Fig. 4: Study on more complex systems.

A Nucleophilic addition-triggered transformations. The investigation on C–N bond insertion, Truce–Smiles rearrangement, and nucleophilic annulation reaction suggests that this chemoselective protocol can be utilized in a broad range of aryne reaction modes. B Study on substrates bearing more than two reaction sites. When an arynophile is much more reactive toward benzyne, it can be trapped by simple benzyne so that subsequent chemoselective control between other arynophiles with matched reactivity could occur. By contrast, a less reactive reaction site will keep inert with respect to any aryne species.