Multicatalytic methodologies require the precise orchestration of the kinetics of subprocesses occurring under common conditions. Therefore, we initiated our studies by gaining insight into alkyne-allene isomerization and the development of hydrocyanation of the corresponding allene. For the first process, we selected internal alkyne 1a equipped with ethyl ester moiety as EWG (Figure ), with a range of base catalysts (Figure ) in DCM at 40 o C. We found that the weakest organic bases (Entries 1-3) and the heterogenic catalyst (Entry 4) did not promote a reaction. In contrast, the clean formation of allene 2a was observed with slightly stronger bases (Entries 5-8), achieving the highest mole fraction of 2a when triethylamine was used (Entry 5). In turn, utilization of the strongest base in the set results in partial (DBU, Entry 9) or complete decomposition (t-BuOK, Entry 10) of 1a. Further, we performed detailed studies of the profile of the isomerization reaction in time with a different loading of TEA under NMR control (Figure , red points). The data revealed that the process ultimately results in a mixture of 1a and 2a with an equimolar ratio, while the 40 mol% loading is required to achieve a final composition within 12 h. The equimolar ratio of 1a/2a represents the equilibrium state as proved by the studies of isomerization, starting from pure allene 2a to 1a, resulting in the same symmetrical profile as the isomerization from pure alkyne 1a under the same conditions (Figure , blue points). These findings provide the foundation for leveraging reversible alkyne-allene isomerization as a key activation step in the proposed dual-catalytic hydrocyanation strategy.