In our own work (Scheme 1, D1), phenol nucleophiles were used in the desymmetrization step under ureidopeptide bifunctional iminophosphorane (BIMP) catalysis, 155-168 however, to obtain high levels of enantioselectivity, phenol nucleophiles bearing an ortho-substituent were required, inherently limiting the scope of the reaction. Additionally, the optimal leaving group, 2-nitro-6-methyl-phenolate, 169 is a relatively weak Brønsted base, rendering the turnover of the optimal superbasic BIMP catalyst inefficient, which, in turn, forces an excessive 15 mol% catalyst loading to ensure high conversion of the starting material to product. The second stage enantiospecific displacement was also not without its limitations. While the remaining nitrophenol leaving group could be smoothly displaced with a variety of biologically relevant alkyl alcohols, thiols and amines, reactions with biologically relevant aromatic alcohols as well as displacement with carbon-based nucleophiles was either inefficient or led to the formation of significant amounts of byproducts. Finally, the ortho-substituted phenols introduced in the first stage could not be easily displaced, most probably due to a combination of steric effects and decreased electrophilicity at the now alkyl alcohol derived phosphonate esters.