Premature birth is a steadily increasing unmet medical need, for which new "tocolytic" agents are required to arrest contractions and delay labor. A peptide-based approach was developed to produce modulators of the prostaglandin F2α receptor as a novel target for tocolytic development. In this strategy, the solution-phase synthesis and alkylation of aza-glycyl-proline building blocks were key for the preparation of a series of modulators exhibiting biased signaling. An optimized method is now provided for making the aza-Gly-Pro unit with minimum side product, and alkylation of the unit is described to illustrate the library diversification step. Conditions have been reported for selectively unmasking the protecting groups at the N- and C-terminal of the aza-dipeptide unit and for its introduction into analogs that modulate the signaling of the PGF2α receptor. The merits of this protocol for azapeptide synthesis have thus been demonstrated by the synthesis of inhibitors of myometrial contraction exhibiting potential as prototypes for developing tocolytics to treat preterm labor.