Despite numerous reactions involving an EWG-conjugated allene, we have not found any report of their TM-free hydrocyanation. Thus, we attempt to develop such a transformation with allenoate 2a and acetone cyanohydrin (AC) as a safer HCN alternative, under the conditions previously employed for 1a to 2a isomerization (Figure ). Since the catalytic activation of allenoates is dominated by phosphine catalysis, we tested a range of phosphines as prospective catalysts for the envisioned process (Figure ). Gratifyingly, nitrile 3a was obtained with an excellent yield and good stereoselectivity (91% and Z/E = 4.4, respectively) when triphenylphosphine was employed (Entry 1). It is worth emphasizing that no formation of any other regioisomers was detected, as indicated by 1 H NMR.