Emerging as an alternative to transition-metals, main-group catalysis underwent great progress over the past decades. [1] In this respect, P-hydrido-1,3,2-diazaphospholenes (DAP-H) have received considerable attention since their initial discovery [2] linked to their unique hydridicity [3] an umpolung of the P-H polarity, a feature attributable to the 6π delocalization effect of their heterocyclic core. [4] Synthetic applications of DAP-H are dominated by stoichiometric or catalytic hydride transfer processes across a broad range of polarized unsaturated compounds, [5] including carbonyls, [6] imines, [7] N=N bonds, [8] CO2, [9] and pyridines, [10] as well as Michael acceptors [11] . Particularly, DAP-catalyzed conjugate reduction of enoates leads to a versatile phosphorus enol intermediate, providing an attractive platform for consecutive α-functionalizations (Scheme 1a). Very few of synthetic applications involving reductive αfunctionalization strategy have been reported. Kinjo disclosed a C-C bond formation of the phosphorus enols with nitriles after phosphor-boron exchange. [11] We recently reported a highly selective 1,4-reduction of allyl acrylates triggering Ireland-Claisen rearrangement to form α-allyl carboxylic acids in a diastereoselective manner. [12] While DAP-catalysis emerged as a promising tool for some enantioselective hydride-transfer reactions recently, [13] asymmetric reductive α-functionalization strategy, especially to create chiral carbon-heteroatom bonds remains elusive and challenging. Enantiopure α-hydroxyl amides are prominent motifs displayed in natural products and biologically active compounds e.g. vitamin B5, [14] aeruginopeptin 228A, [15] and fulvanine A [16] (Figure ). There is significant interest in the development of efficient synthetic methods to access such chiral α-hydroxyamides. [17] In this respect, the creation of the oxygen stereocenter can be built by an enantiospecific rearrangement process. The Mislow-Evans reaction is a reversible -sigmatropic rearrangement of allylic sulfoxide to sulfenate ester, typically shifted toward the more thermodynamically stable sulfoxide (Scheme 1b). [18] In the presence of an additional external reductant, such as thiophiles or phosphites, reductive cleavage of the sulfenate esters provides allylic alcohols. The concerted rearrangement generally proceeds with good diastereo control. The stereogenic center of the sulfur atom is transmitted to the carbon atom through a five-membered transition state. Lu reported an aza-Mislow-Evans rearrangement of O-silyl N-sulfinyl N,O-ketene acetals generated from chiral tertbutyl sulfinamides yielding α-sulfenyloxylamides. [19] The pivotal silylation step requires stoichiometric amounts of a strong base and cryogenic temperature in order to mitigate the degradation of sensitive sulfinamides under basic conditions. [20] Figure . Natural products containing chiral α-hydroxy amides.