be barrierless, arguably because the pathway is pseudopericyclic and exothermic.