Our initial studies found that glycosylations with armed 39,40 2-deoxyglucosyl chlorides yielded promising results with highly nucleophilic primary and secondary alcohols. However, subsequent efforts to effect glycosylation of complex nucleophiles with 2-deoxyglycosyl chlorides proved unsuccessful, as we found that the HCl byproduct generated could not be trapped efficiently enough to avoid substrate decomposition via Ferrier rearrangements. Given the especially successful application of glycosyl phosphates in stereospecific glycosylations promoted by bis-thioureas, we refocused our efforts towards identifying 2-deoxy glucosyl phosphate derivatives with the appropriate balance of stability and reactivity properties. Glucosyl phosphates bearing electron-rich arming protecting groups such as benzyl ethers were found to undergo immediate decomposition during attempted preparation and/or isolation. Even disarmed 2-deoxyglucose derivatives bearing carboxylate protecting groups proved too unstable in the case of diaryl phosphate derivatives. However, analogous dialkyl phosphate derivatives were synthesized from the corresponding thioglucosides and found to be benchstable and readily purified. Evaluation of this class of electrophiles in the 2-deoxyglucosylation of threonine derivative 3a led to identification of glucosyl phosphate 2a as displaying the most promising levels of reactivity and selectivity for formation of the β-glucoside product. Extensive evaluation of reaction conditions revealed the optimal solvent, concentration, temperature, and reaction time for the model 2-deoxyglucosylation of 3a and molecular sieves as a crucial additive to sequester the phosphoric acid leaving group and minimize electrophile hydrolysis (see Supporting Information for details). Catalyst optimization efforts included extensive variation of the pyrrolidine substituents, as these components had proven to be crucial handles for tuning reactivity and selectivity in previous glycosylation studies. In the case of the model 2-deoxyglucosylation reaction, bis-thiourea derivative 1a, which bears an electron-rich 5-N-methyl indolyl substituent in the "northern" fragment and an unsubstituted pyrrolidine in the "southern" fragment, was found to be the most effective with respect to both β-selectivity and yield, the latter feature resulting from minimization of glucal side-product formation arising from elimination.