Asymmetric copper-catalyzed hydrophosphinylation of ethynylazaarenes to access P -chiral 2-azaaryl-ethylphosphine oxides

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-chirality. Mechanistic investigations reveal that the interaction between the chiral Cu(i) complex and azaarenes promotes the kinetic resolution of SPOs. The robustness of this method is further demonstrated by its ability to incorporate deuterium atoms into the olefins, highlighting its potential relevance in pharmaceutical applications.