Metal-Free Oxyacetoxylation of Arylynamines and Ynamides To Construct α-Acetoxyl Amides

Ynamides/arylynamines are challenging substrates for oxyacetoxylation, especially due to various reactive sites of the N-heteroaryl ring. Herein, we report a metal-free PhI(OAc)₂-mediated oxyacetoxylation of arylynamines/ynamides to provide α-acetoxyl amides in good to excellent yields. The transformation completes in a short time to afford solely the product in a highly regio- and chemo-selective manner through β-iodo keteneiminium intermediate, without functionalising the N-heteroaryl moiety.