We investigated the feasibility of the enantiospecific DAPcatalyzed reductive aza-Mislow-Evans rearrangement using (R)-N-(tert-butylsulfinyl)-N-(4-methoxyphenyl) cinnamamide (1a) as the model substrate (Table ). After optimization of different variables and conditions, exposure of 1a to 5 mol% DAP-OBn precatalyst and 2.1 equivalents of pinacolborane in THF at ambient temperature smoothly induced the reductive -rearrangement (Entry 1). The corresponding α-hydroxy amide 2a was formed in 79% yield and an enantiomeric ratio of 94:6. Conveniently, the employed reaction conditions directly cleaved the S-O bond of the sulfenate intermediate. The use of one equivalent of pinacolborane drastically reduces the yield of 2a and is accompanied by substantial amounts α-sulfenyloxy carboxamide (Table , Entry 2). This observation is an evidence of the hypothesized dual role of the DAP-H and indicates that 2 equivalents of reductants is the theoretically required amount. A lower reaction temperature (0 ºC) only slightly increased the enantiospecificity at the expense a significantly reduced yield (Entry 3). An increase of the reaction temperature decreased the enantiospecificity (Entry 4). The evaluation of additional terminal reductant revealed that both catecholborane and phenylsilane boost the enantiomeric ratio of 1a to 99:1 (Entries 5-6). However, this advantage was accompanied by lower yields. Diphenylsilane was not a competent terminal reductant for this reaction ( . Control experiments clearly confirmed that necessity of both DAP catalyst and reductant for process . Table . Optimization of the reductive Aza-Mislow-Evans process [a] Entry Variation from optimal conditions Yield of 2a (%) [b] er [c] 9