Cyclic Diaryl λ 3 ‐Bromanes as a Precursor for Regiodivergent Alkynylation Reactions

Regiodivergent reactions are a fascinating tool to rapidly access molecular diversity while using identical coupling partners. We have developed a new approach for regiodivergent synthesis using the dual character of hypervalent bromines. In addition to the recently reported reactivity of hypervalent bromines as aryne precursors, the first transition metal‐catalyzed reaction is reported. Accordingly, the development of these two complementary transformations allows for the alteration of regioselectivity to furnish both ortho ‐ and meta‐ substituted alkynylation products. Mechanistic and computational studies show how these selectivities are controlled.