Thionyl fluoride (SOF 2 ) is an underutilized reagent that is yet to be extensively studied for its synthetic applications. We previously reported that it is a powerful reagent for both the rapid syntheses of acyl fluorides and for one-pot peptide couplings, but the full scope of these nucleophilic acyl substitutions had not been explored. Herein, we report one-pot thionyl fluoridemediated syntheses of peptides and amides (35 examples, 45− 99% yields) that were not explored in our previous study. The scope of thionyl fluoride-mediated nucleophilic acyl substitutions was also expanded to encompass esters (24 examples, 64−99% yields) and thioesters (11 examples, 24−96% yields). In addition, we demonstrate that the scope of thionyl fluoride-mediated onepot reactions can be extended beyond nucleophilic acyl substitutions to mild reductions of carboxylic acids using NaBH 4 (13 examples, 33−80% yields).