Two‐Directional Annelation: Dual Benzyne Cycloadditions Starting from Bis(sulfonyloxy)diiodobenzene

Double up: Dual cycloadditions of benzynes are demonstrated from bis(sulfonyloxy)diiodobenzene I, which can be viewed as a synthetic equivalent of 3-alkoxy-1,4-benzdiyne II. Importantly, selective halogen–lithium exchange of I enables the tandem generation of benzynes and dual cycloadditions with arynophiles 1 and 2, thus allowing the rapid construction of various highly functionalized bis-cycloadducts.