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A highly efficient asymmetric [1,3]- and [3,3]-O-to-C sigmatropic rearrangement of 3-allyloxy-4 H -chromenones and their analogues was developed. Chiral N , N '-dioxide complexes of 3d late transition metal complexes enabled two mechanistically different processes, giving a series of optically active 2,2-disubstituted chromane-3,4-diones and 2-allyl-3-hydroxy-4 H -chromen-4-ones as well as their related compounds in excellent yield and enantioselectivity. Systemic mechanistic studies and DFT calculation revealed the nature of the vinyl ether unit of the substrate, which biased regioselectivity via a stepwise tight ion pair pathway and a concerted pericyclic pathway, respectively. The enantioselectivity of the two processes is also disclosed., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)