Aryne intermediates are compatible with several reaction classes and therefore primed to diversify arene scaffolds. We used arene 1g to highlight both cycloaddition and nucleophilic addition via dehydrogenative aryne coupling (Scheme 4). The yields over two-steps are moderate to high (65-92%) and arene functionalization is accomplished in a matter of hours with only chromatographic purification of the final coupling product 3a-d (Scheme 4). Scheme 4. Survey of arynophiles. a a Conditions are identical to Scheme 2. Yields: step 2, overall.