To address this, we developed a process combining TEA-catalyzed alkyne-allene isomerization with β-selective hydrocyanation of conjugated allenes. To achieve direct CN addition, we proposed increasing the concentration of the "naked" nucleophilic CN anion using a suitable catalyst, such as a CN salt with a bulky, non-coordinating cation like tetrabutylammonium (TBA). Implementation of this strategy by replacing the phosphine catalyst with TBACN in the γ-selective catalytic system resulted in a new dual-catalytic relay leading to regioisomer 3a' in 72% yield with an E/Z ratio of ~3:1 (Figure ), with no formation of regioisomer 3a. This approach enabled the complementary regioselective system, providing an unprecedented regiodivergent synthesis of nitriles via alkyne hydrocyanation. The intrinsic relationship between the position of the introduced CN group and the ester EWG offers complementary post-functionalization opportunities to those previously demonstrated (Figure ). For instance, we synthesized γ-amino acid 17, a derivative of the versatile drug Pregabalin, and the five-membered lactone 18, both readily accessible from vinyl nitrile 3a' (Figure ).