Ortho‐alkynyl biaryls react in the presence of catalytic amount of Brønsted acids to give phenanthrenes in high yields under mild conditions. The activity and selectivity of this transformation are governed by the substitution pattern of the diarylalkyne moiety. Selectivity shifts are observed between the carbophilic Lewis and Brønsted acid‐catalyzed cycloisomerization involving alkyne activation.magnified image
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