Diastereoselective, Zinc-Catalyzed Alkynylation of α‑Bromo Oxocarbenium Ions

We have developed a bromination/alkynylation sequence that enables efficient transformation of simple cyclic enol ethers to difunctionalized products. The success of this strategy relies on a highly diastereselective, zinc-catalyzed addition of terminal alkynes to α-bromo oxocarbenium ions, formed in situ via ionization of acetal precursors. Using this method, trans-α-alkynyl-β-halo pyran and furan derivatives can be prepared with high diastereoselectivity and excellent functional group tolerance.