Arynes and Cyclohexyne in Natural Product Synthesis

This Minireview highlights recent advances in the field of aryne and cyclohexyne chemistry that have allowed the extraordinary reactivity of these entities to be harnessed during the course of natural product syntheses. The syntheses presented rely on the use of these reactive species in chemoselective transformations and follow unprecedented synthetic strategies that are inspiring for the practitioners of synthetic organic chemistry. Highly reactive! The latest developments in the field of aryne and angle‐strained cycloalkyne chemistry have led to recent applications of benzynes, indolynes, and cyclohexyne in natural product syntheses. The inherent reactivity of these intermediates can be harnessed to rapidly increase molecular complexity. The syntheses presented are highly instructive for synthetic organic chemists.