Our methodology exhibits excellent tolerance of different functional groups preinstalled in the alkyne structure (1q-y), with yields above 90% in most cases. Notably, a rare opportunity for site-selective hydrofunctionalization is enabled, as demonstrated by the efficient functionalization of alkynes containing additional double or triple bonds (1q-t). To further evaluate the generality of our approach, we tested substrates with different EWGs, such as ketones and amides. Compounds 3z-3ad were readily obtained under standard or modified conditions, demonstrating that the TM-free hydrocyanation strategy is general with varied distal EWGs, enabling the functionalization of a plethora of alkynes. Encouraged by the versatility of our methodology when applied to simple alkynes, we further evaluated complex natural product derivatives (Figure ). Notably, products originating from families of terpenoids (4a-b), sugars (4c), steroids (4d-e), and amino acids (4f-g) were efficiently obtained with yields in a range of 77-97%, good stereoselectivity (Z/E in a range of 4.3-6.2) and exclusive regioselectivity. It is worth emphasizing that even the presence of a conjugated double bond (4d), usually active in nucleophilic addition, does not impact the selectivity of alkyne hydrocyanation. The broad tolerance for a wide range of polyfunctional compounds proves the robustness of our methodology, underscoring its synthetic potential.