We therefore investigated the effects of reaction dynamics using the VRAI-selectivity approach (Figure .C). A VRAI-selectivity calculation is performed for every selected low-energy TS1. The analyses were performed with TS1 as the first transition state (TS I ) and INT2 as the intermediate structure. The product geometries come from the quick reaction coordinate calculations of the most stable TS2 structure that leads to the aldehyde, ketone or epoxide. The percentage population for each pathway was obtained by multiplying the product percentage from VRAI-selectivity analyses and the percentage population of the TS1 from ΔΔG ‡ . By accounting for the effects of reaction dynamics, we successfully predicted the major product chemoselectively and stereoselectively for the reaction with Cat-B. The energy profiles for the ketone selective reaction with Cat-C and Cat-D are similar to that of the reaction with Cat-B. We repeated the product percentage calculation with and without considering reaction dynamics. The predicted percentages incorporating VRAI-selectivity calculations show much better agreement with the experimental results and suggest that the chemoselectivity is significantly influenced by reaction dynamics. The structures on the diagram are named according to the C4 and C5 stereochemistry and numbered based on their energy ranking. For example, TS2(RS-C1) is the most stable RS TS2 that leads to an aldehyde product. The PES of the epoxide selective reaction is noticeable different from the ketone selective reactions (Figure .A and B). Firstly, in minor pathways via TS1(SS-4), TS1(SR-1) and TS1(SR-2), the process beyond TS1 is barrierless and leads to the final product directly. Secondly, in the major pathway (ie via TS1(SS-1)), the syn-periplanar insertion (i.e. the inserting shifting group at the syn-periplanar position to the leaving nitrogen) has comparable kinetic barrier to the antiperiplanar insertion. The most stable TS1 structure, TS1(SS-1), contributes to both SR and SS epoxide. Unlike in other reactions, INT3 structures presents as a stable intermediate in the energy profile (ΔG ‡ (TS3) > 0 kcal mol -1 ) and can lead to both ketone (R/S) and aldehyde (R/S) upon 1,2-shift of the key group. Thus, all possible six products were considered in the VRAI-selectivity calculations for this reaction. The product percentages were calculated with and without incorporating VRAI-selectivity results. The predicted percentages with VRAI-selectivity calculations show a much closer match with the experimental result. The same conclusion as for the ketone selective reaction can be drawn. The stereoselectivity is controlled kinetically by TS1, while the chemoselectivity is determined by the reaction dynamics of the process beyond TS1.