P-chirogenic phosphines are becoming increasingly popular as they show great potential as ligands in metal catalysed organic transformation. Evaluation of ligand efficiency is often based both on optimization of reaction conditions and the structure of the ligand itself. Herein, we report the synthesis of a 24-membered library of P-chirogenic phosphine-boranes where a 1,4-substituted triazole is incorporated via a Cu-catalyzed [3+2] cycloaddition, as well as the application of the ligands in different asymmetric transformations.