Experimental and theoretical studies were carried out to highlight the influence of mild Lewis acid catalysts on the cycloadditions leading to stereochemically defined tetrasubstituted isoxazolidines. Considerable acceleration and increased exo stereoselectivity were observed for lithium triflate and magnesium bromide catalyzed processes. DFTbased reactivity indices reflected the differences in polar character of the catalyzed and uncatalyzed pathways. The regioselectivities were predicted from interaction energy calculations. Finally, the transition states were successfully located and the extent of bond formation analyzed. The catalytic acceleration was rationalized by density functional theory (DFT) calculated activation parameters. The rate constant ratios with Eyring's transition state theory (TST) rate equation and total partition functions were also theoretically evaluated to further rationalize the observed catalytic acceleration. © Springer-Verlag 2012.