An Untethered and Formal Intermolecular Hexadehydro-Diels–Alder Reaction: Alkynylboronates with 2‑(1,3-Butadiynyl)pyridines

We show that 2-diynylpyridine and a Bpin-terminated monoyne or diyne will cross-react to form benzyne intermediates. These reactive intermediates are captured by various in situ trapping agents to give products of three-component reactions. Various control reactions, substrate modification, binding studies, and DFT analysis suggest that a small amount of a noncovalent Lewis acid–base complex is the active species within which the diyne and diynophile engage to produce the benzyne. Only a single isomeric benzyne is formed when a Bpin-diyne is used; this selectivity is rationalized by the geometric distortion seen in the DFT-computed diradical intermediate.