With a better insight into the steps toward our envisaged dual-catalytic hydrocyanation, we attempted to merge them into a one-pot system (Table ). Notably, both catalytic processes were found to be orthogonal, affording regioselective hydrocyanation of 1a in 94% yield with good stereoselectivity (Z/E = 4.2) in the presence of TEA and PPh₃ at 40 o C in 12 h in dichloromethane (Entry 1). Increasing the reaction scale slightly improved the efficiency, nearly reaching a quantitative yield (Entry 2). Interestingly, under dual-catalytic conditions, the stereoselectivity of the formation of alkyne 3a is almost identical to that of the process starting from the corresponding allene intermediate 2a (compare Entry 1 and Figure ). It is worth emphasizing that the stereochemistry of HCN addition achieved here represents a rare example of anti-selective hydrocyanation of internal alkynes. Notably, the simultaneous engagement of both catalysts is essential to ensure reactivity (Entries 3-4). Similarly, the role of the trivalent phosphine catalyst proved critical for a reaction to take place (Entry 5). In turn, lowering the temperature and concentration or reducing the catalyst loadings decreases the yield to a range of 71-81%, while the stereoselectivity remains unaffected (Entries 6-10). Dual-catalytic hydrocyanation can also proceed with good yield (71-83%) in other common solvents like acetonitrile, tetrahydrofuran, and toluene (Entries 11-13).