Mechanistic Insights into the Cascade Reactivity of 1,6-Enynes with Arylsulfonyl Chlorides

A comprehensive mechanistic study of the transformations of 1,6-enyne derivatives with radical species was conducted using density functional theory (DFT) computations. The combined conceptual DFT and DFT analyses elucidate the mechanistic features governing the cascade reactivity of 1,6-enynes with arylsulfonyl chlorides, including the origin of the observed regioselectivity and the nature of the key radical intermediate. The results indicate that the reaction proceeds via the regioselective addition of an arylsulfonyl radical to the α,β-unsaturated carbonyl moiety of the 1,6-enyne derivatives.