We envisioned an all-in-one three-step cascade reductive aza-Mislow-Evans protocol exploiting 1,3,2-diazaphospholenes catalysis operating under mild, base-free conditions at ambient temperature (Scheme 1c). The sequence is triggered by an initial 1,4-hydride transfer from the catalytically generated DAP-H, which would result in phosphorus enol species INT-A. The high polarization of INT-A would readily trigger the -sigmatropic rearrangement at low temperature. In turn, product INT-B will be a suitable substrate for DAP-H inducing directly reductive cleavage of S-O bond to release target α-hydroxyl amide 2. Therefore, without any extra operational step for the reduction, the targeted enantioenriched α-hydroxyl amides 2 are obtained. We believed that such cascade process would provide a facile and convenient approach to access chiral α-hydroxy amides.