Zinc‐Catalyzed Dehydrogenative Alkynylation of BN‐Polycyclic Aromatics

We report a zinc‐catalyzed dehydrogenative alkynylation of BN‐polycyclic aromatics with terminal alkynes, enabling efficient access to BN‐embedded phenylacetylene scaffolds via direct B─H/C─H coupling. This transformation proceeds under mild conditions with broad substrate scope, accommodating diverse BN‐polycyclic aromatics and aryl, heteroaryl, and alkyl alkynes, as well as functionally complex substrates, with excellent functional group tolerance. The method is scalable and enables facile downstream derivatization. Photophysical studies reveal tunable absorption and emission properties governed by π‐extension and BN incorporation, distinct from all‐carbon analogues. Mechanistic studies support a pathway involving alkynyl–zinc intermediates and rate‐determining B─H activation, accompanied by H 2 evolution. This work provides a general and efficient strategy for constructing BN‐containing π‐conjugated systems with potential in functional materials and molecular design.