Yes / Ynamides/arylynamines are challenging substrates for oxyacetoxylation, especially due to various reactive sites of 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 without functionalising N-heteroaryl moiety, in a highly regio- and chemo-selective manner through β-iodo keteneiminium intermediate.

Yes / Herein, we report a catalyst-free ‘click’ reaction: metal-free [2 + 2] cycloaddition–retro-electrocyclisation (CA–RE) of arylynamines with the sluggish acceptor tetracyanoquinodimethane (TCNQ) to provide orthogonal electron-push–pull light-harvesting small molecules: N-heterocyclic dicyanoquinodimethane-substituted methylene malononitriles. Ynamines are reactive alkynes and tend to induce over-reactions with the CA–RE adducts. The reactivity of arylynamines was balanced properly by ensuring the electrondensity of the nitrogen atom was delocalised more over the aromatic rings than the triple bond. / This work was supported by Guangxi Natural Science Foundation (2020JJA120032). / Research Development Fund Publication Prize Award winner, April 2022.