Alcohol‐Directed Carboamination of Conjugated Enynes

ABSTRACT We report a Pd‐catalyzed carboamination of conjugated enynes for the direct synthesis of functionalized allenic amines. The reaction proceeds through a selective 1,4‐coupling of anilines and aryl triflates with enynes, utilizing a free alcohol as a native directing group. The obtained allenes undergo versatile transformations, including cyclization to dihydropyrans, hydroamination, and tandem carboamination sequences. Notably, the use of primary anilines enables a second carboamination to generate multifunctionalized 3‐pyrroline heterocycles through dual C‐N bond formation with two distinct aryl triflates. The transformation represents a novel approach to allene synthesis and heterocycle construction through sequential carboamination events.