Serendipitous discovery of enantiodivergence in asymmetric epoxidation: After several rounds of optimization (See Table -I in Supporting Information) involving variation in the catalyst loading, temperature, diazoacetamide, aldehyde silyl group and the amount of DMSO used in catalyst generation. The best results were obtained for the reaction of 2a and 1b using 20 mol% of the borate complex of VANOL prepared without any added DMSO. Under these conditions, the reaction conducted at 0 °C gives the cis-epoxide 13 in 63% yield and 78% ee (Scheme 3). We then turned to the analogous, here-to-fore unknown aluminate complexes of VANOL. The catalyst was generated by treating two equivalents of the ligand with one equivalent of trimethylaluminum in toluene at room temperature for 30 minutes. The findings reveal that the aluminum catalyst is superior to the boron catalyst. Using only 10 mol% of aluminate (S)-VANOL complex as the catalyst at 0 °C, 13 was obtained in 63% yield and 83% ee (Scheme 3). Incredibly, this slight increase in ee with the aluminate (S)-VANOL complex was accompanied by a reversal in the direction of the asymmetric induction relative to reaction of the borate (S)-VANOL complex. Therefore, under otherwise identical reaction conditions and with the same enantiomer of the chiral ligand, a simple switch in the Lewis acid from boron to aluminum has led to the discovery of a perfectly enantiodivergent 7 asymmetric epoxidation reaction.