Figure 1.

Scope of the (2‐aminophenyl)benzothioether substrate. Reaction conditions: thiol (1 mmol), ⁱPrMgCl (2.2 mmol), and aryne precursor (1.2 mmol) were stirred at −78 °C for 45 min, then warmed to 0 °C. The resulting intermediate Grignard was quenched with 1.5 mol of R¹R²N—OBz in the presence of CuCl (10 mol %) and phenanthroline (10 mol %; see SI). [a] An additional zincation step was performed by adding ZnCl₂ (0.5 equiv) after the initial thiolate addition. The thermal ellipsoids of the X‐ray structure of 7 d were set at 50 %.19